CN102343283B - Vertically aligned layered double hydroxides (LDHs) film and application thereof in structured catalysis - Google Patents
Vertically aligned layered double hydroxides (LDHs) film and application thereof in structured catalysis Download PDFInfo
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- CN102343283B CN102343283B CN 201110204361 CN201110204361A CN102343283B CN 102343283 B CN102343283 B CN 102343283B CN 201110204361 CN201110204361 CN 201110204361 CN 201110204361 A CN201110204361 A CN 201110204361A CN 102343283 B CN102343283 B CN 102343283B
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- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 10
- 150000004679 hydroxides Chemical class 0.000 title abstract 2
- 238000002360 preparation method Methods 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 230000003197 catalytic effect Effects 0.000 claims abstract description 28
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 238000004332 deodorization Methods 0.000 claims abstract description 15
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical class [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 32
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 29
- 229960001545 hydrotalcite Drugs 0.000 claims description 29
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 29
- 229910021645 metal ion Inorganic materials 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 150000001450 anions Chemical class 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 239000011229 interlayer Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims 5
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 239000000758 substrate Substances 0.000 abstract description 7
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000003208 petroleum Substances 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- -1 cobalt sulfonated phthalocyanine Chemical class 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention discloses a vertically aligned layered double hydroxides (LDHs) film and a preparation method thereof, and belongs to the technical field of an inorganic functional material and controlled preparation thereof. The vertically aligned LDHs film has the characteristics of good stability, high catalysis efficiency, longer catalysis life, easy regeneration procedure and the like in the event that the film is applied to structured catalytic oxidation deodorization of mercaptan. The preparation method of a structured catalyst comprises the following steps: preparing vertically aligned binary and ternary LDHs films on a pure aluminum substrate by an in-situ growth method; calcining the obtained LDHs films at the temperature of 400-500 DEG C to obtain a complex metal oxide film; and then loading cobalt sulfonated phthalocyanine (CoSPc) on the complex metal oxide film to obtain the structured catalyst. The obtained catalyst can be applied to catalytic oxidation of mercaptan and shows the advantages of high catalytic activity and longer catalysis life, thus having potential application prospect in deodorization in petroleum industry.
Description
Affiliated field
The invention belongs to inorganic functional material and controlled preparing technical field thereof, be specifically related to a kind of vertically oriented hydrotalcite film and preparation method thereof, be applied to structuring catalytic oxidation mercaptan deodorization aspect, has good stability, the catalytic efficiency height, long catalytic life and be easy to characteristics such as regeneration.
Background technology
Mercaptan is the faintly acid organic sulfur compound, is present in most of oil products (as kerosene, naphtha, aviation fuel, liquefied gas etc.).Mercaptan corrosivity is big, and smell is abominable, the serious harm health, but also be a kind of radical initiator, have a strong impact on quality and the stability of oil product.Remove mercaptan, be converted into the disulphide of nontoxic odorless, this process is commonly referred to " deodorization ".Most widely used in desulfurizing oil industry at present is that Uop Inc. releases Merox catalytic oxidation desulfurization alcohol technology.This technology mainly is in strongly basic medium (as NaOH solution), is catalyst with sulfonated phthalocyanine cobalt or poly-phthalocyanine cobalt, and air is that oxidant is that harmless disulphide is dissolved in the oil product with mercaptan oxidation, thereby removes mercaptan.But there is following drawback in this technology: (1) produces a large amount of useless smelly alkali lye, increases the burden that oil plant disposes waste liquid, serious environment pollution; (2) Phthalocyanine-like Catalysts is not long service life, and the catalyst failure problem is serious.Therefore, many chemists are actively being sought a large amount of uses that a kind of cost solid base lower and that environmental pollution is lighter replaces liquid base.
Hydrotalcite (LDHs) di-hydroxyl composite metal oxidate that is otherwise known as, be that a class is used anionic inorganic lamellar material very widely, it is to be arranged in order and the crystal that forms along the third dimension by the laminate of two-dimensional, the mutual high degree of dispersion of divalence and trivalent metal hydroxides also constitutes the main body laminate with covalent bond, and be rich in positive charge; Interlayer anion evenly distributes, and with electrostatic interaction dynamic balance body layer plate electric charge, makes crystal be electroneutral.Be composite metal oxide (MMO) with the LDHs high-temperature roasting, the specific area of Yin Qigao, strong basicity and heat endurance have wide application at aspects such as base catalysis, catalyst carriers in recent years.But this MMO powder is easy to run off in catalytic process, and with product difficulty separate.Therefore, how avoiding the loss of solid base in catalytic process is again a problem demanding prompt solution.
Hydrotalcite film with growth in situ method preparation has unified orientation, and film and substrate be with covalent bonds, and adhesion is stronger, difficult drop-off.After becoming composite metal oxide (MMO) film after the calcining of LDHs oriented film, still keeping original orientation and the adhesion stronger with substrate.Therefore, compare with powder, the phthalocyanine cobalt is loaded on the catalyst for preparing on this structuring MMO film have following advantage: (1) can make catalyst run off in course of reaction and be controlled effectively; (2) the special structural approach characteristics that have of this MMO film have determined that this film can provide unified alkalescence, and basic site evenly disperses; (3) the even dispersion of basic site can make the phthalocyanine cobalt be adsorbed on more uniformly on the film, further reduces the gathering of phthalocyanine cobalt, thereby improves activity of such catalysts and service life.Therefore, this film catalyst is expected under no liquid alkali condition mercaptan efficiently be removed.Up to now, domestic and international still haveing nothing to do, be prepared into structure catalyst carries out catalytic applications to the mercaptan system document and patent report in this at aluminium substrate preparation ternary LDHs film and with this ternary film.
Summary of the invention
The object of the present invention is to provide a kind of vertically oriented hydrotalcite film and preparation method thereof, be applied to structuring catalytic oxidation mercaptan deodorization aspect, have good stability, catalytic efficiency height, long catalytic life and be easy to characteristics such as regeneration.Its technical scheme is: by the growth in situ method, prepare vertical orientated binary, ternary houghite film in the fine aluminium substrate, the hydrotalcite film that obtains is obtained composite metal oxide film 400-500 ℃ of calcining, be structural catalyst behind the load sulfonated phthalocyanine cobalt then.
The vertically oriented hydrotalcite film of the present invention's preparation is the compound that is assembled in order by interlayer anion and positively charged laminate; The main body laminate is that metal cation and hydroxide ion constitute octahedron with covalent bond, forms its structure and shepardite Mg (OH) by sharing seamed edge
2Structural similarity; This vertically oriented hydrotalcite film is binary or ternary houghite film, namely is made up of two or three metallic element on the houghite laminate; The expression general formula of binary type hydrotalcite film is: M
2+ 1-xM
3+ x(OH)
2(Y
N-)
X/nMH
2O, M
2+Represent bivalent metal ion Mg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Mn
2+Or Fe
2+, M
3+Represent trivalent metal ion Al
3+, Fe
3+, Cr
3+, Mn
3+, Co
3+Or V
3+, Y
N-Represent interlayer anion CO
3 2-, NO
3 -, SO
4 2-, Cl
-, Br
-In one or more, n is the charge number of interlayer anion, n is 1 or 2,0.2≤x≤0.4,0≤m≤2; The ternary houghite expression formula is: (M
I 2+M
II 2+)
1-xM
3+ x(OH)
2(Y
N-)
X/nMH
2O, wherein M
I 2+And M
II 2+Represent bivalent metal ion Mg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Mn
2+Or Fe
2+, M
I 2+And M
II 2+Different; M
3+Represent trivalent metal ion Al
3+, Fe
3+, Cr
3+, Mn
3+, Co
3+Or V
3+, Y
N-Represent interlayer anion CO
3 2-, NO
3 -, SO
4 2-, Cl
-, Br
-In one or more, n is the charge number of interlayer anion, n is 1 or 2,0.2≤x≤0.4,0≤m≤2.
Concrete preparation technology of the present invention is as follows:
1. the preparation of vertical orientated binary type hydrotalcite film:
A. choose 1-800cm
2Aluminium flake, earlier with acetone ultrasonic cleaning 10-20min, use the ultrasonic 10-20min of ethanol then, use deionized water ultrasonic cleaning 5-10min at last, to guarantee that oil stain is removed clean on the aluminium flake, take out the aluminium flake that cleans up standby;
B. prepare the bivalent metal ion M of solubility
2+With the mixed solution of urea, bivalent metal ion M wherein
2+Concentration is 0.01-1mol/L, urea and M
2+Mol ratio be 2-6;
C. the aluminium flake of steps A preparation is vertically put into the mixed solution of 100-1000ml B step preparation, reacted 1-48 hour down at 50-150 ℃, then aluminium flake is taken out, dry under the normal temperature, namely obtain vertical orientated binary type hydrotalcite film.
2. the preparation of vertical orientated ternary houghite film:
A. choose 1-800cm
2Aluminium flake, earlier with acetone ultrasonic cleaning 10-20min, use the ultrasonic 10-20min of ethanol then, use deionized water ultrasonic cleaning 5-10min at last, to guarantee that oil stain is removed clean on the aluminium flake, take out the aluminium flake that cleans up standby;
B. prepare the bivalent metal ion M of solubility
I 2+With the mixed solution of urea, bivalent metal ion M wherein
I 2+Concentration is 0.01-1mol/L, urea and M
I 2+Mol ratio be 2-6;
C. prepare the bivalent metal ion M of solubility
I 2+, M
II 2+With the mixed solution of urea, wherein M
I 2+/ M
II 2+Mol ratio is 1-50, M
I 2+Concentration is 0.01-1mol/L, urea/(M
I 2++ M
II 2+) mol ratio be 2-6;
D. the aluminium flake of steps A preparation is vertically put into the solution of 100-1000ml B step preparation, reacted 1-48 hour down at 50-150 ℃, put into the solution of 100-1000ml C step preparation after then aluminium flake being taken out rapidly, reaction is 1-48 hour under identical temperature, aluminium flake is taken out, dry under the normal temperature, namely obtain vertical orientated ternary houghite film.
Described M
2+, M
I 2+And M
II 2+Represent bivalent metal ion Mg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Mn
2+Or Fe
2+, M
I 2+And M
II 2+Different; M
3+Represent trivalent metal ion Al
3+, Fe
3+, Cr
3+, Mn
3+, Co
3+Or V
3+
Binary or the ternary vertically oriented hydrotalcite film of preparation are applied to structuring catalytic oxidation mercaptan deodorization reaction.
The concrete steps of described structuring catalytic oxidation mercaptan deodorization reaction are:
A. compound concentration is the sulfonated phthalocyanine cobalt methanol solution of 10ppm-60ppm, fully stirs sulfonated phthalocyanine cobalt to be uniformly dispersed in 6-12 hour;
B. with 1-800cm
2400-550 ℃ of calcining of the binary of above-mentioned preparation or ternary vertically oriented hydrotalcite film 2-8 hour, put into sulfonated phthalocyanine cobalt liquor load 1-5 hour of steps A preparation then, take out then under the vacuum condition and dry, namely obtain structural catalyst, this structural catalyst stores under vacuum condition;
C. preparing the concentrations of mercaptans scope is the normal octane solution 50-500ml of 400ppm-2000ppm, in the there-necked flask of packing into;
D. structural catalyst is put into the solution of step C preparation and stirred, begin catalytic reaction under the room temperature behind the aerating oxygen.
Described structural catalyst forms on the composite metal oxide film basis load sulfonated phthalocyanine cobalt and obtains at calcined precursors binary or ternary vertically oriented hydrotalcite film, this catalyst has been kept the appearance structure of binary or ternary vertically oriented hydrotalcite film, have abundant aperture, its general formula is M
2+ 1-xAl
3+ xO
1.5xM (CoPcS) or (M
I 2+M
II 2+)
1-xAl
3+ xO
1.5xM (CoPcS), wherein M
2+, M
I 2+And M
II 2+Represent bivalent metal ion Mg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Mn
2+Or Fe
2+, M
I 2+And M
II 2+Difference, M
I 2+/ M
II 2+Mol ratio is 1-50; M
I 2+Preferred Mg
2+, M
II 2+Preferred Ni
2+CoPcS represents sulfonated phthalocyanine cobalt; 0.2≤x≤0.4, m is that its scope of content of sulfonated phthalocyanine cobalt is 0＜m＜2.
Above-mentioned prepared structural catalyst signs such as XRD, elementary analysis, ESEM, power spectrum have been carried out, the success of proof binary or ternary hydrotalcite film is synthetic, and the structural catalyst catalysis mercaptan performance of making estimated, the result shows that this catalyst has shown advantages of high catalytic activity and long catalytic life.
The invention has the advantages that: the vertical orientated film of houghite that has synthesized binary or ternary in aluminium substrate, the composite metal oxide that its calcining back is generated still can keep the orientation texture consistent with precursor and the active force stronger with substrate, can avoid the loss of catalyst in catalytic process effectively after being prepared into catalyst like this, and be easy to separate and regeneration.By the preparation condition of modulation hydrotalcite precursor film, can realize to the regulation and control of sulfonated phthalocyanine cobalt load concentration, can realizing the optimization of sulfonated phthalocyanine cobalt optimum load amount to the control of hydrotalcite pattern and composite metal oxide alkali density; Kind and the range of application of this film enriched in the introducing of the third metallic element.The catalytic oxidation that this catalyst is used for mercaptan has embodied very high catalytic activity and long catalytic life, has potential application prospect aspect the deodorization of petroleum industry.
Description of drawings
Fig. 1 is ESEM and the energy spectrogram of the vertical orientated ternary houghite film of embodiment 1 preparation.
Fig. 2 is the XPS figure of the vertical orientated ternary houghite film of embodiment 1 preparation, (a) Mg/Al-LDHs film, (b) Ni/Al-LDHs film, (c) the Ni/Mg/Al-LDHs film of embodiment 1.
Fig. 3 is ESEM and the energy spectrogram of the vertical orientated ternary houghite film of embodiment 2 preparations.
Fig. 4 is the vertical orientated ternary houghite film XRD figure of embodiment 3 preparations.
Fig. 5 is the vertical orientated ternary houghite film scanning Electronic Speculum figure of embodiment 3 preparations.
Fig. 6 is the structure catalyst digital photograph of embodiment 4 preparations.
Fig. 7 is the conversion ratio figure of embodiment 8 structure catalyst catalysis mercaptan, (a) the Ni/Mg/Al-LDHs film after the sulfonated phthalocyanine cobalt load calcining, (b) the powder Ni/Mg/Al-LDHs after the sulfonated phthalocyanine cobalt load calcining, (c) sulfonated phthalocyanine cobalt load Ni/Mg/Al-LDHs film, (d) sulfonated phthalocyanine cobalt load powder Ni/Mg/Al-LDHs, (e) sulfonated phthalocyanine cobalt load aluminium flake, (f) powder that scrapes off from sulfonated phthalocyanine cobalt load calcining back Ni/Mg/Al-LDHs film.
The specific embodiment
Steps A: choose 450cm
2(the aluminium flake of 30cm * 15cm * 0.2cm), then aluminium flake is rolled into the seal cup that tubular is put into 600ml, next earlier with acetone ultrasonic cleaning 15min, uses the ultrasonic 15min of ethanol then, use deionized water ultrasonic cleaning 10min at last, take out the aluminium flake that cleans up standby;
Step B: with the solid Mg (NO of 8.20g (0.032mol)
3)
26H
2The urea of O and 11.64g (0.194mol) is dissolved in the 650mL seal cup, adds the 600ml deionized water and stirring, makes it fully dissolve be uniformly dispersed (solution I);
Step C: with the Mg (NO of 8.20g (0.032mol)
3)
26H
2The O solid, the Ni (NO of 1.86g
3)
26H
2The urea of O and 11.64g (0.194mol) is dissolved in the 650mL seal cup, adds the 600ml deionized water and stirring, makes it fully dissolve be uniformly dispersed (solution II);
Step D: the aluminium flake that steps A is cleaned immerses in the solution I and sealing, then seal cup is put into 70 ℃ of water-baths and reacted 12h, put into the solution II that step C prepares rapidly after taking out aluminium flake, react 12h in 70 ℃ of water-baths, take out the aluminium flake washed with de-ionized water, 60 ℃ of oven dry obtain vertical orientated ternary houghite film, are designated as the Ni/Mg/Al-LDHs film; This hydrotalcite film is the compound that is assembled in order by interlayer anion and positively charged laminate; The main body laminate is that metal cation and hydroxide ion constitute octahedron with covalent bond, forms its structure and shepardite Mg (OH) by sharing seamed edge
2Structural similarity; Be made up of three kinds of metallic elements on this vertically oriented hydrotalcite film laminate, its chemical formula is: (Ni
2+Mg
2+)
1-xAl
3+ x(OH)
2(CO
3 2-)
X/2MH
2O, Ni
2+/ Mg
2+Mol ratio is 2.2, x=0.33, m=0.48.
Steps A: choose 450cm
2(the aluminium flake of 30cm * 15cm * 0.2cm), then aluminium flake is rolled into the seal cup that tubular is put into 600ml, next earlier with acetone ultrasonic cleaning 15min, uses the ultrasonic 15min of ethanol then, use deionized water ultrasonic cleaning 10min at last, take out the aluminium flake that cleans up standby;
Step B: with the solid Mg (NO of 8.20g (0.032mol)
3)
26H
2The urea of O and 11.64g (0.194mol) is dissolved in the 650mL seal cup, adds the 600ml deionized water and stirring, makes it fully dissolve be uniformly dispersed (solution I);
Step C: with the Mg (NO of 8.20g (0.032mol)
3)
26H
2The O solid, the Ni (NO of 0.47g
3)
26H
2The urea of O and 11.64g (0.194mol) is dissolved in the 650mL seal cup, adds the 600ml deionized water and stirring, makes it fully dissolve be uniformly dispersed (solution II);
Step D: the aluminium flake that steps A is cleaned immerses in the solution I and sealing, then seal cup is put into 70 ℃ of water-baths and reacted 12h, put into the solution II that step C prepares rapidly after taking out aluminium flake, react 12h in 70 ℃ of water-baths, take out the aluminium flake washed with de-ionized water, 60 ℃ of oven dry obtain vertical orientated ternary houghite film, are designated as the Ni/Mg/Al-LDHs film; This hydrotalcite film is the compound that is assembled in order by interlayer anion and positively charged laminate; The main body laminate is that metal cation and hydroxide ion constitute octahedron with covalent bond, forms its structure and shepardite Mg (OH) by sharing seamed edge
2Structural similarity; Be made up of three kinds of metallic elements on this vertically oriented hydrotalcite film laminate, its chemical formula is: (Ni
2+Mg
2+)
1-xAl
3+ x(OH)
2(CO
3 2-)
X/2MH
2O, Ni
2+/ Mg
2+Mol ratio is 1.2, x=0.35, m=0.49.
Embodiment 3
Steps A: choose 450cm
2(the aluminium flake of 30cm * 15cm * 0.2cm), then aluminium flake is rolled into the seal cup that tubular is put into 600ml, next earlier with acetone ultrasonic cleaning 15min, uses the ultrasonic 15min of ethanol then, use deionized water ultrasonic cleaning 10min at last, take out the aluminium flake that cleans up standby;
Step B: with the solid Zn (NO of 9.50g (0.032mol)
3)
26H
2The urea of O and 11.64g (0.194mol) is dissolved in the 650mL seal cup, adds the 600ml deionized water and stirring, makes it fully dissolve be uniformly dispersed (solution I);
Step C: with the Zn (NO of 9.50g (0.032mol)
3)
26H
2The O solid, the Cu (NO of 1.89g
3)
26H
2The urea of O and 11.64g (0.194mol) is dissolved in the 650mL seal cup, adds the 600ml deionized water and stirring, makes it fully dissolve be uniformly dispersed (solution II);
Step D: the aluminium flake that steps A is cleaned immerses in the solution I and sealing, then seal cup is put into 70 ℃ of water-baths and reacted 12h, put into the solution II that step C prepares rapidly after taking out aluminium flake, react 24h in 70 ℃ of water-baths, take out the aluminium flake washed with de-ionized water, 60 ℃ of oven dry obtain vertical orientated ternary houghite film, are designated as the Cu/Zn/Al-LDHs film; This hydrotalcite film is the compound that is assembled in order by interlayer anion and positively charged laminate; The main body laminate is that metal cation and hydroxide ion constitute octahedron with covalent bond, forms its structure and shepardite Mg (OH) by sharing seamed edge
2Structural similarity; Be made up of three kinds of metallic elements on this vertically oriented hydrotalcite film laminate, its chemical formula is: (Cu
2+Zn
2+)
1-xAl
3+ x(OH)
2(CO
3 2-)
X/2MH
2O, Cu
2+/ Zn
2+Mol ratio is 2.0, x=0.36, m=0.51.
Steps A: choose 450cm
2(the aluminium flake of 30cm * 15cm * 0.2cm), then aluminium flake is rolled into the seal cup that tubular is put into 600ml, next earlier with acetone ultrasonic cleaning 15min, uses the ultrasonic 15min of ethanol then, use deionized water ultrasonic cleaning 10min at last, take out the aluminium flake that cleans up standby;
Step B: with the solid Mg (NO of 8.20g (0.032mol)
3)
26H
2The urea of O and 11.64g (0.194mol) is dissolved in the 650mL seal cup, adds the 600ml deionized water and stirring, makes it fully dissolve be uniformly dispersed (solution I);
Step C: with the Mg (NO of 8.20g (0.032mol)
3)
26H
2The O solid, the Ni (NO of 1.86g
3)
26H
2The urea of O and 11.64g (0.194mol) is dissolved in the 650mL seal cup, adds the 600ml deionized water and stirring, makes it fully dissolve be uniformly dispersed (solution II);
Step D: the aluminium flake that steps A is cleaned immerses in the solution I and sealing, then seal cup is put into 70 ℃ of water-baths and reacted 24h, put into the solution II that step C prepares rapidly after taking out aluminium flake, react 24h in 70 ℃ of water-baths, take out the aluminium flake washed with de-ionized water, 60 ℃ of oven dry obtain vertical orientated ternary houghite film, are designated as the Ni/Mg/Al-LDHs film; This hydrotalcite film is the compound that is assembled in order by interlayer anion and positively charged laminate; The main body laminate is that metal cation and hydroxide ion constitute octahedron with covalent bond, forms its structure and shepardite Mg (OH) by sharing seamed edge
2Structural similarity; Be made up of three kinds of metallic elements on this vertically oriented hydrotalcite film laminate, its chemical formula is: (Ni
2+Mg
2+)
1-xAl
3+ x(OH)
2(CO
3 2-)
X/2MH
2O, Ni
2+/ Mg
2+Mol ratio is 2.2, x=0.33, m=0.48;
Step e: take by weighing the 7.5mg sulfonated phthalocyanine cobalt and be dissolved in the methyl alcohol of 250ml and stir 6h (solution III), standby;
Step F: LDHs film calcining under 500 ℃ that step D is obtained obtained the Ni/Mg/AlMMO film in 3 hours;
Step G: the MMO film that step F is obtained is cut into 140cm
2Little cylinder was immersed in the solution III load sulfonated phthalocyanine cobalt 1 hour then, and cylinder is taken out, and dried under vacuum condition, namely obtained structural catalyst.
Embodiment 5
Steps A: choose 450cm
2(the aluminium flake of 30cm * 15cm * 0.2cm), then aluminium flake is rolled into the seal cup that tubular is put into 600ml, next earlier with acetone ultrasonic cleaning 15min, uses the ultrasonic 15min of ethanol then, use deionized water ultrasonic cleaning 10min at last, take out the aluminium flake that cleans up standby;
Step B: with the solid Mg (NO of 8.20g (0.032mol)
3)
26H
2The urea of O and 11.64g (0.194mol) is dissolved in the 650mL seal cup, adds the 600ml deionized water and stirring, makes it fully dissolve be uniformly dispersed (solution I);
Step C: with the Mg (NO of 8.20g (0.032mol)
3)
26H
2The O solid, the Ni (NO of 0.93g
3)
26H
2The urea of O and 11.64g (0.194mol) is dissolved in the 650mL seal cup, adds the 600ml deionized water and stirring, makes it fully dissolve be uniformly dispersed (solution II);
Step D: the aluminium flake that steps A is cleaned immerses in the solution I and sealing, then seal cup is put into 70 ℃ of water-baths and reacted 24h, put into the solution II that step C prepares rapidly after taking out aluminium flake, react 36h in 70 ℃ of water-baths, take out the aluminium flake washed with de-ionized water, 60 ℃ of oven dry obtain vertical orientated ternary houghite film, are designated as the Ni/Mg/Al-LDHs film; This hydrotalcite film is the compound that is assembled in order by interlayer anion and positively charged laminate; The main body laminate is that metal cation and hydroxide ion constitute octahedron with covalent bond, forms its structure and shepardite Mg (OH) by sharing seamed edge
2Structural similarity; Be made up of three kinds of metallic elements on this vertically oriented hydrotalcite film laminate, its chemical formula is: (Ni
2+Mg
2+)
1-xAl
3+ x(OH)
2(CO
3 2-)
X/2MH
2O, Ni
2+/ Mg
2+Mol ratio is 1.7, x=0.32, m=0.55;
Step e: take by weighing the 7.5mg sulfonated phthalocyanine cobalt and be dissolved in the methyl alcohol of 250ml and stir 6h (solution III), standby;
Step F: LDHs film calcining under 500 ℃ that step D is obtained obtained the Ni/Mg/AlMMO film in 3 hours;
Step G: the MMO film that step F is obtained is cut into 140cm
2Little cylinder was immersed in the solution III load sulfonated phthalocyanine cobalt 1 hour then, and cylinder is taken out, and dried under vacuum condition, namely obtained structural catalyst; This catalyst has been kept the appearance structure of vertical orientated ternary houghite film, has abundant aperture, and its general formula is (Ni
2+Mg
2+)
1-xAl
3+ xO
1.5xM (CoPcS), Ni
2+/ Mg
2+Mol ratio is 1.7, x=0.32, m=0.012.
Steps A: choose 450cm
2(the aluminium flake of 30cm * 15cm * 0.2cm), then aluminium flake is rolled into the seal cup that tubular is put into 600ml, next earlier with acetone ultrasonic cleaning 15min, uses the ultrasonic 15min of ethanol then, use deionized water ultrasonic cleaning 10min at last, take out the aluminium flake that cleans up standby;
Step B: with the solid Mg (NO of 8.20g (0.032mol)
3)
26H
2The urea of O and 11.64g (0.194mol) is dissolved in the 650mL seal cup, adds the 600ml deionized water and stirring, makes it fully dissolve be uniformly dispersed (solution I);
Step C: the aluminium flake that steps A is cleaned immerses in the solution I and sealing, then seal cup is put into 70 ℃ of water-baths and is reacted 36h, takes out the aluminium flake washed with de-ionized water, and 60 ℃ of oven dry obtain vertical orientated binary type hydrotalcite film, are designated as the Mg/Al-LDHs film; The compound that this hydrotalcite film is assembled in order by interlayer anion and positively charged laminate; The main body laminate is that metal cation and hydroxide ion constitute octahedron with covalent bond, forms its structure and shepardite Mg (OH) by sharing seamed edge
2Structural similarity; Be made up of two kinds of metallic elements on this vertically oriented hydrotalcite film laminate, its expression formula is: Mg
2+ 1-xAl
3+ x(OH)
2(CO
3 2-)
X/2MH
2O, x=0.34, m=0.83.
Step D: take by weighing the 7.5mg sulfonated phthalocyanine cobalt and be dissolved in the methanol solution of 250ml and stir 6h (solution II), standby;
Step e: LDHs film calcining under 500 ℃ that step C is obtained obtained MgAl MMO film in 5 hours;
Step F: the MMO film that step e is obtained is cut into 140cm
2Little cylinder was immersed in the solution II load sulfonated phthalocyanine cobalt 1 hour then, and cylinder is taken out, and dried under vacuum condition, namely obtained structural catalyst; This catalyst has been kept the appearance structure of vertical orientated binary type hydrotalcite film, has abundant aperture, and its general formula is Mg
2+ 1-xAl
3+ xO
1.5xM (CoPcS), x=0.34, m=0.015.
Embodiment 7
Steps A. it is standby that preparation n-octyl mercaptan concentration is that the normal octane solution 250ml of 1000ppm puts into the there-necked flask of 300ml;
Step B. is 140cm with area
2The Mg/Al structural catalyst of embodiment 6 preparation be rolled into tube, be suspended from the solution, aerating oxygen also stirs, and begins catalytic reaction under the normal temperature.
Steps A. it is standby that preparation n-octyl mercaptan concentration is that the normal octane solution 250ml of 1000ppm puts into the there-necked flask of 300ml;
Step B. is 140cm with area
2The Ni/Mg/Al structural catalyst of embodiment 5 preparation be rolled into tube, be suspended from the solution, aerating oxygen also stirs, and begins catalytic reaction under the normal temperature.
Claims (7)
1. the application of a vertical orientated binary type hydrotalcite membrane structure catalytic oxidation mercaptan deodorization reaction is characterized in that, the concrete steps of described structuring catalytic oxidation mercaptan deodorization reaction are:
A. compound concentration is the sulfonated phthalocyanine cobalt methanol solution of 10ppm-100ppm, fully stirs sulfonated phthalocyanine cobalt to be uniformly dispersed in 6-12 hour;
B. with 1-800cm
2400-550 ℃ of calcining of vertical orientated binary type hydrotalcite film 2-8 hour, put into sulfonated phthalocyanine cobalt liquor load 1-5 hour of steps A preparation then, take out then under the vacuum condition and dry, namely obtain structural catalyst, this structural catalyst stores under vacuum condition;
C. preparing the concentrations of mercaptans scope is the normal octane solution 50-500ml of 400ppm-2000ppm, in the two mouthfuls of bottles of packing into;
D. structural catalyst is put into the solution of step C preparation and stirred, begin catalytic reaction under the room temperature behind the aerating oxygen;
The preparation method of described vertical orientated binary type hydrotalcite film is:
1). choose 1-800cm
2Aluminium flake, earlier with acetone ultrasonic cleaning 10-20min, use the ultrasonic 10-20min of ethanol then, use deionized water ultrasonic cleaning 5-10min at last, to guarantee that oil stain is removed clean on the aluminium flake, take out the aluminium flake that cleans up standby;
2). the bivalent metal ion M of preparation solubility
2+With the mixed solution of urea, bivalent metal ion M wherein
2+Concentration is 0.01-1mol/L, urea and M
2+Mol ratio be 2-6;
3). the aluminium flake of step 1) preparation is vertically put into 100-1000ml step 2) mixed solution of preparation, 50-150 ℃ of reaction 1-48 hour down, then aluminium flake is taken out, dry under the normal temperature, namely obtain vertical orientated binary type hydrotalcite film;
Described M
2+Represent bivalent metal ion Mg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Mn
2+Or Fe
2+
The compound that described vertical orientated binary type hydrotalcite film is assembled in order by interlayer anion and positively charged laminate; The main body laminate is that metal cation and hydroxide ion constitute octahedron with covalent bond, forms its structure and shepardite Mg (OH) by sharing seamed edge
2Structural similarity; Be made up of two kinds of metallic elements on this vertically oriented hydrotalcite film laminate, its expression general formula is: M
2+ 1-xM
3+ x(OH)
2(Y
N-)
X/nMH
2O, M
2+Represent bivalent metal ion Mg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Mn
2+Or Fe
2+, M
3+Represent trivalent metal ion Al
3+, Y
N-Represent interlayer anion CO
3 2-, NO
3 -, SO
4 2-, Cl
-, Br
-In one or more, n is the charge number of interlayer anion, n is 1 or 2,0.2≤x≤0.4,0≤m≤2.
2. the application of a kind of vertical orientated binary type hydrotalcite membrane structure catalytic oxidation mercaptan deodorization reaction according to claim 1, it is characterized in that, described structural catalyst load sulfonated phthalocyanine cobalt on the vertical orientated binary type hydrotalcite film formation composite metal oxide film basis of calcined precursors obtains, this catalyst has been kept the appearance structure of vertical orientated binary type hydrotalcite film, have abundant aperture, its general formula is M
2+ 1-xAl
3+ xO
1.5xM (CoPcS), wherein M
2+Represent bivalent metal ion Mg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Mn
2+Or Fe
2+, CoPcS represents sulfonated phthalocyanine cobalt, 0.2≤x≤0.4, and m is that its scope of content of sulfonated phthalocyanine cobalt is 0＜m＜2.
3. the preparation method of a vertical orientated ternary houghite film is characterized in that, its concrete preparation process is:
A. choose 1-800cm
2Aluminium flake, earlier with acetone ultrasonic cleaning 10-20min, use the ultrasonic 10-20min of ethanol then, use deionized water ultrasonic cleaning 5-10min at last, to guarantee that oil stain is removed clean on the aluminium flake, take out the aluminium flake that cleans up standby;
B. prepare the bivalent metal ion M of solubility
I 2+With the mixed solution of urea, bivalent metal ion M wherein
I 2+Concentration is 0.01-1mol/L, urea and M
I 2+Mol ratio be 2-6;
C. prepare the bivalent metal ion M of solubility
I 2+, M
II 2+With the mixed solution of urea, wherein M
I 2+/ M
II 2+Mol ratio is 1-50, M
I 2+Concentration is 0.01-1mol/L, urea/(M
I 2++ M
II 2+) mol ratio be 2-6;
D. the aluminium flake of steps A preparation is vertically put into the solution of 100-1000mlB step preparation, reacted 1-48 hour down at 50-150 ℃, put into the solution of 100-1000mlC step preparation after then aluminium flake being taken out rapidly, reaction is 1-48 hour under identical temperature, aluminium flake is taken out, dry under the normal temperature, namely obtain vertical orientated ternary houghite film;
Described M
I 2+And M
II 2+Represent bivalent metal ion Mg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Mn
2+Or Fe
2+, M
I 2+And M
II 2+Different.
4. the vertical orientated ternary houghite film that obtains of method according to claim 3 is characterized in that this hydrotalcite film is the compound that is assembled in order by interlayer anion and positively charged laminate; The main body laminate is that metal cation and hydroxide ion constitute octahedron with covalent bond, forms its structure and shepardite Mg (OH) by sharing seamed edge
2Structural similarity; Be made up of three kinds of metallic elements on this vertically oriented hydrotalcite film laminate, its expression formula is: (M
I 2+M
II 2+)
1-xM
3+ x(OH)
2(Y
N-)
X/nMH
2O, wherein M
I 2+And M
II 2+Represent bivalent metal ion Mg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Mn
2+Or Fe
2+, M
I 2+And M
II 2+Different; M
3+Represent trivalent metal ion Al
3+, Y
N-Represent interlayer anion CO
3 2-, NO
3 -, SO
4 2-, Cl
-, Br
-In one or more, n is the charge number of interlayer anion, n is 1 or 2,0.2≤x≤0.4,0≤m≤2.
5. the application of a kind of vertical orientated ternary houghite membrane structure catalytic oxidation mercaptan deodorization reaction according to claim 3.
6. the application of a kind of vertical orientated ternary houghite membrane structure catalytic oxidation mercaptan deodorization reaction according to claim 5 is characterized in that, the concrete steps of described structuring catalytic oxidation mercaptan deodorization reaction are:
A. compound concentration is the sulfonated phthalocyanine cobalt methanol solution of 10ppm-100ppm, fully stirs sulfonated phthalocyanine cobalt to be uniformly dispersed in 6-12 hour;
B. with 1-800cm
2400-550 ℃ of calcining of vertical orientated ternary houghite film 2-8 hour, put into sulfonated phthalocyanine cobalt liquor load 1-5 hour of steps A preparation then, take out then under the vacuum condition and dry, namely obtain structural catalyst, this structural catalyst stores under vacuum condition;
C. preparing the concentrations of mercaptans scope is the normal octane solution 50-500ml of 400ppm-2000ppm, in the two mouthfuls of bottles of packing into;
D. structural catalyst is put into the solution of step C preparation and stirred, begin catalytic reaction under the room temperature behind the aerating oxygen.
7. the application of a kind of vertical orientated ternary houghite membrane structure catalytic oxidation mercaptan deodorization reaction according to claim 6, it is characterized in that, described structural catalyst load sulfonated phthalocyanine cobalt on the vertical orientated ternary houghite film formation composite metal oxide film basis of calcined precursors obtains, this catalyst has been kept the appearance structure of vertical orientated ternary houghite film, have abundant aperture, its general formula is (M
I 2+M
II 2+)
1-xAl
3+ xO
1.5xM (CoPcS), wherein M
I 2+And M
II 2+Represent bivalent metal ion Mg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Mn
2+Or Fe
2+, M
I 2+And M
II 2+Difference, M
I 2+/ M
II 2+Mol ratio is 1-50; CoPcS represents sulfonated phthalocyanine cobalt; 0.2≤x≤0.4, m is that its scope of content of sulfonated phthalocyanine cobalt is 0＜m＜2.
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| CN102895884B (en) * | 2012-10-29 | 2014-10-29 | 东南大学 | Coating-free solid alkali ceramic catalytic membrane and preparation method thereof |
| CN103755714B (en) * | 2014-01-27 | 2015-12-02 | 福州大学 | A kind of Phthalocyanine-hydrocomplex complex and its preparation method and application |
| CN104365662A (en) * | 2014-10-17 | 2015-02-25 | 中国科学院海洋研究所 | Magnesium-aluminum compound metal oxide antibacterial thin film material as well as preparation and application thereof |
| CN104907079A (en) * | 2015-05-07 | 2015-09-16 | 北京化工大学 | Preparation method of mixed metal oxide thin film catalyst for hydrocarbon oxidation reaction |
| CN106868483B (en) * | 2017-02-28 | 2019-03-29 | 北京石油化工学院 | A kind of preparation method of aluminium and aluminum alloy surface ternary houghite film |
| CN107541718B (en) * | 2017-09-01 | 2020-01-21 | 苏州云舒新材料科技有限公司 | Preparation method of hydrotalcite-based magneto-optical film material |
| CN107913723B (en) * | 2017-12-08 | 2020-06-23 | 山东理工大学 | Chromium-containing three-dimensional nickel-aluminum hydrotalcite-like film and preparation method and application thereof |
| CN108097058B (en) * | 2017-12-29 | 2019-11-22 | 北京化工大学 | A kind of carbon dioxide selectivity osmotic membrane and its preparation method and application |
| CN108726582A (en) * | 2018-06-27 | 2018-11-02 | 江苏大学 | One kind is based on ultra-thin laminated double hydroxide nanometer sheet material of ferronickel vanadium and its preparation method and application |
| CN110230072B (en) * | 2019-05-06 | 2021-02-09 | 湖北大学 | Preparation method and application of N-NiZnCu LDH/rGO nanosheet array material on foamed nickel |
| CN110560065B (en) * | 2019-08-23 | 2022-08-05 | 万华化学集团股份有限公司 | Metal carrier supported catalyst, preparation method and application thereof in preparation of m-xylylenediamine |
| CN110711553B (en) * | 2019-11-20 | 2022-05-17 | 广州大学 | Hydrotalcite-pseudo-boehmite composite film and preparation method and application thereof |
| CN113388269B (en) * | 2021-06-18 | 2022-05-31 | 浙江华源颜料股份有限公司 | Heat-resistant iron oxide green pigment and synthesis method thereof |
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| CN1768940A (en) * | 2005-11-03 | 2006-05-10 | 北京化工大学 | Hydrotalcite like structurization catalyst with mica as matrix and preparation method |
| CN1792449A (en) * | 2005-12-06 | 2006-06-28 | 北京化工大学 | Aluminium-based pseudo-hydrotalcite structuralization catalyst, and its prepn. method |
| CN101285185A (en) * | 2008-03-21 | 2008-10-15 | 北京化工大学 | Preparation method of corrosion resistant hydrotalcite-like film at surface of aluminum and aluminum alloy parts |
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| CN101285185A (en) * | 2008-03-21 | 2008-10-15 | 北京化工大学 | Preparation method of corrosion resistant hydrotalcite-like film at surface of aluminum and aluminum alloy parts |
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