CN105413751B - A kind of preparation method of montmorillonite/polyaniline complex solid base catalyst - Google Patents
A kind of preparation method of montmorillonite/polyaniline complex solid base catalyst Download PDFInfo
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- CN105413751B CN105413751B CN201510748492.7A CN201510748492A CN105413751B CN 105413751 B CN105413751 B CN 105413751B CN 201510748492 A CN201510748492 A CN 201510748492A CN 105413751 B CN105413751 B CN 105413751B
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- montmorillonite
- base catalyst
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- 229910052901 montmorillonite Inorganic materials 0.000 title claims abstract description 64
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 239000007787 solid Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 24
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 8
- 238000009830 intercalation Methods 0.000 claims abstract description 8
- 230000002687 intercalation Effects 0.000 claims abstract description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 5
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 4
- 239000001632 sodium acetate Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 2
- 239000004575 stone Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000002585 base Substances 0.000 description 26
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000005815 base catalysis Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 silicon aluminate Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 2
- 238000002383 small-angle X-ray diffraction data Methods 0.000 description 2
- 235000011091 sodium acetates Nutrition 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000006000 Knoevenagel condensation reaction Methods 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- IXSZQYVWNJNRAL-UHFFFAOYSA-N etoxazole Chemical compound CCOC1=CC(C(C)(C)C)=CC=C1C1N=C(C=2C(=CC=CC=2F)F)OC1 IXSZQYVWNJNRAL-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method of montmorillonite/polyaniline complex solid base catalyst：Use FeCl3Carried out between montmorillonite layer after intercalation, then forerunner's product is prepared with HCl, aniline, the polyaniline that montmorillonite is combined finally is changed into the polyaniline of eigenstate using ethylene glycol, sodium acetate.The preparation process of montmorillonite of the present invention/polyaniline complex solid base catalyst is simple, prepare it is with low cost, the features such as with good catalytic activity.
Description
Technical field
The present invention relates to a kind of preparation method of montmorillonite/polyaniline complex solid base catalyst.
Background technology
Montmorillonite is a kind of natural layer silicon aluminate crystal of nanoscale, with stronger surface electronegativity, compares table
Area is big, adsorptivity is strong, water swelling, suspension the features such as, have a laudatory title of " omnipotent clay mineral ", distributed in nature extensively,
It is cheap, it is safe and harmless.001 crystal face of montmorillonite is very small, passes through cation exchange, it would be desirable to metal ion exchanged enter
Enter interlayer, intercalation compound can be formed.
Polyaniline is considered as most to have one of conducting polymer of actual application prospect.Its anti-corrosion of metal, electromagnetic shielding,
Application in terms of gas sensor just moves towards the industrialization.Due to PANI have prepare cost it is low, insoluble in most of organic molten
The characteristics of agent and water, it shows incomparable excellent catalysis in organic transformation reaction as catalyst or catalyst carrier
Performance.
Base catalyzed reactions are one of important reactions of chemical industry, and base catalyzed reactions include double bond isomerization reaction, esterification
Reaction, ester exchange reaction, Knoevenagel condensation reactions and Michael addition reactions etc., Knoevenagel contractings therein
The dehydration condensation that reaction is carbonyls and activity methene compound is closed, for the formation of carbon-carbon double bond, this is anti-
It should be widely used in terms of baroque fine chemicals preparation.
Compared with liquid alkali catalyst, solid base catalyst has the following advantages that：Catalyst is easily from reactant mixture
Separate；High selectivity, high catalytic activity, reaction condition is gentle；Post catalyst reaction regenerating easily, can be recycled；Ring
Border is friendly, it is to avoid use polar solvent or consisting of phase-transferring agent, corrosion-free to equipment；Reaction process process continuous can be made, raising is set
Standby production capacity；It can be applied in high temperature even gas phase reaction；Solid base catalyst is without C-C key fracture energies, under high temperature
Reaction will not cause carbon distribution.Therefore the friendly solid base catalyst of development environment is significant.
The content of the invention
It is an object of the invention to provide a kind of preparation method of montmorillonite/polyaniline complex solid base catalyst.
To realize the object of the invention, the technical solution adopted in the present invention is as follows：
A kind of preparation method of montmorillonite/polyaniline complex solid base catalyst, methods described is：Use FeCl3It is de- covering
Carried out between rock layers after intercalation, then with HCl, aniline prepare forerunner's product, finally will be with montmorillonite using ethylene glycol, sodium acetate
Compound polyaniline changes into the polyaniline of eigenstate, and the montmorillonite/polyaniline complex solid base catalyst is made.
Further, the method for the invention is carried out as follows：
(1) by 10 ~ 60gFeCl3, 1 ~ 15g montmorillonites, with 1 ~ 1.3L deionized water dissolving, 50 ~ 60 DEG C of 1 ~ 5h of stirring,
Filtering, dries, obtains intercalation FeCl3Montmorillonite;
(2) the intercalation FeCl obtained in step (1) is taken3Montmorillonite 2 ~ 3g, 1 ~ 2.2mlHCl, 50 ~ 60ml deionizations are water-soluble
Solution is in there-necked flask, and 50 ~ 65 DEG C of temperature control pours into 1 ~ 6ml aniline in three-necked flask, after 2 ~ 3h of reaction, filters, washing,
50 ~ 65 DEG C are dried to obtain montmorillonite polyaniline complex solid base catalyst presoma；
(3) by the montmorillonite polyaniline complex solid base catalyst presoma obtained in 1.2 ~ 1.8g steps (2), 1 ~ 4g second
Sour sodium, 10 ~ 60ml ethylene glycol is incorporated with the water heating kettle of polytetrafluoroethyllining lining after stirring, 373 ~ 483k constant temperature 1 ~
9h, takes out product, filters, and dries, obtains montmorillonite/polyaniline complex solid base catalyst.
In the step (1), the FeCl3Quality is 50 ~ 60g.
In the step (1), the mixing time is 3 ~ 5h.
In the step (1), deionized water is with 1 ~ 1.2L.
In the step (2), the HCl consumptions are 2 ~ 2.2ml.
In the step (2), the aniline consumption is 5 ~ 6ml.
In the step (3), the temperature is 473 ~ 483k.
In the step (3), the constant temperature time is 8 ~ 9h.
Montmorillonite of the present invention/polyaniline complex solid base catalyst and preparation method thereof takes full advantage of montmorillonite
As the catalytic performance of the excellent performance of carrier material, and polyaniline, so as to improve the base catalysis performance of polyaniline.The present invention
The montmorillonite of offer/polyaniline complex solid base catalyst has preferable base catalysis performance.
Brief description of the drawings
Fig. 1 is that embodiment 1 prepares ultraviolet-visible spectrogram in montmorillonite/polyaniline complex solid base catalyst.Wherein A
It is the UV-visible spectrum of montmorillonite, B is the UV-visible spectrum of montmorillonite/polyaniline complex solid base catalyst.
Fig. 2 is that embodiment 1 prepares small angle X-ray diffraction in montmorillonite/polyaniline complex solid base catalyst（XRD）Figure
Spectrum.Wherein A is the small angle XRD spectrum of montmorillonite, and B is the small angle XRD spectrum of montmorillonite/polyaniline complex solid base catalyst.
Fig. 3 is that montmorillonite/polyaniline complex solid base catalyst prepared by embodiment 1 reacts in catalysis Knoevenagel
In apply mechanically active figure.
Specific embodiment
Illustrated embodiment below in conjunction with the accompanying drawings, the invention will be further described.
Embodiment 1
By 52.20gFeCl3, 10g montmorillonites, with 1L deionized water dissolving, 60 DEG C of stirring 4h are filtered, are dried, obtain
Montmorillonite B；By 2.65g montmorillonite B, 2mlHCl, 50ml deionized water dissolvings in there-necked flask, 60 DEG C of temperature control, by 5ml benzene
Amine is poured into three-necked flask, after reaction 2h, is filtered, washing, 60 DEG C are dried to obtain product C, by 1.4g C, 3.6g sodium acetates,
50ml ethylene glycol is incorporated with the water heating kettle of polytetrafluoroethyllining lining after stirring, in 473k constant temperature 8h, takes out product, mistake
Filter, dries, obtains montmorillonite/polyaniline complex solid base catalyst.
Embodiment 2
By 50.20gFeCl3, 8g montmorillonites, with 1.1L deionized water dissolving, 60 DEG C of stirring 4.5h are filtered, are dried, obtain
To montmorillonite B；By 2.8g montmorillonite B, 2.1mlHCl, 55ml deionized water dissolvings in there-necked flask, 60 DEG C of temperature control will
5.5ml aniline is poured into three-necked flask, after reaction 2.5h, is filtered, washing, 60 DEG C are dried to obtain product C, by 1.5g C, 3.8g
Sodium acetate, 55ml ethylene glycol is incorporated with the water heating kettle of polytetrafluoroethyllining lining after stirring, in 478k constant temperature 8.5h, is taken out
Product, is filtered, and is dried, is obtained montmorillonite/polyaniline complex solid base catalyst.
Embodiment 3
By 54.20gFeCl3, 11g montmorillonites, with 1.2L deionized water dissolving, 60 DEG C of stirring 5h are filtered, are dried, obtain
To montmorillonite B；By 3g montmorillonite B, 2.2mlHCl, 60ml deionized water dissolvings in there-necked flask, 60 DEG C of temperature control, by 6ml
Aniline is poured into three-necked flask, after reaction 3h, is filtered, washing, 60 DEG C are dried to obtain product C, by 1.6g C, 4g sodium acetates,
60ml ethylene glycol is incorporated with the water heating kettle of polytetrafluoroethyllining lining after stirring, in 483k constant temperature 9h, takes out product, mistake
Filter, dries, obtains montmorillonite/polyaniline complex solid base catalyst.
The UV analyses of 1 montmorillonite of annex/polyaniline complex solid base catalyst：
As shown in figure 1, montmorillonite-loaded polyaniline has a strong absworption peak at 360nm, be phenyl ring in polyaniline chain π-
π * transition.Absworption peak at 610nm represents the presence of quinone ring.It is polyaniline in eigenstate to illustrate montmorillonite-loaded polyaniline.
The small angle XRD analysis of 2 montmorillonites of annex/polyaniline complex solid base catalyst：
As shown in Fig. 2 as can be seen from the figure after montmorillonite-loaded polyaniline, the angle of diffraction 2 of its crystal face (001)Diminish,
Corresponding interlamellar spacing d (001) increases, illustrate that montmorillonite supports big by polyaniline.
3 montmorillonites of annex/polyaniline complex solid base catalyst applies mechanically catalytic activity：
As shown in figure 3, montmorillonite/polyaniline complex solid alkali has good base catalysis activity, while this catalyst
Activity does not have obvious reduction after utilization is repeated 3 times.
Claims (7)
1. a kind of preparation method of montmorillonite/polyaniline complex solid base catalyst, it is characterised in that methods described is：Use FeCl3
Carried out between montmorillonite layer after intercalation, then forerunner's product is prepared with HCl, aniline, will finally covered using ethylene glycol, sodium acetate
The compound polyaniline of de- stone changes into the polyaniline of eigenstate, and the montmorillonite/polyaniline complex solid base catalyst is made；
Methods described is carried out as follows：
(1) by 10~60g FeCl3, 1~15g montmorillonites, with 1~1.3L deionized water dissolving, 50~60 DEG C of 1~5h of stirring,
Filtering, dries, obtains intercalation FeCl3Montmorillonite；
(2) the intercalation FeCl obtained in step (1) is taken3Montmorillonite 2~3g, 1~2.2ml HCl, 50~60ml deionized water dissolvings
In there-necked flask, 50~65 DEG C of temperature control pours into 1~6ml aniline in three-necked flask, after 2~3h of reaction, filters, washing,
50~65 DEG C are dried to obtain montmorillonite/polyaniline complex solid base catalyst presoma；
(3) by the montmorillonite obtained in 1.2~1.8g steps (2)/polyaniline complex solid base catalyst presoma, 1~4g second
Sour sodium, 10~60ml ethylene glycol is incorporated with the water heating kettle of polytetrafluoroethyllining lining after stirring, in 373~483K constant temperature 1
~9h, takes out product, filters, washs and dries, obtains montmorillonite/polyaniline complex solid base catalyst.
2. a kind of preparation method of montmorillonite/polyaniline complex solid base catalyst as claimed in claim 1, it is characterised in that
In the step (1), the FeCl3Quality is 50~60g.
3. a kind of preparation method of montmorillonite/polyaniline complex solid base catalyst as claimed in claim 1, it is characterised in that
In the step (1), the mixing time is 3~5h.
4. a kind of preparation method of montmorillonite/polyaniline complex solid base catalyst as claimed in claim 1, it is characterised in that
In the step (2), the HCl consumptions are 2~2.2ml.
5. a kind of preparation method of montmorillonite/polyaniline complex solid base catalyst as claimed in claim 1, it is characterised in that
In the step (2), the aniline consumption is 5~6ml.
6. a kind of preparation method of montmorillonite/polyaniline complex solid base catalyst as claimed in claim 1, it is characterised in that
In the step (3), the temperature is 473~483K.
7. a kind of preparation method of montmorillonite/polyaniline complex solid base catalyst as claimed in claim 1, it is characterised in that
In the step (3), the constant temperature time is 8~9h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6136909A (en) * | 1999-05-20 | 2000-10-24 | Industrial Technology Research Institute | Preparation of conductive polymeric nanocomposite |
| CN1381530A (en) * | 2002-03-25 | 2002-11-27 | 浙江大学 | Polyphenylamine composition with clay ore as carrier and its preparing process |
| CN104741096A (en) * | 2015-03-16 | 2015-07-01 | 中国科学院兰州化学物理研究所 | Preparation method of magnetic clay mineral/polyaniline composite adsorption material |
-
2015
- 2015-11-07 CN CN201510748492.7A patent/CN105413751B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6136909A (en) * | 1999-05-20 | 2000-10-24 | Industrial Technology Research Institute | Preparation of conductive polymeric nanocomposite |
| CN1381530A (en) * | 2002-03-25 | 2002-11-27 | 浙江大学 | Polyphenylamine composition with clay ore as carrier and its preparing process |
| CN104741096A (en) * | 2015-03-16 | 2015-07-01 | 中国科学院兰州化学物理研究所 | Preparation method of magnetic clay mineral/polyaniline composite adsorption material |
Non-Patent Citations (1)
| Title |
|---|
| 原位插层聚合法制备聚苯胺/蒙脱石纳米复合导电材料的研究;胡傲厚 等;《非金属矿》;20100531;第33卷(第3期);第5-8页 * |
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