CN104773807A - Application of Co(salen) catalytic paper in lignin oxidation - Google Patents
Application of Co(salen) catalytic paper in lignin oxidation Download PDFInfo
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- CN104773807A CN104773807A CN201510130919.7A CN201510130919A CN104773807A CN 104773807 A CN104773807 A CN 104773807A CN 201510130919 A CN201510130919 A CN 201510130919A CN 104773807 A CN104773807 A CN 104773807A
- Authority
- CN
- China
- Prior art keywords
- lignin
- salen
- paper
- oxidation
- catalytic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 60
- VZHHNBNSMNNUAD-UHFFFAOYSA-N cobalt 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound [Co].OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VZHHNBNSMNNUAD-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 230000003647 oxidation Effects 0.000 title claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 claims description 43
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 102000004190 Enzymes Human genes 0.000 description 8
- 108090000790 Enzymes Proteins 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004886 process control Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101100006982 Mus musculus Ppcdc gene Proteins 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- -1 ion diallyl dimethyl ammoniumchloride Chemical class 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Paper (AREA)
- Catalysts (AREA)
Abstract
Belongying to lignin catalytic oxidation technologies, the invention discloses application of Co(salen) catalytic paper in lignin oxidation. According to the method provided by the invention, in the presence o CO(salen) catalytic paper and H2O2, catalytic oxidation treatment is carried out on lignin. The invention adopts pollution-free catalytic oxidation technology, and the technology has the characteristics of small raw material consumption and no demanding requirement for environmental conditions, various performance of lignin degradation is significantly improved, and reagent consumption is significantly reduced.
Description
Technical field
The present invention relates to the application of a kind of Co (salen) catalysis paper in lignin oxidation, is the technology of the catalyzed oxidation lignin that is improved.
Background technology
The greatest problem of world today's facing mankind is economic sustainable development, this renewable natural resources needing people to develop to make new advances produces technique and the technology of material, but the exploitation of environmentally friendly efficient catalytic lignin oxidation is more and more subject to common concern.High-level efficiency highly active catalyzed oxidation lignin should have good reaction efficiency and reaction preference.Therefore, the key issue that efficient highly active catalyzer is lignin oxidation field is researched and developed.
Lot of experiments research shows, biological enzyme is limited to raising lignin oxidation effectiveness, and biological enzyme preparation difficulty, responsive to envrionment conditions.And then, have developed and there is analogue enztme (the i.e. imitative enzyme) compound even more superior with natural enzyme functional similarity.Imitative enzyme catalysis has the advantage of biological enzyme and chemical catalysis, is another the direct effective new way realizing lignin Green Chemistry.Imitative enzyme catalysis is utilized to obtain the speed of response needed, but also there is many problems in catalysis technique large-scale application, be difficult to after having reacted be separated completely and reclaim, address these problems and just catalyzer must be fixed on suitable carrier, and immobilized catalyzer reduces due to specific surface area, reaction mass transfer rate-constrained, can cause the adsorption of catalyzer to reduce, thus catalytic activity is declined.In order to prepare the catalyzer of high activity immobilization, high specific surface area must be kept immobilized simultaneously.Thus, explore be easy to be separated and to reclaim and the key that to be catalysis technique practical of the immobilization technology with highly active catalyzer.
Porous is flexible and catalysis paper that is that be easy to control will be a kind of functional materials having application prospect, and be widely used in large quantity research, in order to the advantage in conjunction with imitative enzyme and catalysis paper, with reference to related documents, synthesize Co (salen) catalysis paper, be applied to lignin catalytic oxidation.Adopt Co (salen) catalysis paper catalyzed oxidation lignin, the reactive behavior of lignin can be increased, strengthen the reaction efficiency of hydrogen peroxide etc. and lignin, thus improve the degradation property of lignin, and be more conducive to the recycling of catalyzer.But Co (salen) catalysis paper and hydrogen peroxide form new catalyzed oxidation lignin technique, have not yet to see relevant technology report.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of technique of catalyzed oxidation lignin of improvement, and its Technology is easily implemented, pollution-free, and the degradation property improving lignin is effective, improve lignin degradation properties obvious, and catalyzer is easy to recycling.
Solve the scheme that technical problem of the present invention adopts and mainly comprise following steps:
At Co (salen) catalysis paper, H
2o
2under existent condition, catalytic oxidation treatment is carried out to lignin.
During to lignin catalytic oxide treatment, in every 0.5 ~ 1 g lignin, add 20 ~ 50mL water, add Co (salen) catalysis paper 0.01 ~ 0.03g, H simultaneously
2o
2solution 0.3 ~ 0.7 mL, processes 1h ~ 3h after mixing at 20 DEG C ~ 80 DEG C.
Described H
2o
2solution to be mass percent concentration be 30% the aqueous solution.
The invention has the beneficial effects as follows:
(1) Co (salen) catalysis paper is as a kind of new catalytic material, not only has easy to use and that catalysis efficiency is high advantage, and is easy to recycling;
(2) amount is few, and process implementing is easy;
(3) improve lignin degradation properties, adopt the technique of Co (salen) catalysis paper catalyzed oxidation lignin, can improve decomposition rate of lignin, decomposition rate of lignin is higher than the 20-30% of traditional C o (salen) powder catalytic effect;
(4) reduce reagent consumption, adopt the technique of Co (salen) catalysis paper catalyzed oxidation lignin, can reduce over hydrogen oxide consumption, hydrogen peroxide consumption is lower than the 20-30% of traditional C o (salen) powder.
Embodiment
Below by embodiment, the present invention is described in further detail, but protection scope of the present invention is not limited to described content.
The application in lignin oxidation of embodiment 1:Co (salen) catalysis paper, concrete operations are as follows:
(1) preparation of double salicylaldehyde contracting triethylenediamine cobalt title complex Co (salen)
the synthesis of A, Salen
Get 2.5g quadrol and 8.5mL salicylic aldehyde is dissolved in 18mL methyl alcohol, in ice-water bath, stir 30min, leave standstill 15min, decompress filter, use lmL washed with diethylether, dry 6h at 33 DEG C, obtains 10.7g faint yellow solid, use 160mL dehydrated alcohol recrystallization again, dry 18h at 33 DEG C, obtains the yellow light tone tabular crystal of 9.4g, is Schiff's base salen, productive rate is 88.0%, fusing point: 125-125.5 DEG C.
, Co (salen) synthesis
Getting 1.3mmoL product Schiff's base obtained in the previous step salen is dissolved in 15mL methyl alcohol, by gained solution and 3mmoL metal-salt CoAc
24H
2o mixes, backflow 1h, and cooling, filtration, vacuum-drying 1h at 50 DEG C, gained red brown solid is Co (salen) title complex, productive rate: 97.75%, fusing point: be greater than 300 DEG C.
(2) synthesis of Co (salen) catalysis paper
Catalysis paper is prepared according to papermaking process; Add 5.0g ceramic fiber, 0.4g CATALYST Co (salen), after adding deionized water, fully mix; Add 0.1g positively charged ion diallyl dimethyl ammoniumchloride (PDADMAC), fully mix; Add 0.5g alumina sol, fully mix; Add 0.1g anionic polyacrylamide (A-PAM), fully mix; Add 0.5g paper pulp, add deionized water, final total material concentration 0.5% w/v, fully mixes; Standard sheet-former is copied into paper-like; By wet paper at oil press pressure pressure 5 min, then at 105 DEG C of baking oven inner dryings; 350 DEG C of thermal treatment 12h, obtain Co (salen)/ceramic fibrous composite material catalysis paper.
(3) method of Co (salen) catalysis paper catalyzed oxidation lignin
At Co (salen) catalysis paper, H
2o
2under existent condition, catalytic oxidation treatment is carried out to lignin; During to lignin catalytic oxide treatment, water 20mL, lignin 0.5g, the temperature of process controls at 20 DEG C, time 1h; During to lignin catalytic oxide treatment, also add CATALYST Co (salen) catalysis paper, Co (salen) catalysis paper consumption 0.01g; During to lignin catalytic oxide treatment, also add oxygenant H
2o
2, mass percent concentration is the H of 30%
2o
2solution 0.3mL; Decomposition rate of lignin is higher than 25% of traditional C o (salen) powder catalytic effect; Hydrogen peroxide consumes lower than 30% of traditional C o (salen) powder.
The application in lignin oxidation of embodiment 2:Co (salen) catalysis paper, concrete operations are as follows:
(1) synthetic method of Co (salen) catalysis paper is with embodiment 1 step (1), (2);
(2) method of Co (salen) catalysis paper catalyzed oxidation lignin
At Co (salen) catalysis paper, H
2o
2under existent condition, catalytic oxidation treatment is carried out to lignin; During to lignin catalytic oxide treatment, water 40mL, lignin 0.7g, the temperature of process controls at 50 DEG C, time 2h; During to lignin catalytic oxide treatment, also add CATALYST Co (salen) catalysis paper, Co (salen) catalysis paper consumption 0.02g; During to lignin catalytic oxide treatment, also add oxygenant H
2o
2, mass percent concentration is the H of 30%
2o
2solution 0.5mL; Decomposition rate of lignin is higher than 30% of traditional C o (salen) powder catalytic effect; Hydrogen peroxide consumes lower than 25% of traditional C o (salen) powder.
The application in lignin oxidation of embodiment 3:Co (salen) catalysis paper, concrete operations are as follows:
(3) synthetic method of Co (salen) catalysis paper is with embodiment 1 step (1), (2);
(4) method of Co (salen) catalysis paper catalyzed oxidation lignin
At Co (salen) catalysis paper, H
2o
2under existent condition, catalytic oxidation treatment is carried out to lignin; During to lignin catalytic oxide treatment, water 50mL, lignin 1g, the temperature of process controls at 80 DEG C, time 3h; During to lignin catalytic oxide treatment, also add CATALYST Co (salen) catalysis paper, Co (salen) catalysis paper consumption 0.03g; During to lignin catalytic oxide treatment, also add oxygenant H
2o
2, mass percent concentration is the H of 30%
2o
2solution 0.7mL; Decomposition rate of lignin is higher than 21% of traditional C o (salen) powder catalytic effect; Hydrogen peroxide consumes lower than 23% of traditional C o (salen) powder.
Claims (3)
1. the application of Co (salen) catalysis paper in lignin oxidation, is characterized in that: at Co (salen) catalysis paper and H
2o
2under existent condition, catalyzed oxidation lignin.
2. the application of Co according to claim 1 (salen) catalysis paper in lignin oxidation, it is characterized in that: during to lignin catalytic oxide treatment, in every 0.5 ~ 1 g lignin, add 20 ~ 50mL water, add Co (salen) catalysis paper 0.01 ~ 0.03g, H simultaneously
2o
2solution 0.3 ~ 0.7 mL, processes 1h ~ 3h after mixing at 20 DEG C ~ 80 DEG C.
3. the application of Co according to claim 2 (salen) catalysis paper in lignin oxidation, is characterized in that: H
2o
2solution to be mass percent concentration be 30% the aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510130919.7A CN104773807B (en) | 2015-03-25 | 2015-03-25 | Application of Co(salen) catalytic paper in lignin oxidation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510130919.7A CN104773807B (en) | 2015-03-25 | 2015-03-25 | Application of Co(salen) catalytic paper in lignin oxidation |
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| Publication Number | Publication Date |
|---|---|
| CN104773807A true CN104773807A (en) | 2015-07-15 |
| CN104773807B CN104773807B (en) | 2017-04-12 |
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| CN201510130919.7A Expired - Fee Related CN104773807B (en) | 2015-03-25 | 2015-03-25 | Application of Co(salen) catalytic paper in lignin oxidation |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105113308A (en) * | 2015-08-12 | 2015-12-02 | 昆明理工大学 | Process of pulp oxygen delignification catalysis based on M(salen) catalytic paper and surfactant |
| CN106045004A (en) * | 2016-07-20 | 2016-10-26 | 昆明理工大学 | Process for catalytic degradation of chlorine bleaching effluent through laccase-M (salen) one-pot method |
| CN106190216A (en) * | 2016-07-20 | 2016-12-07 | 昆明理工大学 | The technique of M (salen) catalysis paper catalytically liquefying biomass in a kind of ionic liquid |
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2015
- 2015-03-25 CN CN201510130919.7A patent/CN104773807B/en not_active Expired - Fee Related
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105113308A (en) * | 2015-08-12 | 2015-12-02 | 昆明理工大学 | Process of pulp oxygen delignification catalysis based on M(salen) catalytic paper and surfactant |
| CN105113308B (en) * | 2015-08-12 | 2017-07-25 | 昆明理工大学 | The catalysis pulp oxygen delignification technique of paper and surfactant is catalyzed based on M (salen) |
| CN106045004A (en) * | 2016-07-20 | 2016-10-26 | 昆明理工大学 | Process for catalytic degradation of chlorine bleaching effluent through laccase-M (salen) one-pot method |
| CN106190216A (en) * | 2016-07-20 | 2016-12-07 | 昆明理工大学 | The technique of M (salen) catalysis paper catalytically liquefying biomass in a kind of ionic liquid |
| CN106045004B (en) * | 2016-07-20 | 2019-07-05 | 昆明理工大学 | The technique of laccase-M (salen) one kettle way catalytic degradation chloro-bleaching effluents |
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| CN104773807B (en) | 2017-04-12 |
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