CN104773807B - 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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- CN104773807B CN104773807B CN201510130919.7A CN201510130919A CN104773807B CN 104773807 B CN104773807 B CN 104773807B CN 201510130919 A CN201510130919 A CN 201510130919A CN 104773807 B CN104773807 B CN 104773807B
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- Prior art keywords
- lignin
- salen
- paper
- catalysis
- oxidation
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- 229920005610 lignin Polymers 0.000 title claims abstract description 59
- 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 43
- 230000003647 oxidation Effects 0.000 title claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 39
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000006555 catalytic reaction Methods 0.000 claims description 36
- 230000008569 process Effects 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 9
- 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 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 17
- 238000005516 engineering process Methods 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 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
- 239000003054 catalyst Substances 0.000 description 11
- 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
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001602688 Pama Species 0.000 description 1
- 229920001131 Pulp (paper) Polymers 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
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 cation diallyl dimethyl ammoniumchlorides Chemical class 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
- 239000013078 crystal Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002171 ethylene diamines Chemical class 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
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000003622 immobilized catalyst Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002023 wood Substances 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 a kind of application of Co (salen) catalysis paper in lignin oxidation, is an improved catalysis oxidation
The technology of lignin.
Background technology
The greatest problem of world today's facing mankind is economic sustainable development, and it is new that this needs people to develop
The technique and technology of renewable natural resources production material, however, the exploitation of environmentally friendly efficient catalytic lignin oxidation is got over
To be more subject to common concern.The highly active catalysis oxidation lignin of high efficiency should have good reaction efficiency and reaction selectivity.Cause
This, the efficient highly active catalyst of research and development is the key issue that lignin aoxidizes field.
Lot of experiments research shows that enzyme is limited to improving lignin oxidation effectiveness, and enzyme prepares difficulty, to ring
Border condition responsive.Further, have developed with the analogue enztme even more superior with native enzyme functional similarity（Imitate enzyme）Chemical combination
Thing.Imitative enzyme catalysiss have the advantages that both biological enzyme and chemical catalysis, are to realize another of lignin Green Chemistry directly
And effective new way.The response speed for needing is obtained using imitative enzyme catalysis, but catalysis technique large-scale application is also present
Many problems, are difficult to be kept completely separate and reclaimed after the completion of reaction, and to solve these problems must just be fixed on catalyst
On suitable carrier, and immobilized catalyst is reduced due to specific surface area, and reaction mass transfer rate-constrained can cause catalyst
Adsorption is reduced, so that catalysis activity declines.In order to prepare the catalyst of high activity immobilization, it is necessary to immobilized same
When keep high specific surface area.Thus, exploration be easily isolated and reclaim and with the immobilization technology of highly active catalyst
It is the practical key of catalysis technique.
The flexible and easily controllable catalysis paper of porous will be a kind of functional material of great application prospect, and be widely used in
In numerous studies, in order to combine the advantage of both imitative enzyme and catalysis paper, with reference to relevant document, synthesize Co (salen) catalysis paper,
It is applied to lignin catalytic oxidation.Paper catalysis oxidation lignin is catalyzed using Co (salen), the reactivity of lignin can be increased, strengthened
The reaction efficiency of hydrogen peroxide etc. and lignin, so as to improve the degradability of lignin, and the more conducively recycling of catalyst.
But Co (salen) is catalyzed paper and constitutes new catalysis oxidation lignin technique with hydrogen peroxide, has not yet to see the technology report of correlation
Road.
The content of the invention
The technical problem to be solved is to provide a kind of technique of improved catalysis oxidation lignin, its Technology
Easily implement, pollution-free, the degradability effect for improving lignin is good, improve lignin degradation properties substantially, and catalyst is easy to
Recycling.
The scheme that the technical problem of the solution present invention is adopted mainly is comprised the steps of：
Paper, H are catalyzed in Co (salen)2O2Under conditions of presence, catalytic oxidation treatment is carried out to lignin.
During to lignin catalytic oxidation processes, 20～50mL water is added in per 0.5～1 g lignins, while adding Co
(salen) 0.01～0.03g of paper, H are catalyzed2O2The mL of solution 0.3～0.7, after mixing at 20 DEG C～80 DEG C process 1h～3h.
The H2O2Solution is aqueous solution that mass percent concentration is 30%.
The invention has the beneficial effects as follows:
(1) Co (salen) catalysis paper is not only high with easy to use and catalysis efficiency as a kind of new catalytic material
Advantage, and be easily recycled；
(2) measure seldom, process implementing is easy；
(3) lignin degradation properties are improved, the technique for being catalyzed paper catalysis oxidation lignin using Co (salen) can be improved
Decomposition rate of lignin, 20-30% of the decomposition rate of lignin higher than tradition Co (salen) powder catalytic effect；
(4) reagent consumption is reduced, the technique for being catalyzed paper catalysis oxidation lignin using Co (salen) can reduce hydrogen peroxide
Consume, 20-30% of the hydrogen peroxide consumption less than tradition Co (salen) powder.
Specific embodiment
The present invention is described in further detail below by embodiment, but protection scope of the present invention be not limited to it is described
Content.
Embodiment 1：Co (salen) is catalyzed paper and applies in lignin oxidation, and concrete operations are as follows：
(1) preparation of double salicylaldehyde contracting triethylenediamine cobalt coordination compound Co (salen)
The synthesis of A, Salen
Take 2.5g ethylenediamines and 8.5mL salicylides are dissolved in 18mL methanol, 30min is stirred in ice-water bath, stand
15min, reduce pressure sucking filtration, is washed with lmL ether, and at 33 DEG C 6h is dried, and obtains 10.7g faint yellow solids, then with the anhydrous second of 160mL
Alcohol recrystallization, at 33 DEG C 18h is dried, and obtains 9.4g Huang light tone flat crystals, as Schiff's base salen, and yield is 88.0%, is melted
Point：125-125.5℃.
, Co (salen) synthesis
Take 1.3mmoL product Schiff's base salen obtained in the previous step to be dissolved in 15mL methanol, by resulting solution with
3mmoL slaine CoAc2•4H2O mixes, and flow back 1h, cools down, filters, 1h is vacuum dried at 50 DEG C, and gained red brown solid is
Co (salen) coordination compound, yield：97.75%, fusing point：More than 300 DEG C.
（2）Co (salen) is catalyzed the synthesis of paper
Catalysis paper is prepared according to papermaking process；Add 5.0g ceramic fibres, 0.4g catalyst Co (salen), plus deionization
After water, it is sufficiently mixed；Plus 0.1g cation diallyl dimethyl ammoniumchlorides (PDADMAC), it is sufficiently mixed；Plus 0.5g oxidations
Alumina gel, is sufficiently mixed；Plus 0.1g PAMAs (A-PAM), it is sufficiently mixed；Plus 0.5g paper pulp, plus deionized water,
The final w/v of total material concentration 0.5%, is sufficiently mixed；Paper-like is copied on standard sheet former；By wet paper in hydraulic press pressure
5 min are pushed, is then dried in 105 DEG C of baking ovens；350 DEG C of heat treatment 12h, obtain Co (salen)/ceramic fibre composite wood
Material catalysis paper.
(3) method that Co (salen) is catalyzed paper catalysis oxidation lignin
Paper, H are catalyzed in Co (salen)2O2Under conditions of presence, catalytic oxidation treatment is carried out to lignin；To lignin catalytic oxygen
Change when processing, water 20mL, lignin 0.5g, the temperature control of process at 20 DEG C, time 1h；During to lignin catalytic oxidation processes, also
Add catalyst Co (salen) catalysis paper, Co (salen) catalysis paper consumption 0.01g；During to lignin catalytic oxidation processes, also
Add oxidant H2O2, mass percent concentration is 30% H2O2Solution 0.3mL；Decomposition rate of lignin is higher than tradition Co
(salen) the 25% of powder catalytic effect；Hydrogen peroxide consumption is less than the 30% of tradition Co (salen) powder.
Embodiment 2：Co (salen) is catalyzed paper and applies in lignin oxidation, and concrete operations are as follows：
（1）The synthetic method of Co (salen) catalysis paper is with the step of embodiment 1（1）、（2）；
（2）The method that Co (salen) is catalyzed paper catalysis oxidation lignin
Paper, H are catalyzed in Co (salen)2O2Under conditions of presence, catalytic oxidation treatment is carried out to lignin；To lignin catalytic oxygen
Change when processing, water 40mL, lignin 0.7g, the temperature control of process at 50 DEG C, time 2h；During to lignin catalytic oxidation processes, also
Add catalyst Co (salen) catalysis paper, Co (salen) catalysis paper consumption 0.02g；During to lignin catalytic oxidation processes, also
Add oxidant H2O2, mass percent concentration is 30% H2O2Solution 0.5mL；Decomposition rate of lignin is higher than tradition Co
(salen) the 30% of powder catalytic effect；Hydrogen peroxide consumption is less than the 25% of tradition Co (salen) powder.
Embodiment 3：Co (salen) is catalyzed paper and applies in lignin oxidation, and concrete operations are as follows：
（3）The synthetic method of Co (salen) catalysis paper is with the step of embodiment 1（1）、（2）；
（4）The method that Co (salen) is catalyzed paper catalysis oxidation lignin
Paper, H are catalyzed in Co (salen)2O2Under conditions of presence, catalytic oxidation treatment is carried out to lignin；To lignin catalytic oxygen
Change when processing, water 50mL, lignin 1g, the temperature control of process at 80 DEG C, time 3h；During to lignin catalytic oxidation processes, also add
Catalyst Co (salen) catalysis paper, Co (salen) catalysis paper consumption 0.03g are entered；During to lignin catalytic oxidation processes, also add
Oxidant H is entered2O2, mass percent concentration is 30% H2O2Solution 0.7mL；Decomposition rate of lignin is higher than tradition Co (salen)
The 21% of powder catalytic effect；Hydrogen peroxide consumption is less than the 23% of tradition Co (salen) powder.
Claims (2)
1. application of a kind of Co (salen) catalysis paper in lignin oxidation, it is characterised in that：Paper and H are catalyzed in Co (salen)2O2
Under conditions of presence, catalysis oxidation lignin.
2. application of Co (salen) the catalysis paper according to claim 1 in lignin oxidation, it is characterised in that：To lignin
During catalytic oxidation treatment, 20～50mL water is added in per 0.5～1 g lignins, while addition Co (salen) catalysis paper 0.01～
0.03g、H2O2The mL of solution 0.3～0.7, after mixing at 20 DEG C～80 DEG C process 1h～3h；
H2O2Solution is aqueous solution that mass percent concentration is 30%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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) |
| CN106190216B (en) * | 2016-07-20 | 2017-12-22 | 昆明理工大学 | The technique that M (salen) is catalyzed 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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| JP2007126776A (en) * | 2005-11-02 | 2007-05-24 | Nisshin Kagaku Kenkyusho:Kk | Method for treatment of waste paper pulp and deinking assistant |
| CN101565909B (en) * | 2009-04-14 | 2011-12-07 | 昆明理工大学 | Little-chlorine and little-pollution bleaching process for paper pulp biomimetic pretreatment |
| CN102776796B (en) * | 2012-07-23 | 2014-08-06 | 昆明理工大学 | Technology for catalyzing and bleaching paper pulp with immobilized Schiff alkali metals |
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| TiO2-沸石复合纸板制备中助留剂的作用;陈万春等;《造纸化学品》;20060430;第18卷(第2期);全文 * |
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