CN104788687A - Process for catalyzing and oxidizing lignin by using Salen-porphyrin complexes - Google Patents
Process for catalyzing and oxidizing lignin by using Salen-porphyrin complexes Download PDFInfo
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- 229920005610 lignin Polymers 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 41
- 230000001590 oxidative effect Effects 0.000 title abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims description 40
- 230000003647 oxidation Effects 0.000 claims description 33
- 238000007254 oxidation reaction Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 27
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 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 description 21
- 238000000354 decomposition reaction Methods 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 11
- 229960001701 chloroform Drugs 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 102000004190 Enzymes Human genes 0.000 description 8
- 108090000790 Enzymes Proteins 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003480 eluent Substances 0.000 description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000004886 process control Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- -1 porphyrin metal complex Chemical class 0.000 description 3
- 150000004032 porphyrins Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CLFRCXCBWIQVRN-UHFFFAOYSA-N 2,5-dihydroxybenzaldehyde Chemical compound OC1=CC=C(O)C(C=O)=C1 CLFRCXCBWIQVRN-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HFVIYAZBVIGNAN-UHFFFAOYSA-N 1,1-dibromodecane Chemical compound CCCCCCCCCC(Br)Br HFVIYAZBVIGNAN-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 244000297179 Syringa vulgaris Species 0.000 description 1
- 235000004338 Syringa vulgaris Nutrition 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
The invention discloses a process for catalyzing and oxidizing lignin by using Salen-porphyrin complexes and belongs to the lignin catalyzing and oxidizing technology. The method catalyzes and oxidizes the lignin under the condition of existence of the Salen-porphyrin complexes and H2O2. The method adopts the pollution-free catalyzing and oxidizing technology, is less in raw material amount, has no strict requirements on environmental conditions, significantly improves the lignin and degrades various properties, and can significantly reduce drug consumption.
Description
Technical field
The present invention relates to a kind of technique of Salen-metalloporphyrin complex catalyzed oxidation lignin, is the technology of the catalyzed oxidation lignin that is improved.
Background technology
In recent years due to the shortage of resource and the raising to environmental protection requirement, the exploitation of eco-friendly efficient catalytic lignin oxidizing process is more and more subject to common concern.Efficient highly active catalytic oxylignin should have good reaction preference and efficiency.Therefore, the research of efficient high activated catalyst is a key issue in lignin oxidation field.
It is limited that research shows that biological enzyme improves lignin oxidation effectiveness, biological enzyme preparation difficulty, responsive to envrionment conditions.Therefore, have developed there is imitative enzyme (analogue enztme) 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.The imitative enzyme compound that can be applicable to xylogen degradation has Metalloporphyrins and non-porphyrin metal complex.The research of metal metalloporphyrin complex shows, Metalloporphyrins has very high selective catalysis activity as the mimetic enzyme catalyst of oxylignin, but its synthesis is more difficult.The non-porphyrin metal complex salen compounds being easy to synthesize, coordination structure and metalloporphyrin are similar have various structures, synthetic route simply, low cost, be easy to prepare, the metal ion of coordination is easy to change and catalytic efficiency advantages of higher, and catalyzed oxidation lignin has good effect.
Nineteen ninety, Kazuhiro Maruyama reports the salen-porphyrin binuclear compound (two catalytic active center title complex) as metalloenzyme active centre model.The two centered complex of salen-porphyrin has the advantage of salen and porphyrin simultaneously: the catalytic selectivity that the easy synthesis of salen, high-level efficiency and porphyrin are superior, its reason is that salen complex structure and metalloporphyrin complex structure organically combine, not only increase catalytic active center, and influence each other between active centre, improve catalytic effect and catalytic selectivity, catalytic effect and catalytic selectivity are higher than the salen title complex of single centre title complex and metalloporphyrin complex.For the advantage in conjunction with salen and this two classes title complex of porphyrin, with reference to related documents, synthesize Salen-metalloporphyrin complex, be applied to lignin catalytic oxidation.Adopt Salen-metalloporphyrin complex catalyzed oxidation lignin, the reactive behavior of lignin can be increased, strengthen the reaction efficiency of hydrogen peroxide etc. and lignin, thus improve efficiency and the selectivity of xylogen degradation.But Salen-metalloporphyrin complex 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 Salen-metalloporphyrin complex catalyzed oxidation lignin, this technique is a kind of technique of catalyzed oxidation lignin of improvement, its Technology is easily implemented, pollution-free, the degradation property improving lignin is effective, improves lignin degradation properties obvious.
Solve the scheme that technical problem of the present invention adopts as follows: at Salen-metalloporphyrin complex, 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 Salen-metalloporphyrin complex 1 ~ 3mg, 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 is the solution of mass percent concentration 30%.
Salen-metalloporphyrin complex is that such as reference literature obtains: Zhao little Jing, Ruan Wenjuan by the obtained material of existing method, Zhu Zhiang, golden dawn, Fan Sheng. the synthesis of porphyrin-salen compound and fluorescent property research. organic chemistry, 26(8): 1087-1092.
The invention has the beneficial effects as follows:
(1) Salen complex structure and metalloporphyrin complex structure organically combine, not only increase catalytic active center, and influence each other between active centre, improve catalytic effect and catalytic selectivity, catalytic effect and catalytic selectivity are higher than the salen title complex of single centre title complex and metalloporphyrin complex;
(2) consumption is few, and process implementing is easy;
(3) improve lignin degradation properties, adopt the technique of Salen-metalloporphyrin complex catalyzed oxidation lignin, can decomposition rate of lignin be improved, the salen title complex of decomposition rate of lignin higher than single centre title complex and the 20-30% of metalloporphyrin complex;
(4) reduce reagent consumption, adopt the technique of Salen-metalloporphyrin complex catalyzed oxidation lignin, hydrogen oxide consumption can be reduced over, the salen title complex of hydrogen peroxide consumption lower than single centre title complex and the 20-30% of metalloporphyrin complex.
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 technique of embodiment 1:Salen-metalloporphyrin complex catalyzed oxidation lignin, concrete operations are as follows:
(1) preparation of Salen-metalloporphyrin complex
5,10,15-triphenyl-20-p-hydroxybenzene porphyrin (HPTPP; 5,10,15-triphenyl-20-mesohydroxylphenylporphyrin) synthesis:
By 23g p-Hydroxybenzaldehyde and 57ml dissolution of benzaldehyde in the propionic acid of 2000ml, be placed in the three-necked bottle of 3000ml, mechanical stirring reflux, temperature remains on 133 DEG C, reflux after 20 minutes, 52ml is newly steamed pyrroles to be dissolved in 150ml propionic acid and slowly to drip to reaction system, temperature drops to 126 DEG C and continues reaction 30 minutes, reaction mixture sat is after 12 hours, the mode of rotary evaporation in vacuo is utilized to remove the propionic acid of 1/2nd, add isopyknic ethanol after slightly cold, place suction filtration after 24 hours; Precipitation absolute ethanol washing, dries and obtains atropurpureus solids crude product; Neutral alumina dry method crosses post, and trichloromethane does eluent; First lilac band is by product tetraphenylporphyrin (TPP), and the second band is compound 5,10,15-triphenyl-20-p-hydroxybenzene porphyrin (HPTPP); Dried HPTPP is crossed again neutral alumina column to purify, select the mixed solvent of trichloromethane and sherwood oil 1:1 to do eluent, obtain sterling.
synthesis:
9ml salicylic aldehyde, 8g O-Phenylene Diamine, 10g 2,5-Dihydroxy benzaldehyde are dissolved in about 571ml trichloromethane, in stirred at ambient temperature, stopped reaction after 20 hours.Have yellow mercury oxide to generate, solution is orange.After filtration, reaction soln concentrates, and neutral aluminum oxide column chromatography is purified, and trichloromethane does eluent; First band is symmetrical salen-1, and the second band is asymmetric salen-2(is required salen-OH), the 3rd band is symmetrical dihydroxyl salen-3; In yellow solid after product is concentrated, silica gel column chromatography is purified, and obtains sterling.
the synthesis of brominated alkanes:
By 2.5mmol(0.83g) salen-OH part and 25mmol(7.5g) dibromo-decane is dissolved in 200ml and newly steams in acetone, adds 37.5mmol(5.175g) K
2cO
3, quick backflow, lucifuge is reacted after 5 hours and is stopped, removing acetone, chloroform extraction, and repeatedly washs with distilled water, extraction collected organic layer; Filter after utilizing dried over anhydrous sodium carbonate, reaction mixture neutral aluminum oxide column chromatography is purified, and trichloromethane does eluent, collects yellow band, then does eluent with methylene dichloride and repeatedly purify, and products obtained therefrom is glassy yellow thick solid.
210
part (HPSC
10
) synthesis:
Anhydrous potassium carbonate is placed in 20ml acetone rapid stirring to pasty state, adds HPTPP, stirring at normal temperature is after 10 minutes, with HPTPP:salen (CH
2)
10the ratio of Br=1:1.5 adds salen (CH
2)
10br, under normal temperature, lucifuge stirs stopped reaction after 17 hours, removing acetone, and add trichloromethane and dissolve, inorganics is repeatedly gone out in washing, and organic over anhydrous dried over sodium sulfate is filtered.Thick product silica gel column chromatography is purified, and trichloromethane makes eluent.
210
(MPSC
10
) synthesis (M, metal=Cu, Co, Fe, Mn, Zn):
By product HPSC obtained in the previous step
10be dissolved in 20ml trichloromethane, return stirring, after 10 minutes, adds acetate
(metal in acetate compound
m is Cu, Co, Fe, Mn, Zn)saturated methanol solution 10ml, return stirring stopped after 5 hours, and distilled water wash is repeatedly, removing inorganics, collected organic layer, filters with after anhydrous sodium sulfate drying, silica gel column chromatography is purified, and trichloromethane makes eluent, finally obtains Salen-metalloporphyrin complex catalyzer.
(2) technique of Salen-metalloporphyrin complex catalyzed oxidation lignin
Salen-metalloporphyrin complex (
mPTPP-(CH 2 ) 10 -salenM(MPSC 10 ), M is Cu), H
2o
2condition under, 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 adds catalyst S alen-metalloporphyrin complex, Salen-metalloporphyrin complex consumption 1mg, during to lignin catalytic oxide treatment, also adds oxygenant H
2o
2, mass percent concentration is the H of 30%
2o
2solution 0.3mL.Decomposition rate of lignin is 70%, adopt this technique, decomposition rate of lignin is higher than the salen title complex of single centre title complex and 20% of metalloporphyrin complex, and hydrogen peroxide consumes 40%, adopt this technique, hydrogen peroxide consumption is lower than the salen title complex of single centre title complex and 20% of metalloporphyrin complex.
The technique of embodiment 2:Salen-metalloporphyrin complex catalyzed oxidation lignin, concrete operations are as follows:
(1) preparation of the preparation of Salen-metalloporphyrin complex is with reference to embodiment 1(1);
(2) technique of Salen-metalloporphyrin complex catalyzed oxidation lignin
Salen-metalloporphyrin complex ((
mPTPP-(CH 2 ) 10 -salenM(MPSC 10 ), M is Co)), H
2o
2condition under, 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 S alen-metalloporphyrin complex, Salen-metalloporphyrin complex consumption 2mg; 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 75%, adopts this technique, and decomposition rate of lignin is higher than the salen title complex of single centre title complex and 25% of metalloporphyrin complex; Hydrogen peroxide consumes 45%, and adopt this technique, hydrogen peroxide consumption is lower than the salen title complex of single centre title complex and 25% of metalloporphyrin complex.
The technique of embodiment 3:Salen-metalloporphyrin complex catalyzed oxidation lignin, concrete operations are as follows:
(1) preparation of the preparation of Salen-metalloporphyrin complex is with reference to embodiment 1(1);
(2) technique of Salen-metalloporphyrin complex catalyzed oxidation lignin
Salen-metalloporphyrin complex ((
mPTPP-(CH 2 ) 10 -salenM(MPSC 10 ), M is Fe)), H
2o
2condition under, 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 S alen-metalloporphyrin complex, Salen-metalloporphyrin complex consumption 3mg, during to lignin catalytic oxide treatment, also adds oxygenant H
2o
2, mass percent concentration is the H of 30%
2o
2solution 0.7mL; Decomposition rate of lignin is 80%, adopts this technique, and decomposition rate of lignin is higher than the salen title complex of single centre title complex and 25% of metalloporphyrin complex; Hydrogen peroxide consumes 50%, and adopt this technique, hydrogen peroxide consumption is lower than the salen title complex of single centre title complex and 30% of metalloporphyrin complex.
The technique of embodiment 4:Salen-metalloporphyrin complex catalyzed oxidation lignin, concrete operations are as follows:
(1) preparation of the preparation of Salen-metalloporphyrin complex is with reference to embodiment 1(1);
(2) technique of Salen-metalloporphyrin complex catalyzed oxidation lignin
Salen-metalloporphyrin complex ((
mPTPP-(CH 2 ) 10 -salenM(MPSC 10 ), M is Mn)), H
2o
2condition under, catalytic oxidation treatment is carried out to lignin; During to lignin catalytic oxide treatment, water 30mL, lignin 0.6g, the temperature of process controls at 40 DEG C, time 1.5h; During to lignin catalytic oxide treatment, also add catalyst S alen-metalloporphyrin complex, Salen-metalloporphyrin complex consumption 1.5mg, during to lignin catalytic oxide treatment, also adds oxygenant H
2o
2, mass percent concentration is the H of 30%
2o
2solution 0.4mL; Decomposition rate of lignin is 76%, adopts this technique, and decomposition rate of lignin is higher than the salen title complex of single centre title complex and 24% of metalloporphyrin complex; Hydrogen peroxide consumes 45%, and adopt this technique, hydrogen peroxide consumption is lower than the salen title complex of single centre title complex and 24% of metalloporphyrin complex.
The technique of embodiment 5:Salen-metalloporphyrin complex catalyzed oxidation lignin, concrete operations are as follows:
(1) preparation of the preparation of Salen-metalloporphyrin complex is with reference to embodiment 1(1);
(2) technique of Salen-metalloporphyrin complex catalyzed oxidation lignin
Salen-metalloporphyrin complex ((
mPTPP-(CH 2 ) 10 -salenM(MPSC 10 ), M is Zn)), H
2o
2condition under, catalytic oxidation treatment is carried out to lignin; During to lignin catalytic oxide treatment, water 45mL, lignin 0.8g, the temperature of process controls at 70 DEG C, time 2.5h; During to lignin catalytic oxide treatment, also add catalyst S alen-metalloporphyrin complex, Salen-metalloporphyrin complex consumption 2.5mg, during to lignin catalytic oxide treatment, also adds oxygenant H
2o
2, mass percent concentration is the H of 30%
2o
2solution 0.6mL; Decomposition rate of lignin is 78%, adopts this technique, and decomposition rate of lignin is higher than the salen title complex of single centre title complex and 22% of metalloporphyrin complex; Hydrogen peroxide consumes 48%, and adopt this technique, hydrogen peroxide consumption is lower than the salen title complex of single centre title complex and 26% of metalloporphyrin complex.
Claims (3)
1. a technique for Salen-metalloporphyrin complex catalyzed oxidation lignin, is characterized in that: at Salen-metalloporphyrin complex and H
2o
2under existent condition, catalytic oxidation treatment is carried out to lignin.
2. the technique of Salen-metalloporphyrin complex catalyzed oxidation lignin according to claim 1, is characterized in that: during to lignin catalytic oxide treatment, adds 20 ~ 50mL water, add Salen-metalloporphyrin complex 1 ~ 3mg, H simultaneously in every 0.5 ~ 1 g lignin
2o
2solution 0.3 ~ 0.7 mL, processes 1h ~ 3h after mixing at 20 DEG C ~ 80 DEG C.
3. the technique of Salen-metalloporphyrin complex catalyzed oxidation lignin according to claim 2, is characterized in that: H
2o
2solution is the solution of mass percent concentration 30%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237588A (en) * | 2015-10-19 | 2016-01-13 | 昆明理工大学 | Method for promoting degradation of degradation-resistant lignin by uniting activator and double center coordination complex |
| CN106008189A (en) * | 2016-05-23 | 2016-10-12 | 昆明理工大学 | Method for catalytically converting veratryl alcohol into veratraldehyde |
| CN109824497A (en) * | 2019-03-06 | 2019-05-31 | 华南理工大学 | A kind of method that microwave cooperating catalysis of metalloporphyrin oxidative degradation alkali lignin prepares single benzene ring compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101109160A (en) * | 2007-08-10 | 2008-01-23 | 昆明理工大学 | Novel non-chlorine bleaching technique for bamboo pulp |
| CN102776796A (en) * | 2012-07-23 | 2012-11-14 | 昆明理工大学 | Technology for catalyzing and bleaching paper pulp with immobilized Schiff alkali metals |
-
2015
- 2015-03-25 CN CN201510130811.8A patent/CN104788687A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101109160A (en) * | 2007-08-10 | 2008-01-23 | 昆明理工大学 | Novel non-chlorine bleaching technique for bamboo pulp |
| CN102776796A (en) * | 2012-07-23 | 2012-11-14 | 昆明理工大学 | Technology for catalyzing and bleaching paper pulp with immobilized Schiff alkali metals |
Non-Patent Citations (1)
| Title |
|---|
| 柳明星 等: "Salen-卟啉配合物催化氧化DBDO木素模型物", 《纸和造纸》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105237588A (en) * | 2015-10-19 | 2016-01-13 | 昆明理工大学 | Method for promoting degradation of degradation-resistant lignin by uniting activator and double center coordination complex |
| CN106008189A (en) * | 2016-05-23 | 2016-10-12 | 昆明理工大学 | Method for catalytically converting veratryl alcohol into veratraldehyde |
| CN109824497A (en) * | 2019-03-06 | 2019-05-31 | 华南理工大学 | A kind of method that microwave cooperating catalysis of metalloporphyrin oxidative degradation alkali lignin prepares single benzene ring compound |
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