CN102776796A - Technology for catalyzing and bleaching paper pulp with immobilized Schiff alkali metals - Google Patents
Technology for catalyzing and bleaching paper pulp with immobilized Schiff alkali metals Download PDFInfo
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- CN102776796A CN102776796A CN2012102541385A CN201210254138A CN102776796A CN 102776796 A CN102776796 A CN 102776796A CN 2012102541385 A CN2012102541385 A CN 2012102541385A CN 201210254138 A CN201210254138 A CN 201210254138A CN 102776796 A CN102776796 A CN 102776796A
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- 238000004061 bleaching Methods 0.000 title claims abstract description 40
- 238000005516 engineering process Methods 0.000 title claims abstract description 30
- 229920001131 Pulp (paper) Polymers 0.000 title claims abstract description 26
- 229910052783 alkali metal Inorganic materials 0.000 title abstract 3
- 150000001340 alkali metals Chemical class 0.000 title abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000004076 pulp bleaching Methods 0.000 claims abstract description 8
- 150000004965 peroxy acids Chemical class 0.000 claims abstract description 7
- 239000002262 Schiff base Substances 0.000 claims description 36
- 150000004753 Schiff bases Chemical class 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 230000003197 catalytic effect Effects 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 12
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 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 19
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 239000003446 ligand Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000002808 molecular sieve Substances 0.000 description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 241000370738 Chlorion Species 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 108090000790 Enzymes Proteins 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 108010054320 Lignin peroxidase Proteins 0.000 description 1
- 108010059896 Manganese peroxidase Proteins 0.000 description 1
- 101100006982 Mus musculus Ppcdc gene Proteins 0.000 description 1
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Paper (AREA)
Abstract
The invention relates to a technology for catalyzing and bleaching paper pulp with immobilized Schiff alkali metals, belonging to the technology for catalyzing and bleaching paper pulp. The method provided by the invention can ensure that paper pulp is catalyzed and bleached under a condition that immobilized Schiff alkali metals exist in a paper pulp bleaching treatment; and simultaneously peroxy acid and alcohol are added. The method provided by the invention is simple, is carried out easily, and is featured with remarkably effects; and the paper pulp bleaching effect is good.
Description
Technical field
The present invention relates to a kind of immobilized Schiff base metal catalytic bleaching pulp technology, belong to field of papermaking.
Background technology
Association with pulp bleaching is to remove the process that color improves whiteness.Conventional bleaching produces chlorinatedorganic, contaminated environment.Pulping and paper-making had been used chlorine bleach already as far as possible less.Effective degraded of association with pulp bleaching lignin and selectively removing are crucial technology.Therefore, exploitation effectively is still a challenge of association with pulp bleaching with bleaching agent optionally.Adopting the bio-bleaching of whiterot fungi and enzyme is a kind of selection.The reaction of some lignin peroxidases and manganese peroxidase enzymatic can be by non-enzyme compound catalysis, and these imitative enzyme systems have obtained paying attention to, can substitute the lignin degradation enzyme, because they are more economical, uses more easily; In this respect, Schiff base metal complexes is by broad research.Disclosed Schiff base metal complexes exists stability low in the bleaching of paper pulp in the prior art, and poor selectivity, reaction time are long, to the high shortcoming that requires of consersion unit.
Summary of the invention
Technical problem to be solved by this invention provides the technology of a kind of immobilized schiff bases (salen) metal catalytic bleached pulp, and this technology is the imitative enzyme bleaching technology of an improved paper pulp, and its technology is implemented easily, and is pollution-free, and bleaching effect is good.
It is following to solve the scheme that technical problem of the present invention adopts: in bleaching is handled, guarantee under the condition that immobilized Schiff base metal exists paper pulp to be bleached processing, be added into peroxy acid and alcohol simultaneously.
According to the invention in the association with pulp bleaching processing procedure; The consumption of immobilized Schiff base metal is 0.02～0.04% of a pulp quality; The peroxy acid consumption is 0.4～0.6% of a pulp quality, and the consumption of alcohol is the 40-60% of pulp quality, and bleaching is handled 100～140min under 60～80 ℃ of temperature.
Immobilized Schiff base metal according to the invention is a kind of among immobilized Cu-salen, immobilized Mn-salen, immobilized Co-salen, immobilized Fe-salen, immobilized Ni-salen, the immobilized Zn-salen.
Peroxy acid according to the invention is a kind of in Peracetic acid, peroxosulphuric, the peroxyformic acid.
Alcohol is a kind of in methyl alcohol, ethanol, the ethylene glycol among the present invention.
Immobilized Schiff base metal adopts the conventional method preparation among the present invention, as adopting the method in Institutes Of Technology Of Taiyuan's doctorate paper " structure of symmetry and asymmetric metal complex and catalytic performance research in the molecular sieve ".
Mention paper pulp among the present invention and be meant the paper pulp that adopts traditional handicraft or prior art for preparing, and this paper pulp is bleached.
The invention has the beneficial effects as follows:
(1) raw material is easy to get, and consumption is few, and process implementing is easy;
(2) the raising pulp brightness is obvious, adopts immobilized Schiff base metal catalytic pretreatment operation, can improve TCF (completely without chlorine) and float pulp brightness 20-30%ISO eventually;
(3) overall process adopts complete free from chloride bleaching technology, in bleaching process, need not to add alkaline reagent and toxic reagent, the pollution-free generation of bleaching process, and low for equipment requirements, need not logical oxygen press device.
(4) the immobilized stability and the concertedness that has improved catalyst of the catalyst in the application of the present invention improves the selectivity of reaction; The synergy of three types of chemical reagent has obviously improved the degree of bleaching of paper pulp.
The specific embodiment
Through embodiment the present invention is done further explain below, but protection domain of the present invention is not limited to said content.
Embodiment 1: the technology of immobilized Cu-salen catalytic bleaching pulp, and particular content is following:
(1) preparation of immobilized Cu-salen
1. schiff base ligand Salen's is synthetic
Get 2.5g ethylenediamine and 8.5mL salicylide and be dissolved in the 18mL methyl alcohol, in ice-water bath, stir 30min, leave standstill 15min after; Decompress filter is with the washing of 1mL ether, 33 ℃ of following vacuumizes; Get faint yellow solid, again with 160mL absolute ethyl alcohol recrystallization, 33 ℃ of following vacuumizes; Get the glassy yellow crystal, promptly get schiff base ligand salen;
2. immobilized Cu-salen's is synthetic
With 0.6389g CuAc
2H
2O is dissolved in the 400mL deionized water, adds 20g NaY molecular sieve then, at room temperature stirs 24 h, filters out solid, and it is inferior to give a baby a bath on the third day after its birth with deionized water, at 120 ℃ of dry 12h, obtains Cu/Y respectively at last.
Cu/Y and excessive schiff base ligand salen are mixed under nitrogen protection, and mixture is transferred to round-bottomed flask, vacuumizes, and sealing is heated to 150 ℃, keeps 24h.At last, products therefrom is used the acetone extracting, removes unreacted part, and the metal ion that does not cooperate among the molecular sieve NaY is washed with deionized water with the NaCl solion anticommuting of 0.1mol/L at last, up to there not being chlorion, promptly gets immobilized Cu-salen.
(2) technology of immobilized Cu-salen catalytic bleaching pulp is following:
In concentration is 5% paper pulp, add immobilized Cu-salen, CH
3COOOH and CH
3OH handles paper pulp, and the consumption of immobilized Cu-salen is 0.02% of a pulp quality, CH
3The COOOH consumption is 0.4% of a pulp quality, CH
3The consumption of OH is a pulp quality 40%, and bleaching is handled 100min under 80 ℃ of temperature; Float pulp brightness eventually through said method TCF and improve 25%ISO.
Embodiment 2: the technology of immobilized Mn-salen catalytic bleaching pulp, and particular content is following:
(1) preparation of immobilized Mn-salen
1. schiff base ligand Salen's is synthetic
Get 2.5g ethylenediamine and 8.5mL salicylide and be dissolved in the 18mL methyl alcohol, in ice-water bath, stir 30min, leave standstill 15min after; Decompress filter is with the washing of 1mL ether, 33 ℃ of following vacuumizes; Get faint yellow solid, again with 160mL absolute ethyl alcohol recrystallization, 33 ℃ of following vacuumizes; Get the glassy yellow crystal, promptly get schiff base ligand salen;
2. immobilized Mn-salen's is synthetic
With 0.6389g MnAc
34H
2O is dissolved in the 400mL deionized water, adds 20g NaY molecular sieve then, at room temperature stirs 24 h, filters out solid, and it is inferior to give a baby a bath on the third day after its birth with deionized water, at 120 ℃ of dry 12h, obtains Mn/Y respectively at last.
Mn/Y and excessive schiff base ligand salen are mixed under nitrogen protection, and mixture is transferred to round-bottomed flask, vacuumizes, and sealing is heated to 150 ℃, keeps 24h.At last, products therefrom is used the acetone extracting, removes unreacted part, and the metal ion that does not cooperate among the molecular sieve NaY is washed with deionized water with the NaCl solion anticommuting of 0.1mol/L at last, up to there not being chlorion, promptly gets immobilized Mn-salen.
(2) technology of immobilized Mn-salen catalytic bleaching pulp is following:
In concentration is 10% paper pulp, add immobilized Mn-salen, CH
3COOOH and CH
3OH handles paper pulp, and the consumption of immobilized Mn-salen is 0.03%, CH
3The COOOH consumption is 0.5% of a pulp quality, CH
3The OH consumption is 50% of a pulp quality, and bleaching is handled 140min under 60 ℃ of temperature; Float pulp brightness eventually through said method TCF and improve 30%ISO.
Embodiment 3: the technology of immobilized Co-salen catalytic bleaching pulp, and particular content is following:
(1) preparation of immobilized Co-salen
1. schiff base ligand Salen's is synthetic
Get 2.5g ethylenediamine and 8.5mL salicylide and be dissolved in the 18mL methyl alcohol, in ice-water bath, stir 30min, leave standstill 15min after; Decompress filter is with the washing of 1mL ether, 33 ℃ of following vacuumizes; Get faint yellow solid, again with 160mL absolute ethyl alcohol recrystallization, 33 ℃ of following vacuumizes; Get the glassy yellow crystal, promptly get schiff base ligand salen;
2. immobilized Co-salen's is synthetic
With 0.6389g CoAc
2H
2O is dissolved in the 400mL deionized water, adds 20g NaY molecular sieve then, at room temperature stirs 24 h, filters out solid, and it is inferior to give a baby a bath on the third day after its birth with deionized water, at 120 ℃ of dry 12h, obtains Co/Y respectively at last.
Co/Y and excessive schiff base ligand salen are mixed under nitrogen protection, and mixture is transferred to round-bottomed flask, vacuumizes, and sealing is heated to 150 ℃, keeps 24h.At last, products therefrom is used the acetone extracting, removes unreacted part, and the metal ion that does not cooperate among the molecular sieve NaY is washed with deionized water with the NaCl solion anticommuting of 0.1mol/L at last, up to there not being chlorion, promptly gets immobilized Co-salen.
(2) technology of immobilized Co-salen catalytic bleaching pulp is following:
In concentration is 7% paper pulp; Add immobilized Co-salen, peroxosulphuric and ethanol paper pulp is handled, the consumption of immobilized Co-salen is 0.04%, and the peroxosulphuric consumption is 0.6% of a pulp quality; Amount of ethanol is 60% of a pulp quality, and bleaching is handled 120min under 70 ℃ of temperature; Float pulp brightness eventually through said method TCF and improve 20%ISO.
Embodiment 4: the technology of immobilized Fe-salen catalytic bleaching pulp, and particular content is following:
(1) preparation of immobilized Fe-salen
1. schiff base ligand Salen's is synthetic
Get 2.5g ethylenediamine and 8.5mL salicylide and be dissolved in the 18mL methyl alcohol, in ice-water bath, stir 30min, leave standstill 15min after; Decompress filter is with the washing of 1mL ether, 33 ℃ of following vacuumizes; Get faint yellow solid, again with 160mL absolute ethyl alcohol recrystallization, 33 ℃ of following vacuumizes; Get the glassy yellow crystal, promptly get schiff base ligand salen;
2. immobilized Fe-salen's is synthetic
With 0.6389g FeAc
2Be dissolved in the 400mL deionized water, add 20g NaY molecular sieve then, at room temperature stir 24 h, filter out solid, it is inferior to give a baby a bath on the third day after its birth with deionized water, at 120 ℃ of dry 12h, obtains Fe/Y respectively at last.
Fe/Y and excessive schiff base ligand salen are mixed under nitrogen protection, and mixture is transferred to round-bottomed flask, vacuumizes, and sealing is heated to 150 ℃, keeps 24h.At last, products therefrom is used the acetone extracting, removes unreacted part, and the metal ion that does not cooperate among the molecular sieve NaY is washed with deionized water with the NaCl solion anticommuting of 0.1mol/L at last, up to there not being chlorion, promptly gets immobilized Fe-salen.
(2) technology of immobilized Fe-salen catalytic bleaching pulp is following:
In concentration is 8% paper pulp; Adding immobilized Fe-salen, peroxyformic acid and ethylene glycol handles paper pulp; The consumption of immobilized Fe-salen is 0.02%; The peroxyformic acid consumption is 0.6% of a pulp quality, and the ethylene glycol consumption is 55% of a pulp quality, and bleaching is handled 130min under 65 ℃ of temperature; Float pulp brightness eventually through said method TCF and improve 23%ISO.
Embodiment 5: the technology of immobilized Ni-salen catalytic bleaching pulp, and particular content is following:
(1) preparation of immobilized Ni-salen
1. schiff base ligand Salen's is synthetic
Get 2.5g ethylenediamine and 8.5mL salicylide and be dissolved in the 18mL methyl alcohol, in ice-water bath, stir 30min, leave standstill 15min after; Decompress filter is with the washing of 1mL ether, 33 ℃ of following vacuumizes; Get faint yellow solid, again with 160mL absolute ethyl alcohol recrystallization, 33 ℃ of following vacuumizes; Get the glassy yellow crystal, promptly get schiff base ligand salen;
2. immobilized Ni-salen's is synthetic
With 0.6389g NiAc
2Be dissolved in the 400mL deionized water, add 20g NaY molecular sieve then, at room temperature stir 24 h, filter out solid, it is inferior to give a baby a bath on the third day after its birth with deionized water, at 120 ℃ of dry 12h, obtains Ni/Y respectively at last.
Ni/Y and excessive schiff base ligand salen are mixed under nitrogen protection, and mixture is transferred to round-bottomed flask, vacuumizes, and sealing is heated to 150 ℃, keeps 24h.At last, products therefrom is used the acetone extracting, removes unreacted part, and the metal ion that does not cooperate among the molecular sieve NaY is washed with deionized water with the NaCl solion anticommuting of 0.1mol/L at last, up to there not being chlorion, promptly gets immobilized Ni-salen.
(2) technology of immobilized Ni-salen catalytic bleaching pulp is following:
In concentration is 9% paper pulp; Add immobilized Ni-salen, Peracetic acid and methyl alcohol paper pulp is handled, the consumption of immobilized Fe-salen is 0.03%, and the Peracetic acid consumption is 0.5% of a pulp quality; Methanol usage is 45% of a pulp quality, and bleaching is handled 120min under 70 ℃ of temperature; Float pulp brightness eventually through said method TCF and improve 24%ISO.
Embodiment 6: the technology of immobilized Zn-salen catalytic bleaching pulp, and particular content is following:
(1) preparation of immobilized Zn-salen
1. schiff base ligand Salen's is synthetic
Get 2.5g ethylenediamine and 8.5mL salicylide and be dissolved in the 18mL methyl alcohol, in ice-water bath, stir 30min, leave standstill 15min after; Decompress filter is with the washing of 1mL ether, 33 ℃ of following vacuumizes; Get faint yellow solid, again with 160mL absolute ethyl alcohol recrystallization, 33 ℃ of following vacuumizes; Get the glassy yellow crystal, promptly get schiff base ligand salen;
2. immobilized Zn-salen's is synthetic
With 0.6389g ZnAc
2Be dissolved in the 400mL deionized water, add 20g NaY molecular sieve then, at room temperature stir 24 h, filter out solid, it is inferior to give a baby a bath on the third day after its birth with deionized water, at 120 ℃ of dry 12h, obtains Zn/Y respectively at last.
Zn/Y and excessive schiff base ligand salen are mixed under nitrogen protection, and mixture is transferred to round-bottomed flask, vacuumizes, and sealing is heated to 150 ℃, keeps 24h.At last, products therefrom is used the acetone extracting, removes unreacted part, and the metal ion that does not cooperate among the molecular sieve NaY is washed with deionized water with the NaCl solion anticommuting of 0.1mol/L at last, up to there not being chlorion, promptly gets immobilized Zn-salen.
(2) technology of immobilized Zn-salen catalytic bleaching pulp is following:
In concentration is 6% paper pulp; Add immobilized Zn-salen, Peracetic acid and ethanol paper pulp is handled, the consumption of immobilized Zn-salen is 0.04%, and the Peracetic acid consumption is 0.6% of a pulp quality; Methanol usage is 50% of a pulp quality, and bleaching is handled 110min under 75 ℃ of temperature; Float pulp brightness eventually through said method TCF and improve 25%ISO.
Claims (5)
1. the technology of immobilized Schiff base metal catalytic bleaching pulp is characterized in that: in the association with pulp bleaching processing procedure, guarantee under the condition of immobilized Schiff base metal existence paper pulp to be bleached processing, add peroxy acid and alcohol simultaneously.
2. press the technology of the described immobilized Schiff base metal catalytic bleaching pulp of claim 1; It is characterized in that: in the association with pulp bleaching processing procedure; The consumption of immobilized Schiff base metal is 0.02～0.04% of a pulp quality; The peroxy acid consumption is 0.4～0.6% of a pulp quality, and the consumption of alcohol is the 40-60% of pulp quality, and bleaching is handled 100～140min under 60～80 ℃ of temperature.
3. by the technology of claim 1 or 2 described immobilized Schiff base metal catalytic bleaching pulps, it is characterized in that: immobilized Schiff base metal is a kind of among immobilized Cu-salen, immobilized Mn-salen, immobilized Co-salen, immobilized Fe-salen, immobilized Ni-salen, the immobilized Zn-salen.
4. by the technology of claim 1 or 2 described immobilized Schiff base metal catalytic bleaching pulps, it is characterized in that: peroxy acid is a kind of in Peracetic acid, peroxosulphuric, the peroxyformic acid.
5. by the technology of the described immobilized Schiff base metal catalytic bleaching pulp of claim 3, it is characterized in that: a kind of in methyl alcohol, ethanol, the ethylene glycol of alcohol.
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Cited By (5)
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| CN104762847A (en) * | 2015-03-25 | 2015-07-08 | 昆明理工大学 | A pulp delignification process catalyzed by immobilized M([H4]salen) |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104762847A (en) * | 2015-03-25 | 2015-07-08 | 昆明理工大学 | A pulp delignification process catalyzed by immobilized M([H4]salen) |
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| CN106040298A (en) * | 2015-08-24 | 2016-10-26 | 湖北航天化学技术研究所 | Curing catalyst for composite solid propellant, and preparation method thereof |
| CN106040298B (en) * | 2015-08-24 | 2018-10-09 | 湖北航天化学技术研究所 | A kind of curing catalysts and preparation method thereof for composite solidpropellant |
| CN106012638A (en) * | 2016-05-23 | 2016-10-12 | 昆明理工大学 | Process for bleaching membrane-shaped M ([H4] salen) catalytic paper pulp |
| CN106012638B (en) * | 2016-05-23 | 2017-11-10 | 昆明理工大学 | Membranaceous M ([H4] salen) it is catalyzed the technique of association with pulp bleaching |
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