CN106012638A - Process for bleaching membrane-shaped M ([H4] salen) catalytic paper pulp - Google Patents
Process for bleaching membrane-shaped M ([H4] salen) catalytic paper pulp Download PDFInfo
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- CN106012638A CN106012638A CN201610342734.7A CN201610342734A CN106012638A CN 106012638 A CN106012638 A CN 106012638A CN 201610342734 A CN201610342734 A CN 201610342734A CN 106012638 A CN106012638 A CN 106012638A
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- China
- Prior art keywords
- salen
- pulp
- membranaceous
- paper pulp
- bleaching
- 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.)
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- 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 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 42
- 229920001131 Pulp (paper) Polymers 0.000 title claims abstract description 23
- 230000008569 process Effects 0.000 title claims abstract description 14
- 238000004061 bleaching Methods 0.000 title claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 title abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 238000004076 pulp bleaching Methods 0.000 claims description 16
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000036284 oxygen consumption Effects 0.000 description 11
- 239000010949 copper Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- 238000004886 process control Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002262 Schiff base Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 108010025899 gelatin film Proteins 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 238000000935 solvent evaporation Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 108010059892 Cellulase Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 235000011158 Prunus mume Nutrition 0.000 description 1
- 244000018795 Prunus mume Species 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/1026—Other features in bleaching processes
- D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/147—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a process for bleaching membrane-shaped M ([H4] salen) catalytic paper pulp. In the presence of membrane-shaped M ([H4] salen) (M equal to Cu, Co, Fe, Mn and Zn), treatment is carried out on the pulp. The process adopts a pollution-free pulp catalytic delignification technology, is less in raw material dose, is free of strict requirement on environmental condition, is capable of obviously improving whiteness and various properties of the paper pulp, and is capable of obviously reducing reagent consumption.
Description
Technical field
The present invention relates to a kind of membranaceous M ([H4] salen) and catalysis association with pulp bleaching technique, be one improve association with pulp bleaching
Technology.
Background technology
In recent years due to the requirement of environmental conservation, association with pulp bleaching industry has shifted towards and utilizes total chlorine free bleaching.For improving paper pulp
The efficiency of delignification, can use the method such as cellulase treatment, chemical catalysis, and the research of current this respect is the most deep.They are with wooden
Some composition effect in element, is formed with the condition of beneficially delignified pulp lignin, improves the bleachability of paper pulp.M ([H2]
Salen) catalysis delignification has been reported.By reduction M ([H2] salen), obtain M ([H4] salen) (M=Cu, Co, Fe,
Mn, Zn), make C=N key become C-N key, improve catalyst activity；By immobilized, improve stablizing of catalyst further
Property and activity, can increase the reactivity of paper pulp lignin, strengthen the reaction efficiency of oxygen etc. and paper pulp lignin, thus improve paper pulp wood
The degradability of element, improves bleaching efficiency.But general immobilized still suffer from the segregative problem of catalyst, film forming can be passed through
Mode by M ([H4] salen) firmly appendix is at matrix surface. avoid catalyst at the separation problem of the process of use.
Summary of the invention
The technical problem to be solved is to provide a kind of membranaceous M ([H4] salen) and catalysis association with pulp bleaching technique,
This technique is the dioxde pulp bleaching process of a kind of improvement, and its Technology is easily implemented, pollution-free, improves the effect of association with pulp bleaching
Good, improve association with pulp bleaching properties obvious.
The scheme that the technical problem of the solution present invention is used is as follows: at membranaceous M ([H4] salen) and O2The condition existed
Under, paper pulp is processed.
Described membranaceous M ([H4] salen) it is Cu ([H4]salen)、Co([H4]salen)、Fe([H4]salen)、Mn
([H4] salen) or Zn ([H4]salen)。
In pulp treatment process, membranaceous M ([H4] salen) and consumption is pulp quality 0.02～0.08%, O2Pressure
Power is 0.1～0.3MPa, and bleaching processes 60～120min at 60～90 DEG C.
M ([H in the present invention4] salen) prepared by existing method, the method referring for example in following document:
(1) Chen, P., Fan, B.B., Song, M.G., Jin, C., Ma, J.H., Li, R.F., 2006.
Zeolite-encapsulated Ru(III) tetrahydro-Schiff base complex: an efficient
heterogeneous catalyst for the hydrogenation of benzene under mild
conditions. Catal. Commun. 7, 969-973.
(2) Jacob, C.R., Varkey, S.P., Ratnasamy, P., 1998. Selective oxidation
over copper and manganese salens encapsulated in zeolites. Micropor. Mesopor.
Mat. 22, 465-474.
(3) Jin, C., Fan, W.B., Jia, Y.J., Fan, B.B., Ma, J.H., Li, R.F., 2006.
Encapsulation of transition metal tetrahydro-Schiff base complexes in zeolite
Y and their catalytic properties for the oxidation of cycloalkanes. J. Mol.
Catal. A: Chem. 249, 23-30.
2, membranaceous M ([H4] salen) preparation of catalyst: prepared by list of references, such as Zou Xiao prunus mume (sieb.) sieb.et zucc., Chen Qisheng, Ke little Xue, thunder
Qin, Zhao Ziming, Liu Xilong, Chen Yan, China hero, Wang Chongtai. PW11Cu/TiO2The preparation of film photocatalyst and visible light catalytic
Performance. Chinese Journal of Inorganic Chemistry, 2015,31(10), the method in 2037-2043；
Under agitation, by 3g M ([H4] salen) be dissolved in the mixed solution of 100mL water and ethanol (water: ethanol volume ratio is 1:
20), then it is added dropwise over sulfuric acid solution, makes the pH value of reaction system be maintained at 2～3；Continuing stirring makes solvent evaporation obtain M
([H4] salen) colloidal sol, place, be aged formation gel after 20 h；Dip-coating method is used to be lifted on slide by this gel
Film, puts into Muffle furnace roasting 3 h, obtains membranaceous M ([H4] salen) catalyst.
The invention has the beneficial effects as follows:
(1) process implementing is easy；
(2) association with pulp bleaching is improved, than general immobilized M ([H4] salen) catalysis pulp bleaching efficiency, paper pulp can be improved white
Degree 20-30%；
(3) reduce reagent consumption, use membranaceous M ([H4] salen) catalysis paper pulp bleaching process, oxygen consumption 20-30% can be reduced
Above.
Detailed description of the invention
Below by embodiment, the present invention is described in further detail, but protection scope of the present invention is not limited to described
Content.
Embodiment 1: membranaceous M ([H4] salen) and catalysis association with pulp bleaching technique, concrete operations are as follows:
(1) Cu ([H4] salen) and preparation
Take 2.5g ethylenediamine and 8.5mL salicylide is dissolved in 18mL methanol, frozen water stirs 30min, after standing 15min,
Reduce pressure sucking filtration with G3 vierics, wash with 1mL ether, at 33 DEG C, be vacuum dried to obtain light yellow crystal, then by the anhydrous second of 160ml
Alcohol recrystallization, is vacuum dried to obtain yellow crystals at 33 DEG C, obtains schiff base ligand salen；
6.32 Schiff's bases are dissolved in 920mL methanol, add 0.42 sodium borohydride (NaBH4), stir 2 hours under room temperature, subtract
Solvent is removed in pressure distillation, and crude product with water is washed, then with ethyl alcohol recrystallization, obtains [H4] Salen part white crystal；
Weigh 2.32g part [H4] salen be dissolved in equipped with 100mL heat methanol flask in, weigh 2.16g Schweinfurt green dissolve
After in 14mL warm water, it is transferred into rapidly above-mentioned methanol solution, is heated to reflux in 1 hour backward flask dripping 2mol/L's
NaOH solution is until there being precipitation to produce, and cooling, with the filtration of G3 funnel, the product obtained is vacuum dried at 50 DEG C, obtains Cu
([H4] salen) coordination compound；
Under agitation, by 3g Cu ([H4] salen) it is dissolved in the mixed solution of 100mL water and ethanol (water: ethanol volume ratio is
1:20), then it is added dropwise over sulfuric acid solution, makes the pH value of reaction system be maintained at 2～3；Continuing stirring makes solvent evaporation obtain M
([H4] salen) colloidal sol, place, be aged formation gel after 20 h；Dip-coating method is used to be lifted on slide by this gel
Film, puts into Muffle furnace roasting 3 h, obtains membranaceous Cu ([H4] salen) catalyst.
(2) membranaceous Cu ([H4] salen) and catalysis association with pulp bleaching technique
At membranaceous Cu ([H4] salen) and exist under conditions of, paper pulp is processed；During to pulp processing, membranaceous M ([H4]
Salen) consumption is the 0.02% of pulp quality, and the temperature of process controls at 60 DEG C, time 60min, during to pulp processing, also
With the addition of O2, O2Pressure be 0.1MPa；This technique is used to improve pulp brightness 20% than general solid-supported catalyst；Oxygen consumption
30%, use this technique can reduce oxygen consumption 20% than general solid-supported catalyst.
Embodiment 2:
(1) membranaceous Co ([H4] salen) and preparation process with reference to the method in embodiment 1 step (1)；
(2) at membranaceous M ([H4] salen) under conditions of (M=Co) exist, paper pulp is processed；During to pulp processing, film
Shape M ([H4] salen) and consumption is pulp quality 0.04%, the temperature of process controls at 75 DEG C, time 90min.To paper pulp
During process, also added O2, O2Pressure be 0.2MPa；This technique is used to improve pulp brightness than general solid-supported catalyst
25%；Oxygen consumption 35%, uses this technique can reduce oxygen consumption 25% than general solid-supported catalyst.
Embodiment 3
(1) membranaceous Fe ([H4] salen) and preparation process with reference to the method in embodiment 1 step (1)；
(2) at membranaceous M ([H4] salen) under conditions of (M=Fe) exist, paper pulp is processed；During to pulp processing, film
Shape M ([H4] salen) and consumption is pulp quality 0.08%, the temperature of process controls at 90 DEG C, time 120min；To paper pulp
During process, also added O2, O2Pressure be 0.3MPa.This technique is used to improve pulp brightness than general solid-supported catalyst
30%；Oxygen consumption 40%, uses this technique can reduce oxygen consumption 30% than general solid-supported catalyst.
Embodiment 4
(1) membranaceous Mn ([H4] salen) and preparation process with reference to the method in embodiment 1 step (1)；
(2) at membranaceous M ([H4] salen) under conditions of (M=Mn) exist, paper pulp is processed；During to pulp processing, film
Shape M ([H4] salen) and consumption is pulp quality 0.05%, the temperature of process controls at 80 DEG C, time 70min；To paper pulp
During process, also added O2, O2Pressure be 0.2MPa.This technique is used to improve pulp brightness than general solid-supported catalyst
30%；Oxygen consumption 40%, uses this technique can reduce oxygen consumption 25% than general solid-supported catalyst.
Embodiment 5
(1) membranaceous Zn ([H4] salen) and preparation process with reference to the method in embodiment 1 step (1)；
(2) at membranaceous M ([H4] salen) under conditions of (M=Zn) exist, paper pulp is processed；During to pulp processing, film
Shape M ([H4] salen) and consumption is pulp quality 0.07%, the temperature of process controls at 70 DEG C, time 100min；To paper pulp
During process, also added O2, O2Pressure be 0.1MPa.This technique is used to improve pulp brightness than general solid-supported catalyst
30%；Oxygen consumption 40%, uses this technique can reduce oxygen consumption 30% than general solid-supported catalyst.
Claims (3)
1. a membranaceous M ([H4] salen) and catalysis association with pulp bleaching technique, it is characterised in that: at membranaceous M ([H4] salen) deposit
Under the conditions, paper pulp is processed, the most membranaceous M ([H4] salen) and in M=Cu, Co, Fe, Mn or Zn.
2. membranaceous the M ([H as described in claim 14] salen) and catalysis association with pulp bleaching technique, it is characterised in that: paper pulp is entered
Row also added O when processing2。
Membranaceous M ([H the most according to claim 24] salen) and catalysis association with pulp bleaching technique, it is characterised in that: at paper pulp
In processing procedure, membranaceous M ([H4] salen) and consumption is pulp quality 0.02～0.08%, O2Pressure be 0.1～
0.3MPa, bleaching processes 60～120min at 60～90 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610342734.7A CN106012638B (en) | 2016-05-23 | 2016-05-23 | Membranaceous M ([H4] salen) it is catalyzed the technique of association with pulp bleaching |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610342734.7A CN106012638B (en) | 2016-05-23 | 2016-05-23 | Membranaceous M ([H4] salen) it is catalyzed the technique of association with pulp bleaching |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106012638A true CN106012638A (en) | 2016-10-12 |
| CN106012638B CN106012638B (en) | 2017-11-10 |
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|---|---|---|---|
| CN201610342734.7A Expired - Fee Related CN106012638B (en) | 2016-05-23 | 2016-05-23 | Membranaceous M ([H4] salen) it is catalyzed the technique of association with pulp bleaching |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN105503649A (en) * | 2016-01-08 | 2016-04-20 | 淮海工学院 | Polyols containing quaternary ammonium cations and Salen or Salophen functional groups and preparation method thereof |
-
2016
- 2016-05-23 CN CN201610342734.7A patent/CN106012638B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN105503649A (en) * | 2016-01-08 | 2016-04-20 | 淮海工学院 | Polyols containing quaternary ammonium cations and Salen or Salophen functional groups and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张娜: "固载化金属salen催化漂白桉木浆研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 邹晓梅、陈启胜等: "PW11Cu/TiO2膜光催化剂的制备及可见光催化性能", 《无机化学学报》 * |
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