CN1100176C - Fully chlorine-free bleaching method for broad-leaved wood sulphate pulp - Google Patents
Fully chlorine-free bleaching method for broad-leaved wood sulphate pulp Download PDFInfo
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- CN1100176C CN1100176C CN00114066A CN00114066A CN1100176C CN 1100176 C CN1100176 C CN 1100176C CN 00114066 A CN00114066 A CN 00114066A CN 00114066 A CN00114066 A CN 00114066A CN 1100176 C CN1100176 C CN 1100176C
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Abstract
The present invention relates to a fully chlorine-free bleaching method for broad-leaved wood sulphate pulp by using a biological enzyme, which has the key point of paper pulp reduction pretreatment. The present invention has the conditions that hypoamidino sulfonic acid, hydrosulfite and dithionite are used as a reduction agent; the added quantity of the reduction agent is 0.2 to 4 wt% of oven dry pulp by weight; the temperature of a reduction reaction is from 40 DEG C to 70 DEG C; the time of the reduction reaction is from 1 hour to 2 hours. Laccase oxidation has the conditions that in the presence of a medium and a nonionic surface active agent, laccase with 100 to 10000 international enzyme activity unit /Kg oven-dry pulp is added, and oxygen is introduced; the temperature of the reaction is from 35 DEG C to 65 DEG C; a pH value is from 5 to 7; the time of the reaction is from 1 hour to 4 hours. On the premise of not changing the performance of paper pulp, with the method, the whiteness of the paper pulp is obviously increased, namely that the whiteness of the paper pulp can be up to over 84% of ISO. The present invention realizes a fully chlorine-free technology and satisfies the requirement of pollution-free environmental protection.
Description
The present invention relates to a kind of dioxde pulp bleaching process, particularly utilize the biology enzyme (fully chlorine-free bleaching method of the broad-leaved wood sulphate pulp of laccase.
The waste water that traditional dioxde pulp bleaching process produces contains a large amount of hypertoxic chlorophenol compounds, forces people to make improvements.In recent years, utilize chlorine dioxide to replace the method for bleaching of the element-free chlorine of chlorine to obtain significant progress.But this method still can produce organochlorine compound in waste water, along with the more and more concern of people to environment, and the technology of various chlorine-free bleachings, as oxygen delignification, hydrogen peroxide floats, and ozone floats etc. and to obtain certain development.But the equipment investment that these methods have is expensive, and the poor selectivity that has has, fiber is have destruction.
Since Wei Kaili in 1986 since (Viikari) at first propose biology enzyme introduced association with pulp bleaching, handled research to utilizing laccase to carry out the delignified pulp lignin, existing in the world many reports.European patent EP-A-408,803 disclose a kind of method of utilizing laccase and chloride compound bleached pulp, and it can reduce the consumption of chemicals, but also contains a spot of organochlorine compound in the waste water that is produced.German patent DE-A-3,636,208 disclose a kind of can delignification or the method for bleached pulp with the lignin degradation enzyme; European patent EP-A-447 in addition, 673 also disclose and utilize laccase and oxidation-reduction potential in the presence of the chemical substance of 0.2～0.5V, have good delignification.
Recently, U.S. Pat 5,691,193 disclose a kind of biology enzyme and hydrogen peroxide fully chlorine-free bleaching method of utilizing, enzyme is handled and is comprised laccase/amboceptor (ABTS or other laccase substrate) in this patent, or rely on chelating agents such as manganese peroxidase/manganese ion/lactic acid or oxalic acid and add a spot of hydrogen peroxide, remove metal ion through chelation treatment then, and alkaline hydrogen peroxide floats.
The objective of the invention is to utilize biotechnology to provide a kind of both pulp brightness good, can keep the fully chlorine-free bleaching method of the constant pollution-free broad-leaved wood sulphate pulp of pulp property again.
The objective of the invention is to realize by following measure:
A kind of fully chlorine-free bleaching method of broad-leaved wood sulphate pulp, this method comprise the following steps: the processing of (1) enzyme; (2) chelation treatment; (3) hydrogen peroxide bleaching; It is characterized in that: comprise the following steps successively and process conditions:
(1) reduction preliminary treatment:
Starch dense 2～12% (weight), broad-leaved wood sulphate pulp adds the reductant by oven dry stock weight 0.2～4% (weight), the disodium edta of 0.5% (weight) and 0.5% (weight) soda ash, under 40～70 ℃, reacted 1～2 hour, clean then;
Reductant is: dithionite, deuto-amidine sulfonic acid or bisulfites;
When paper pulp kappa number reduces to 10 when following, can be without the reduction preliminary treatment;
(2) laccase oxidation:
Through reduction preliminary treatment or unprocessed Kappa number is that broad-leaved wood sulphate pulp 10 below is an adding consumption 100～10 under the amboceptor of 0.2～4% (weight) and non-ionic surface active agent that consumption is 0.1～2% (weight) situation about existing at consumption, the laccase of 000 international enzyme units/kg oven dry stock alive and the oxygen of feeding 0.3～2mPa, reaction temperature is 35～65 ℃, PH is 5～7, and the reaction time is 1～4 hour;
In the above-mentioned technology:
Amboceptor refers to: contain the aromatic compound of N-OH group,
Non-ionic surface active agent refers to: tween, sapn, polyalkylene glycol alkyl ester or polyethylene glycol lauryl ether,
Laccase refers to: from fungi (whiterot fungi) liquid fermentation or solid fermentation liquid,
Each international enzyme unit alive is the amount of the required enzyme of oxidation 1 μ g substrate (ABTS);
(3) chelation treatment:
Through the paper pulp of laccase oxidation, chelation treatment is removed metal ion under neutrallty condition;
(4) hydrogen peroxide bleaching:
Hydrogen peroxide bleaching under the alkali condition.
Before main points of the present invention are laccase oxidation paper pulp, reduce and handle and under the condition that surfactant and amboceptor exist, carry out laccase treatment.Why deposit and reduce processing before the laccase oxidation paper pulp, be to utilize reductant that some functional groups of residual lignin in the paper pulp are reduced into ortho states, improve laccase and lignin reaction performance, because the reaction of laccase and lignin is a free radical proceed, more reduction group has more reaction site, may make lignin be in higher energy state, help the reaction of lignin and chemical reagent and stripping.
The present invention compared with prior art has following outstanding advantage:
1, pulp brightness significantly improves, and through check, the pulp brightness of embodiment 1-6 is all more than 84%ISO.
2, the property retention of paper pulp is constant.
3, this law is pollution-free and technology is simple to operation, has using value, has solved the problem of environmental pollution in paper mill up hill and dale, and social benefit is big.
Embodiment 1: the Eucalyptus kraft bleaching
Step 1: reduction preliminary treatment
The Eucalyptus sulfate pulp, Kappa number 17.5 is starched under dense 2% (weight) condition, adding is by the sodium dithionite of oven dry stock 0.2% (weight), the disodium edta of 0.5% (weight) and 0.5% (weight) soda ash reacted 2 hours down at 40 ℃, cleaned then;
Step 2: laccase oxidation processes
Through reducing pretreated paper pulp is the amboceptor of 0.2% (weight) at consumption: NHA N-acetyl group-hydroxyanilines and consumption are in the presence of the surfactant Tween 80 of 0.2% (weight), the laccase that adds the whiterot fungi solid fermentation liquid of consumption 500 international enzymes units/kg oven dry stock alive, and oxidation starched dense 10% (weight) that transfers to, feed 0.3mPa oxygen, the laccase reactions condition is 50 ℃ of temperature, PH5.0 reacted 4 hours;
Step 3: chelation treatment
Paper pulp after the laccase oxidation processes, it is dense to 10% (weight) that slurry is regulated in washing back, is 1% chelating agent EDTA reaction 0.5 hour with consumption under 6.5,50 ℃ of conditions of PH, to remove metal ion;
Step 4: hydrogen peroxide bleaching
Spend deionised water, it is dense to 10% to regulate slurry again, and under 90 ℃, with hydroperoxidation 4 hours, sodium hydroxide concentration 2.0% in the reaction system, and hydrogen peroxide consumption 2.0% also adds 0.5% magnesium sulfate and 0.2%EDTA in addition.
Embodiment 2: the poplar kraft bleaching
Step 1: reduction preliminary treatment
Under slurry dense 1 0% (weight) condition, add by oven dry stock 1% (weight) deuto-amidine sulfonic acid, the disodium edta of 0.5% (weight) and 0.5% (weight) soda ash reacted 1 hour down at 70 ℃, cleaned then;
Step 2: laccase oxidation processes
Through reducing pretreated paper pulp is the amboceptor of 4% (weight) at consumption: NHB N-benzoyl-hydroxyanilines and consumption are in the presence of the surfactant sapn of 1% (weight), add consumption 10, the laccase of the whiterot fungi solid fermentation liquid of 000 international enzyme units/kg oven dry stock alive, and oxidation starched dense 10% (weight) that transfers to, feed 0.3mPa oxygen, the laccase reactions condition is 65 ℃ of temperature, and PH6.5 reacted 1 hour;
Step 3: chelation treatment
Paper pulp after the laccase oxidation processes, it is dense to 10% (weight) that slurry is regulated in washing back, at PH7, is 1% chelating agent EDTA reaction 0.5 hour with consumption under 50 ℃ of conditions, to remove metal ion;
Step 4: hydrogen peroxide bleaching
Spend deionised water, it is dense to 10% to regulate slurry again, and under 90 ℃, with hydroperoxidation 4 hours, sodium hydroxide concentration 2.0% in the reaction system, and hydrogen peroxide consumption 2.0% also adds 0.5% magnesium sulfate and 0.2%EDTA in addition.
Embodiment 3: the Eucalyptus kraft bleaching
Step 1: reduction preliminary treatment
Under slurry dense 5% (weight) condition, add sodium hydrogensulfite by oven dry stock 4% (weight), the disodium edta of 0.5% (weight) and 0.5% (weight) soda ash reacted 2 hours down at 50 ℃, cleaned then;
Step 2: laccase oxidation processes
Through reducing pretreated paper pulp is the amboceptor of 2% (weight) at consumption: N-E propionyl-hydroxyanilines and consumption are in the presence of the surfactant Tween 80 of 2% (weight), add consumption 2, the laccase of the whiterot fungi solid fermentation liquid of 000 international enzyme units/kg oven dry stock alive, and oxidation starched dense 10% (weight) that transfers to, feed 0.3mPa oxygen, the laccase reactions condition is 45 ℃ of temperature, and PH5.5 reacted 2 hours;
Step 3: chelation treatment
Paper pulp after the laccase oxidation processes, it is dense to 10% (weight) that slurry is regulated in washing back, at PH7, is 1% chelating agent EDTA reaction 0.5 hour with consumption under 70 ℃ of conditions, to remove metal ion;
Step 4: hydrogen peroxide bleaching
Spend deionised water, it is dense to 10% to regulate slurry again, and under 90 ℃, with hydroperoxidation 4 hours, sodium hydroxide concentration 2.0% in the reaction system, and hydrogen peroxide consumption 2.0% also adds 0.5% magnesium sulfate and 0.2%EDTA in addition.
Embodiment 4: the poplar kraft bleaching
Step 1: laccase oxidation processes
The poplar sulfate pulp, Kappa number 17.2, starch Kappa number less than 10 through Extended Delignification sulfate pulp or oxygen delignification hydrochlorate, at consumption is the amboceptor of 1% (weight): NHA N-acetyl group-hydroxyanilines and consumption are in the presence of the surfactant Tween 80 of 1% (weight), add consumption 5, the laccase of the whiterot fungi solid fermentation liquid of 000 international enzyme units/kg oven dry stock alive, and oxidation starched dense 10% (weight) that transfers to, feed 0.3mPa oxygen, the laccase reactions condition is 50 ℃ of temperature, PH6 reacted 1 hour;
Step 2: chelation treatment
Paper pulp after the laccase oxidation processes, it is dense to 12% (weight) that slurry is regulated in washing back, at PH5, is 1% chelating agent EDTA reaction 1 hour with consumption under 60 ℃ of conditions, to remove metal ion;
Step 3: hydrogen peroxide bleaching
Spend deionised water, it is dense to 10% to regulate slurry again, and under 90 ℃, with hydroperoxidation 4 hours, sodium hydroxide concentration 2.0% in the reaction system, and hydrogen peroxide consumption 2.0% also adds 0.5% magnesium sulfate and 0.2%EDTA in addition.
Embodiment 5: the Eucalyptus kraft bleaching
Step 1: reduction preliminary treatment
Under slurry dense 10% (weight) condition, add sodium dithionite by oven dry stock 0.5% (weight), the disodium edta of 0.5% (weight) and 0.5% (weight) soda ash reacted 1 hour down at 65 ℃, cleaned then;
Step 2: laccase oxidation processes
Through reducing pretreated paper pulp is the amboceptor of 1% (weight): VIO at consumption, hippuric acid and consumption are that the polyglycols Arrcostab of 0.5% (weight) exists down, add consumption 2, the laccase of the whiterot fungi liquid fermentation liquid of 000 international enzyme units/kg oven dry stock alive, and oxidation starched dense 10% (weight) that transfers to, and feeding 2mPa oxygen, the laccase reactions condition is 35 ℃ of temperature, PH7 reacted 4 hours;
Step 3: chelation treatment
Paper pulp after the laccase oxidation processes, it is dense to 10% (weight) that slurry is regulated in washing back, at PH6, is 1% chelating agent EDTA reaction 1 hour with consumption under 55 ℃ of conditions, to remove metal ion;
Step 4: hydrogen peroxide bleaching
Spend deionised water, it is dense to 10% to regulate slurry again, and under 90 ℃, with hydroperoxidation 4 hours, sodium hydroxide concentration 2.0% in the reaction system, and hydrogen peroxide consumption 2.0% also adds 0.5% magnesium sulfate and 0.2%EDTA in addition.
Embodiment 6: the poplar kraft bleaching
Step 1: reduction preliminary treatment
Under slurry dense 4% (weight) condition, add sodium dithionite by oven dry stock 0.5% (weight), the disodium edta of 0.5% (weight) and 0.5% (weight) soda ash reacted 2 hours down at 40 ℃, cleaned then;
Step 2: laccase oxidation processes
Through reducing pretreated paper pulp is the amboceptor of 4% (weight) at consumption: HBT 3-carboxylic benzo-aza ring and consumption are in the presence of the polyethylene glycol lauryl ether of 1% (weight), add consumption 5, the laccase of the whiterot fungi liquid fermentation liquid of 000 international enzyme units/kg oven dry stock alive, and oxidation starched dense 10% (weight) that transfers to, feed 1mPa oxygen, the laccase reactions condition is 65 ℃ of temperature, and PH5.0 reacted 2 hours;
Step 3: chelation treatment
Paper pulp after the laccase oxidation processes, it is dense to 12% (weight) that slurry is regulated in washing back, at PH6.5, is 1% chelating agent EDTA reaction 1 hour with consumption under 60 ℃ of conditions, to remove metal ion;
Step 4: hydrogen peroxide bleaching
Spend deionised water, it is dense to 10% to regulate slurry again, and under 90 ℃, with hydroperoxidation 4 hours, sodium hydroxide concentration 2.0% in the reaction system, and hydrogen peroxide consumption 2.0% also adds 0.5% magnesium sulfate and 0.2%EDTA in addition.
Claims (4)
1, a kind of fully chlorine-free bleaching method of broad-leaved wood sulphate pulp, this method comprise the following steps the processing of (1) enzyme, (2) chelation treatment, (3) hydrogen peroxide bleaching, it is characterized in that the condition of laccase oxidation is:
(a) add the laccase that consumption is 100～10,000 an international enzyme units/kg oven dry stock alive under the situation that amboceptor and non-ionic surface active agent exist, and feeding pressure is the oxygen of 0.3～2mPa;
Amboceptor is the aromatic compound that contains the N-OH group, and its consumption is 0.2～4% (weight)
Non-ionic surface active agent is tween, sapn, polyalkylene glycol alkyl ester or polyethylene glycol lauryl ether, and its consumption is 0.1～2% (weight)
(b) the laccase oxidizing reaction temperature is 35～65 ℃;
(c) pH value is 5～7;
(d) the laccase oxidation time is 1～4 hour.
2, the fully chlorine-free bleaching method of a kind of broad-leaved wood sulphate pulp according to claim 1 is characterized in that before the laccase oxidation at first paper pulp is reduced preliminary treatment, and the pretreated condition of reducing is:
(a) add soda ash by the disodium edta and 0.5% (weight) of the reductant, 0.5% (weight) of oven dry stock weight 0.2～4% (weight);
(b) reduction reaction temperature is 40～70 ℃;
(c) the reduction reaction time is 1～2 hour;
(d) reductant is: deuto-amidine sulfonic acid, bisulfites or dithionite.
3, the fully chlorine-free bleaching method of a kind of broad-leaved wood sulphate pulp according to claim 1 and 2, it is characterized in that broad-leaved wood sulphate pulp is meant the conventional sulfate pulp of leaf wood or Extended Delignification sulfate pulp or oxygen delignification sulfate pulp, its slurry is dense to be 2～12% (weight).
4, the fully chlorine-free bleaching method of a kind of broad-leaved wood sulphate pulp according to claim 1 and 2 is characterized in that laccase is from fungi (whiterot fungi) liquid fermentation liquid or solid fermentation liquid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN00114066A CN1100176C (en) | 2000-02-03 | 2000-02-03 | Fully chlorine-free bleaching method for broad-leaved wood sulphate pulp |
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| Application Number | Priority Date | Filing Date | Title |
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| CN00114066A CN1100176C (en) | 2000-02-03 | 2000-02-03 | Fully chlorine-free bleaching method for broad-leaved wood sulphate pulp |
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| CN1260419A CN1260419A (en) | 2000-07-19 |
| CN1100176C true CN1100176C (en) | 2003-01-29 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2189683B1 (en) * | 2001-12-17 | 2005-02-01 | Consejo Superior De Investigaciones Cientificas | NEW PROCEDURE FOR CHLORINE-FREE ENZYMATIC WHITENING OF HIGH-QUALITY PASTES OBTAINED FROM HERBAL OR ARBUSTIVE PLANTS. |
| CN102345241B (en) * | 2011-09-26 | 2013-08-07 | 山东轻工业学院 | Bleaching process of coniferous wood and deciduous wood mixed chemical pulp stewed by sulfate process |
| CN102877346B (en) * | 2012-10-23 | 2014-03-12 | 山东轻工业学院 | Totally chlorine-free bleaching process using coniferous and broadleaf mixed sulfate chemical pulp |
| CN102926261B (en) * | 2012-10-23 | 2014-05-07 | 山东轻工业学院 | Total-chlorine-free bleaching process of coniferous wood and broadleaf wood mixed sodium hydroxide anthraquinone chemical pulp |
| CN103334331B (en) * | 2013-07-17 | 2014-07-30 | 齐鲁工业大学 | TCE bleaching technology for sulfate pulp of growing poplar by biological chemical method |
| CN103362009B (en) * | 2013-07-17 | 2014-08-06 | 齐鲁工业大学 | Rapid-growth poplar sodium hydroxide anthraquinone pulp biochemical method TCF bleaching process |
| CN104611964B (en) * | 2015-01-15 | 2016-04-20 | 陕西科技大学 | A kind of pulping process of Acacia sulphite process high whiteness semi-chemical pulp |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068161A (en) * | 1991-05-17 | 1993-01-20 | 汉斯-彼得·考尔 | Method for delignifying and bleaching lignocellulose-containing material and treating wastewater by using synergistic laccase |
| CN1158647A (en) * | 1994-10-20 | 1997-09-03 | 诺沃挪第克公司 | Bleaching process comprising use of a phenol oxidizing enzyme, a hydrogen peroxide source and an enhancing agent |
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2000
- 2000-02-03 CN CN00114066A patent/CN1100176C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068161A (en) * | 1991-05-17 | 1993-01-20 | 汉斯-彼得·考尔 | Method for delignifying and bleaching lignocellulose-containing material and treating wastewater by using synergistic laccase |
| CN1158647A (en) * | 1994-10-20 | 1997-09-03 | 诺沃挪第克公司 | Bleaching process comprising use of a phenol oxidizing enzyme, a hydrogen peroxide source and an enhancing agent |
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| CN1260419A (en) | 2000-07-19 |
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