CN101109160A - Novel non-chlorine bleaching technique for bamboo pulp - Google Patents
Novel non-chlorine bleaching technique for bamboo pulp Download PDFInfo
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- CN101109160A CN101109160A CNA2007100661038A CN200710066103A CN101109160A CN 101109160 A CN101109160 A CN 101109160A CN A2007100661038 A CNA2007100661038 A CN A2007100661038A CN 200710066103 A CN200710066103 A CN 200710066103A CN 101109160 A CN101109160 A CN 101109160A
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- bleaching
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- pulp
- bamboo pulp
- salen
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- 235000017166 Bambusa arundinacea Nutrition 0.000 title claims abstract description 32
- 235000017491 Bambusa tulda Nutrition 0.000 title claims abstract description 32
- 241001330002 Bambuseae Species 0.000 title claims abstract description 32
- 235000015334 Phyllostachys viridis Nutrition 0.000 title claims abstract description 32
- 239000011425 bamboo Substances 0.000 title claims abstract description 32
- 238000004061 bleaching Methods 0.000 title claims abstract description 32
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000000460 chlorine Substances 0.000 title claims abstract description 16
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 54
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 41
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 238000011282 treatment Methods 0.000 claims abstract description 24
- 229920001131 Pulp (paper) Polymers 0.000 claims abstract description 17
- 238000004076 pulp bleaching Methods 0.000 claims abstract description 12
- 239000002262 Schiff base Substances 0.000 claims abstract description 10
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 10
- 150000004965 peroxy acids Chemical class 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 108090000790 Enzymes Proteins 0.000 claims description 25
- 102000004190 Enzymes Human genes 0.000 claims description 25
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 24
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 22
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 20
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 20
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 10
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000007844 bleaching agent Substances 0.000 claims description 7
- 238000009897 hydrogen peroxide bleaching Methods 0.000 claims description 7
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- 230000009920 chelation Effects 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000002787 reinforcement Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- -1 organic acid salt Chemical class 0.000 abstract description 4
- 238000002203 pretreatment Methods 0.000 abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 1
- 239000011664 nicotinic acid Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 238000003911 water pollution Methods 0.000 abstract 1
- 229940088598 enzyme Drugs 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000002171 ethylene diamines Chemical class 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 231100000167 toxic agent Toxicity 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- KKAJSJJFBSOMGS-UHFFFAOYSA-N 3,6-diamino-10-methylacridinium chloride Chemical compound [Cl-].C1=C(N)C=C2[N+](C)=C(C=C(N)C=C3)C3=CC2=C1 KKAJSJJFBSOMGS-UHFFFAOYSA-N 0.000 description 1
- 108010029541 Laccase Proteins 0.000 description 1
- 108010054320 Lignin peroxidase Proteins 0.000 description 1
- 108010059896 Manganese peroxidase Proteins 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical class O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940059442 hemicellulase Drugs 0.000 description 1
- 108010002430 hemicellulase Proteins 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 108010062085 ligninase Proteins 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001221 xylan Polymers 0.000 description 1
- 150000004823 xylans Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical class O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 description 1
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Abstract
A novel totally chlorine-free bamboo-pulp bleaching process is provided. The invention relates to a novel totally chlorine free (TCF) bamboo-pulp bleaching process, is a new bionic bleaching technology for paper pulp. The invention essentially comprises the following procedures: (1) Synthesizing enzyme-imitated metal salen, using Schiff base salen to react with metallic organic acid salt to synthesize metal salen; (2) Pre-treatment bleaching bamboo pulp, carrying out bleaching pre-treatment on the oxygen delignification sulfate bamboo pulp with metal salen, NaOH, H2O2 and O2 existing; (3) Subsequent TCF bleaching, carrying out three bleaching treatments, namely, alkaline treating enhanced by hydrogen peroxide, bleaching by peroxy acid and bleaching by hydrogen peroxide the bamboo pulp pre-treated by enzyme-imitated metal salen. For the invention, the source is wide, the metal salen is easy to synthesize, the yield rate is high, the cost is low, the consumption is very low; the metal salen is easy to store, has no demanding requirement on the environment, can obviously improve the whiteness of paper pulp, reduce the load of waste water pollution in bleaching, and saves the use of bleaching chemicals.
Description
Technical field
The present invention relates to a kind of bamboo pulp completely without chlorine (TCF) bleaching new technology, is a bionical bleaching technology of novel paper pulp.
Background technology
Because requirement on environmental protection and development of biology, biology enzyme as the catalyst of a kind of high efficiency, high selectivity, are used extensive day by day in association with pulp bleaching industry.Research is at present comparatively goed deep into, is used wider biology enzyme, mainly contains hemicellulase (xylan enzyme, poly-sweet dew enzyme) and ligninase (lignin peroxidase, manganese peroxidase and laccase) two big classes.Some composition effect in they and the paper pulp forms delignification or helps the situation of delignification, and improves the bleachability of paper pulp or improve the whiteness of paper pulp.
Yet natural biology enzyme source is limited, the preparation difficulty, to the environmental condition sensitivity, these shortcomings have all restricted its development and utilization.Therefore, extract the chemical nature of native enzyme, set up its chemical simulation model, development and use have with native enzyme functional similarity even more superior imitative enzyme just becomes one of research focus of contemporary chemistry and imitative enzyme sciemtifec and technical sphere.Imitative enzyme is exactly to have nonprotein molecule or the molecular aggregate that similar active structure to biology enzyme is formed, and it has the advantage of biological enzyme and chemical catalysis, is one of effective way that realizes the green bleaching of paper pulp target.
At present, the imitative enzyme system that is applied to delignified pulp lignin and bleaching has following several: 1. metalloporphyrin complex comprises ferriporphyrin, manganoporphyrin; 2. non-porphyrin metal complex comprises metal phthalocyanine, GIF system, schiff bases, copper-amine complex, PROCESS FOR PRODUCTION OF BINUCLEAR, flavine, methylenum careuleum class etc.Wherein metalloporphyrin complex synthetic method is numerous and diverse, and cost is higher, has limited its practical application in industry.But not the porphyrin metal complex relative cost is cheap, and especially the GIF system need not be synthesized, and is easy and simple to handle, in recent years existing comparatively deep research both at home and abroad.But the GIF system is in xylogen degradation, and is also comparatively serious to cellulosic degraded, influenced the paper strength of paper pulp, and in addition, the consumption of toxicant pyridine is also bigger in the system, and these defectives make it be faced with certain difficulty in commercial Application.
Summary of the invention
Technical problem to be solved by this invention provides a kind of bamboo pulp total chlorine free bleaching new technology, and its raw material sources are wide, and synthetic metal salen is easy, yield is higher, and is with low cost, and consumption is few, be easy to store, environmental condition is not had harsh requirement, it is obvious to improve the every performance of paper pulp.
Solve the scheme that technical problem of the present invention adopts and mainly comprise following steps: 1. synthetic imitative enzyme metal salen, with schiff bases salen and metal organic acid reactant salt, synthesize metal salen; 2. to bamboo pulp bleaching preliminary treatment, at metal salen, NaOH, H
2O
2And O
2Under the condition that exists, oxygen desulfating bamboo pulp is bleached preliminary treatment; 3. follow-up total chlorine free bleaching is handled via the follow-up tri-stage bleaching that alkali treatment section, peroxy acid bleach section and the hydrogen peroxide bleaching section of hydrogen peroxide reinforcement are formed the imitative pretreated bamboo pulp of enzyme of metal salen again.
During to bamboo pulp bleaching preliminary treatment, the weight percent concentration of bamboo pulp is 4%～6%, and the percentage that each raw material accounts for bamboo pulp weight is, the NaOH consumption is 2.4%～3.0%, H
2O
2Consumption is 0.8%～1.0%, metal salen consumption is 0.024%～0.03%, O
2Pressure be 0.16MPa～0.2MPa, pretreated temperature is controlled at 70 ℃～90 ℃, time 3h～5h.To bamboo pulp bleaching preliminary treatment the time, also can add pyridine, the pyridine consumption with metal salen mol ratio be 0.8～1: 1.
The optimum process condition of follow-up total chlorine free bleaching of the present invention is:
1. the alkali treatment section strengthened of hydrogen peroxide, sodium hydroxide concentration 1.6%～2.0%, hydrogen peroxide consumption 0.4%～0.6%, pulp density 8%～12% during processing, 75 ℃～85 ℃ of temperature, 1.5 hours～2.0 hours time;
2. peroxy acid bleach section, chelation treatment magnesium sulfate consumption 0.08%～0.10%, diethylene triamine pentacetic acid (DTPA) consumption 0.4%～0.6%, pulp density 4%～6% during processing, 60 ℃～70 ℃ of temperature, 0.5 hour～1.0 hours time; Paper pulp adds Peracetic acid and bleaches through washing, Peracetic acid consumption 2.6%～3.0%, and pulp density 8%～12% during processing, 60 ℃～70 ℃ of temperature, 1.5 hours～2.0 hours time;
3. hydrogen peroxide bleaching section, sodium hydroxide concentration 1.6%～2.0%, magnesium sulfate consumption 0.08%～0.10%, sodium metasilicate consumption 1.3%～1.5%, diethylene triamine pentacetic acid (DTPA) consumption 0.64%～0.96%, hydrogen peroxide consumption 2.1%～2.5%, pulp density 8%～12% during processing, 80 ℃～90 ℃ of temperature, 2.5 hours～3.0 hours time.
The invention has the beneficial effects as follows:
(1) raw material is easy to get, and the method maturation of synthetic metal salen, easy, and yield is higher;
(2) with low cost, consumption is few, and imitative enzyme pretreatment system cost of material of the present invention is low, is easy to get, and consumption is few, therefore can reduce the processing cost of bamboo pulp greatly, and under identical whiteness required, cost can reduce about 30%;
(3) improve the every performance of paper pulp, adopt imitative enzyme pretreatment process, little to cellulosic degradation, floating paper pulp becomes paper tensile index 6.47%, tear index 7.20%, burst index 2.47% eventually to improve TCF.Tensile index, tear index and burst index are three key indexs of general paper physical property;
(4) the raising pulp brightness is obvious, adopts imitative enzyme pretreatment process, can improve TCF and float pulp brightness 5.3%SBD eventually;
(5) reduce the bleaching effluent pollutional load, adopt imitative enzyme pretreatment process, can reduce bleaching effluent pollutional load 10.2%～28.8%;
(6) save the bleaching dosing, adopt imitative enzyme pretreatment process, under identical whiteness requires, can reduce follow-up Peracetic acid section of floating or the hydrogen peroxide section of floating and float the agent consumption more than 40%;
(7) industrial implementation is easy, and the consumption of toxicant pyridine is minimum in the imitative enzyme pretreatment system, and therefore difficulty is less in commercial Application.Imitative enzyme pretreatment system also can not added pyridine.When imitative enzyme pretreatment system was not added pyridine, TCF floated the high whiteness that paper pulp still can reach 89.6%SBD eventually, has increased 4.4%SBD than blank sample, and viscosity is 629mLg
-1, it is still obvious to improve pulp brightness, and pulp property is still good.
Description of drawings
Fig. 1 is the chemical structural formula of salen;
Fig. 2 is the chemical structural formula of metal salen complex, and wherein M can be multiple metal, as Co, Zn, Ni etc.;
Fig. 3 is the M-salen complex that has pyridine axle part;
Fig. 4 is the synthetic route of metal salen complex.
The specific embodiment
Embodiment 1
Get 2.5 gram ethylenediamines and 8.5 milliliters of salicylides and be dissolved in 18 ml methanol, in ice-water bath, stirred 30 minutes, left standstill 15 minutes, decompress filter, with 1 milliliter of ether washing, 33 ℃ dry 6 hours down, get faint yellow solid.With 160 milliliters of absolute ethyl alcohol recrystallizations, drying is 18 hours under 33 ℃, obtains schiff bases salen again.
Getting 13 mM schiff bases salen is dissolved in 150 ml methanol, other takes by weighing 13 mM Cobalt diacetate tetrahydrates, be dissolved in the warm water, change over to rapidly in the above-mentioned reaction bulb, and generate brown precipitate rapidly, 70 ℃～80 ℃ reflux 1 hour, brown precipitate becomes the kermesinus crystallization, is chilled to room temperature, and crystallization is transferred to sand core funnel, suction filtration is drying to obtain Co-salen.
In weight percent concentration was 6% bamboo pulp, the NaOH consumption was 3.0%, H
2O
2Consumption is 1.0%, metal salen consumption is 0.024%, the pyridine consumption with metal salen mol ratio be 0.9: 1, O
2Pressure be 0.16MPa, to bamboo pulp bleaching preliminary treatment, the temperature of processing is controlled at 70 ℃～90 ℃, time 3h～5h.Carry out follow-up total chlorine free bleaching then and handle, in the alkali treatment section that hydrogen peroxide is strengthened, sodium hydroxide concentration 2.0%, hydrogen peroxide consumption 0.5%, pulp density 8% during processing, 75 ℃ of temperature, 1.75 hours time; In the peroxy acid bleach section, chelation treatment magnesium sulfate consumption 0.08%, diethylene triamine pentacetic acid (DTPA) consumption 0.6%, pulp density 5% during processing, 60 ℃ of temperature, 0.75 hour time, then paper pulp adds Peracetic acid and bleaches through washing, Peracetic acid consumption 2.6%, pulp density 12% during processing, 60 ℃ of temperature, 2.0 hours time; In the hydrogen peroxide bleaching section, sodium hydroxide concentration 1.8%, magnesium sulfate consumption 0.08%, sodium metasilicate consumption 1.5%, diethylene triamine pentacetic acid (DTPA) consumption 0.64%, hydrogen peroxide consumption 2.3%, pulp density 10% during processing, 85 ℃ of temperature, 2.5 hours time.
Embodiment 2
Get 2.0 gram ethylenediamines and 6.8 milliliters of salicylides and be dissolved in 14.4 ml methanol, in ice-water bath, stirred 30 minutes, left standstill 15 minutes, decompress filter, with 1 milliliter of ether washing, 33 ℃ dry 6 hours down, get faint yellow solid.With 128 milliliters of absolute ethyl alcohol recrystallizations, drying is 18 hours under 33 ℃, obtains schiff bases salen again.
Getting 10.4 mM schiff bases salen is dissolved in 120 ml methanol, other takes by weighing 10.4 mM zinc acetate dihydrates, be dissolved in the warm water, change over to rapidly in the above-mentioned reaction bulb, and generate brown precipitate rapidly, 70 ℃～80 ℃ reflux 1 hour, brown precipitate becomes the kermesinus crystallization, is chilled to room temperature, and crystallization is transferred to sand core funnel, suction filtration is drying to obtain Zn-salen.
In weight percent concentration was 5.0% bamboo pulp, the NaOH consumption was 2.4%, H
2O
2Consumption is 0.9%, metal salen consumption is 0.027%, the pyridine consumption with metal salen mol ratio be 0.8: 1, O
2Pressure be 0.18MPa, to bamboo pulp bleaching preliminary treatment, the temperature of processing is controlled at 70 ℃～90 ℃, time 3h～5h.Carry out follow-up total chlorine free bleaching then and handle, in the alkali treatment section that hydrogen peroxide is strengthened, sodium hydroxide concentration 1.6%, hydrogen peroxide consumption 0.6%, pulp density 10% during processing, 85 ℃ of temperature, 1.5 hours time; In the peroxy acid bleach section, chelation treatment magnesium sulfate consumption 0.09%, diethylene triamine pentacetic acid (DTPA) consumption 0.4%, pulp density 4% during processing, 65 ℃ of temperature, 0.5 hour time, then paper pulp adds Peracetic acid and bleaches through washing, Peracetic acid consumption 2.8%, pulp density 10% during processing, 65 ℃ of temperature, 1.75 hours time; In the hydrogen peroxide bleaching section, sodium hydroxide concentration 1.6%, magnesium sulfate consumption 0.09%, sodium metasilicate consumption 1.4%, diethylene triamine pentacetic acid (DTPA) consumption 0.96%, hydrogen peroxide consumption 2.5%, pulp density 8% during processing, 80 ℃ of temperature, 2.75 hours time.
Embodiment 3
Get 3.0 gram ethylenediamines and 10.2 milliliters of salicylides and be dissolved in 21.6 ml methanol, in ice-water bath, stirred 30 minutes, left standstill 15 minutes, decompress filter, with 1.2 milliliters of ether washings, 33 ℃ dry 6 hours down, get faint yellow solid.With 192 milliliters of absolute ethyl alcohol recrystallizations, drying is 18 hours under 33 ℃, obtains schiff bases salen again.
Getting 15.6 mM schiff bases salen is dissolved in 180 ml methanol, other takes by weighing 15.6 mMs, four water acetic acid nickel, be dissolved in the warm water, change over to rapidly in the above-mentioned reaction bulb, and generate brown precipitate rapidly, 70 ℃～80 ℃ reflux 1 hour, brown precipitate becomes the kermesinus crystallization, is chilled to room temperature, and crystallization is transferred to sand core funnel, suction filtration is drying to obtain Ni-salen.
In weight percent concentration was 4% bamboo pulp, the NaOH consumption was 2.7%, H
2O
2Consumption is 0.8%, metal salen consumption is 0.03%, the pyridine consumption with metal salen mol ratio be 1: 1, O
2Pressure be 0.2MPa, to bamboo pulp bleaching preliminary treatment, the temperature of processing is controlled at 70 ℃～90 ℃, time 3h～5h.Carry out follow-up total chlorine free bleaching then and handle, in the alkali treatment section that hydrogen peroxide is strengthened, sodium hydroxide concentration 1.8%, hydrogen peroxide consumption 0.4%, pulp density 12% during processing, 80 ℃ of temperature, 2.0 hours time; In the peroxy acid bleach section, chelation treatment magnesium sulfate consumption 0.1%, diethylene triamine pentacetic acid (DTPA) consumption 0.5%, pulp density 6% during processing, 70 ℃ of temperature, 1.0 hours time, then paper pulp adds Peracetic acid and bleaches through washing, Peracetic acid consumption 3.0%, pulp density 8% during processing, 70 ℃ of temperature, 1.5 hours time; In the hydrogen peroxide bleaching section, sodium hydroxide concentration 2.0%, magnesium sulfate consumption 0.1%, sodium metasilicate consumption 1.3%, diethylene triamine pentacetic acid (DTPA) consumption 0.8%, hydrogen peroxide consumption 2.1%, pulp density 12% during processing, 90 ℃ of temperature, 3.0 hours time.
Claims (4)
1. bamboo pulp total chlorine free bleaching new technology is characterized in that mainly comprising following steps:
1. synthetic imitative enzyme metal salen, with schiff bases salen and metal organic acid reactant salt, synthetic metal salen;
2. to bamboo pulp bleaching preliminary treatment, at metal salen, NaOH, H
2O
2And O
2Under the condition that exists, oxygen desulfating bamboo pulp is bleached preliminary treatment;
3. follow-up total chlorine free bleaching is handled via the follow-up tri-stage bleaching that alkali treatment section, peroxy acid bleach section and the hydrogen peroxide bleaching section of hydrogen peroxide reinforcement are formed the imitative pretreated bamboo pulp of enzyme of metal salen again.
2. by the described bamboo pulp total chlorine free bleaching of claim 1 new technology, it is characterized in that: during to bamboo pulp bleaching preliminary treatment, the weight percent concentration of bamboo pulp is 4.0%～6.0%, and the percentage that each raw material accounts for bamboo pulp weight is, the NaOH consumption is 2.4%～3.0%, H
2O
2Consumption is 0.8%～1.0%, metal salen consumption is 0.024%～0.03%, O
2Pressure be 0.16MPa～0.2MPa, pretreated temperature is controlled at 70 ℃～90 ℃, time 3h～5h.
3. bamboo pulp total chlorine free bleaching new technology according to claim 2 is characterized in that: during to bamboo pulp bleaching preliminary treatment, also added pyridine, the pyridine consumption with metal salen mol ratio be 0.8～1: 1.
4. bamboo pulp total chlorine free bleaching new technology according to claim 3 is characterized in that the process conditions of follow-up total chlorine free bleaching are:
1. the alkali treatment section strengthened of hydrogen peroxide, sodium hydroxide concentration 1.6%～2.0%, hydrogen peroxide consumption 0.4%～0.6%, pulp density 8%～12% during processing, 75 ℃～85 ℃ of temperature, 1.5 hours～2.0 hours time;
2. peroxy acid bleach section, chelation treatment magnesium sulfate consumption 0.08%～0.1%, diethylene triamine pentacetic acid (DTPA) consumption 0.4%～0.6%, pulp density 4%～6% during processing, 60 ℃～70 ℃ of temperature, 0.5 hour～1.0 hours time; Paper pulp adds Peracetic acid and bleaches through washing, Peracetic acid consumption 2.6%～3.0%, and pulp density 8%～12% during processing, 60 ℃～70 ℃ of temperature, 1.5 hours～2.0 hours time;
3. hydrogen peroxide bleaching section, sodium hydroxide concentration 1.6%～2.0%, magnesium sulfate consumption 0.08%～0.1%, sodium metasilicate consumption 1.3%～1.5%, diethylene triamine pentacetic acid (DTPA) consumption 0.64%～0.96%, hydrogen peroxide consumption 2.1%～2.5%, pulp density 8%～12% during processing, 80 ℃～90 ℃ of temperature, 2.5 hours～3.0 hours time.
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|---|---|---|---|
| CN2007100661038A CN101109160B (en) | 2007-08-10 | 2007-08-10 | Novel non-chlorine bleaching technique for bamboo pulp |
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|---|---|---|---|
| CN2007100661038A CN101109160B (en) | 2007-08-10 | 2007-08-10 | Novel non-chlorine bleaching technique for bamboo pulp |
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| CN101109160B CN101109160B (en) | 2010-04-14 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN102852019A (en) * | 2012-09-18 | 2013-01-02 | 四川理工学院 | Totally chlorine-free bleaching method of bamboo pulp for producing Daqian writing and painting paper |
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- 2007-08-10 CN CN2007100661038A patent/CN101109160B/en not_active Expired - Fee Related
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| CN101575820B (en) * | 2009-06-08 | 2011-12-07 | 昆明理工大学 | Method for removing metal ions of paper pulp and bleaching |
| CN102061638B (en) * | 2010-11-12 | 2013-07-10 | 昆明理工大学 | Process for catalytically bleaching pulp by acetate/persulfate |
| CN102061638A (en) * | 2010-11-12 | 2011-05-18 | 昆明理工大学 | Process for catalytically bleaching pulp by acetate/persulfate |
| CN102505472A (en) * | 2011-11-22 | 2012-06-20 | 东华大学 | Method for low-temperature one-bath-one-step pretreatment of pure cotton woven fabric through biomimetic metal |
| CN102587186B (en) * | 2012-03-20 | 2015-03-11 | 昆明理工大学 | Method for bleaching dendrocalamus giganteus chemical pulp |
| CN102587186A (en) * | 2012-03-20 | 2012-07-18 | 昆明理工大学 | Method for bleaching dendrocalamus giganteus chemical 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 |
| CN102776796B (en) * | 2012-07-23 | 2014-08-06 | 昆明理工大学 | Technology for catalyzing and bleaching paper pulp with immobilized Schiff alkali metals |
| CN102852019A (en) * | 2012-09-18 | 2013-01-02 | 四川理工学院 | Totally chlorine-free bleaching method of bamboo pulp for producing Daqian writing and painting paper |
| CN102852019B (en) * | 2012-09-18 | 2014-08-20 | 四川理工学院 | Totally chlorine-free bleaching method of bamboo pulp for producing Daqian writing and painting paper |
| CN103174045A (en) * | 2013-03-28 | 2013-06-26 | 昆明理工大学 | Production method of bark-forming handmade paper bleaching pulp |
| CN103334335A (en) * | 2013-07-12 | 2013-10-02 | 马志强 | Preparation method of pollution-free high-whiteness palm silk paper pulp and application of paper pulp in paper product |
| CN104788687A (en) * | 2015-03-25 | 2015-07-22 | 昆明理工大学 | Process for catalyzing and oxidizing lignin by using Salen-porphyrin complexes |
| 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 |
| CN105113308B (en) * | 2015-08-12 | 2017-07-25 | 昆明理工大学 | The catalysis pulp oxygen delignification technique of paper and surfactant is catalyzed based on M (salen) |
| CN114134748A (en) * | 2021-11-25 | 2022-03-04 | 牡丹江恒丰纸业股份有限公司 | Chlorine-free bleaching method for hemp pulp |
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