CN101321908B - Process of producing high-yield pulp - Google Patents

Process of producing high-yield pulp Download PDF

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Publication number
CN101321908B
CN101321908B CN2006800453791A CN200680045379A CN101321908B CN 101321908 B CN101321908 B CN 101321908B CN 2006800453791 A CN2006800453791 A CN 2006800453791A CN 200680045379 A CN200680045379 A CN 200680045379A CN 101321908 B CN101321908 B CN 101321908B
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tmp
pulp
acid
lignocellulose
paper pulp
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CN101321908A (en
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K·S·M·瓦尔特
E·L·E·瓦克贝里
M·L·保尔森
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Nouryon Chemicals International BV
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Akzo Nobel NV
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
    • D21B1/00—Fibrous raw materials or their mechanical treatment
    • D21B1/02—Pretreatment of the raw materials by chemical or physical means
    • 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
    • D21C9/16—Bleaching ; Apparatus therefor with per compounds
    • D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Paper (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

The present invention relates to a process for preparing a high-yield pulp comprising a) treating a lignocellulose containing material chemically by means of an oxidising system comprising at least one non-enzymatic oxidant substantially free from ozone and chlorine dioxide and an activator at a pH from about 2 to about 6.5; and b) treating the lignocellulose containing material mechanically for a time sufficient to produce a high-yield pulp, wherein the lignocellulose containing material is chemically treated prior to and/or during any mechanical treatment stage, and wherein the lignocellulose containing material is not chemically treated at a pH from about 11.5 to about 14 between stages a) and b).

Description

Produce the method for high-yield pulp
The present invention relates to a kind of method of producing high-yield pulp by lignocellulose-containing materials.
Background technology
The improvement production of ligno-ccllulose product and effective the utilization are the thing with high importance to pulp and paper industry and society.Using natural source manufacturing machine slurrying in the world and chemi-mechanical pulp is effective and efficient manner, because the productive rate height and the environmental impact of these production methods are lower.Mechanical pulp and chemi-mechanical pulp account for about 25% of fibrillation production in the world.A shortcoming of mechanical pulp method is a high energy consumption, and it accounts for about 20% of papermaking energy requirement in the world.Depend on the residing position of mechanical pulp grinding machine in the world, energy accounts for the 25-50% of hot method mechanical pulp (TMP) total production cost separately.About 80% energy consumption is at main line defibrination (main, the second, etc.), in deslagging and the low denseness defibrination in the TMP grinding machine.Energy remaining consumes in pump, agitator, sieve, air blast, fan and Mechanical Driven.This means that most of energy are used for fiber separation and are used to develop fiber so that they are applicable to the final use of defined.Therefore, it is highly important that the appropriate method that finds the reduction energy to consume.Yet if if the intensity of paper pulp or paper significantly reduces simultaneously or environmental effect is subjected to remarkable infringement, the method that reduces energy consumption in manufacturing machine slurry process has limited interest for conventional products.
EP 494 519 A1 relate to a kind of comprising with containing the alkaline peroxide solution impregnation fragment of stabilization of peroxide agent, and the method for fiber separation was mechanically wherein anticipated wood shavings before the peroxide dipping then.Yet the method for EP 494 519 A1 relates to expensive fund input and do not produce enough energy savings under the condition of keeping paper pulp yield and pulp property.
The low fibre length or the strength character that an object of the present invention is in being applied to the high yield cooking method for processing simply, to reduce energy consumption and can significantly not fall the paper pulp of producing.Another object of the present invention provides such method and keeps paper pulp yield at acceptable level.Another object of the present invention provides a kind of method easily that need not significant fund input.Another purpose provides a kind of basic treatment section that do not exist and improves simultaneously or the method for not appreciable impact gained high-yield pulp performance such as strength character at least.
Summary of the invention
The present invention relates to a kind of method for preparing high-yield pulp, it comprises:
A) by comprising at least a non-enzymatic catalysis oxidant and activator and not conforming to oxidation system chemical treatment lignocellulose-containing materials under about 2 to about 6.5 pH of ozone and chlorine dioxide substantially; With
B) the lignocellulose-containing materials mechanical treatment is enough to produce time of high-yield pulp, wherein before any mechanical treatment section and/or among the chemical treatment lignocellulose-containing materials, and wherein not section a) and b) between under about 11.5 to about 14 pH the chemical treatment lignocellulose-containing materials.
According to an embodiment, pH is about 2.5 to about 6, for example about 2.5 to about 5.5 or about 3 to about 5.5 according to appointment 3 to about 4.According to an embodiment, pH is about 3.5 to about 5.
According to an embodiment, lignocellulose-containing materials not section a) and b) between be about 7 to about 14, for example about 8 to about 14 or about 9 to about 14 according to appointment 10 to about 14 or about 10.5 to about 14 or about 11 to about 14 times chemical treatments at pH.
According to an embodiment, lignocellulose-containing materials is not about 7 to about 14, for example about 8 to about 14 or about 9 to about 14 according to appointment 10 to about 14 or about 10.5 to about 14 or about 11 to about 14 or about 11.5 to about 14 times chemical treatments at pH a) in section before.
The term high-yield pulp can for example comprise mechanical pulp (MP), RMP (RMP), pressure RMP (PRMP), hot method mechanical pulp (TMP), hot forensic chemistry mechanical pulp (TMCP), high temperature TMP (HT-TMP) RTS-TMP, hot method paper pulp (Thermopulp), ground wood pulp (GW), Stone Ground Wood (SGW), pressure ground wood pulp (PGW), super-pressure ground wood pulp (PGW-S), heating ground wood pulp (TGW), heating Stone Ground Wood (TSGW), chemi-mechanical pulp (CMP), chemistry correct grinding mechanical pulp (CRMP), preheating method wood chip chemi-mechanical pulp (CTMP), high temperature CTMP (HT-CTMP), the hot method mechanical pulp of sulphite for modification (SMTMP), screening reject CTMP (CTMP R), ground wood CTMP (G-CTMP), semi-chemical pulp (SC), neutral sulphite semichemical pulp (NSSC), high yield sulfite pulp (HYS), biochemistry slurry (BRMP), paper pulp or its any modification and the combination of producing according to OPCO method, explosion method slurrying, Bi-Vis method, dilution water sulfonation method (dilution water sulfonation process (DWS)), sulfonation long fiber method (SLF), chemical treatment long fiber method (CTLF), long fiber CMP method (LFCMP).According to an embodiment, the yield of high-yield pulp is at least about 60%, for example at least about 70%, or at least about 80%, or at least about 85%.According to an embodiment, the yield of high-yield pulp is at least about 90% as at least about 95%.Paper pulp can be bleached pulp or brown stock.
According to an embodiment, lignocellulose-containing materials comprises not defibrated wood.According to an embodiment, lignocellulose-containing materials comprises the lignocellulose-containing materials of mechanical treatment.According to an embodiment, oxidation system applies between two mechanical treatment sections.Lignocellulose-containing materials for example can comprise log, raw material in small, broken bits, and it comprises wood materials, as wood particle (as wood shavings, wood chips, lumber fibre and sawdust form) and the fiber that comprises the annual or perennial plant of non-timber.Wood material can be derived from hardwood or cork class, birch for example, and beech, poplar such as European poplar, alder, Eucalyptus, maple, locust tree mixes tropical hard wood, pine such as torch pine, China fir, Chinese hemlock spruce, larch, dragon spruce such as Picea mariana or Norway spruce and composition thereof.Non-wooden plant material for example can be by the straw of cereal crops, reed canary grass, and reed, flax, hemp, mestha, jute, ramie, sisal hemp, abaca, coir fibre, bamboo, bagasse or its combination provide.
According to an embodiment, oxidant is selected from peralcohol, Halogen oxidant, oxygen, nitrogen oxide or its combination.The oxidation system that maybe advantageously comprises the non-enzymatic catalysis oxidant does not contain ozone substantially, because ozone does not provide enough paper pulp yields and is generally more expensive substitute owing to low selectivity.Term " does not contain ozone substantially " and is meant that oxidation system comprises less than 5 weight % based on the gross weight of oxidation system, for example less than 2 weight % or less than 1 weight % ozone (calculating with 100%).Term " does not contain chlorine dioxide substantially " and is meant that oxidation system comprises less than 5 weight % based on the gross weight of oxidation system, or less than 2 weight % or less than 1 weight % chlorine dioxide (calculating with 100%).
According to an embodiment, non-enzymatic catalysis oxidant and activator can before any mechanical treatment section or among any position add.According to an embodiment, with oxidation system at one before the mechanical treatment section or several processing sections or in the mechanical treatment section, be applied to lignocellulose-containing materials.According to an embodiment, processing applies oxidation system as interlude between two mechanical treatment sections.According to an embodiment, this method is used two or three mechanical treatment sections such as defibrination section, and available oxidation system is handled lignocellulose-containing materials between them.Yet, also can use the section of any other number that comprises or several reject refining sections.According to an embodiment, oxidation system is applied to the reject refining section.
Activator be can be in the presence of the non-enzymatic catalysis oxidant any suitable substance of accelerated oxidation.According to an embodiment, activator is selected from metal ion, TAED, cyanamide, copper sulphate, ferric sulfate and composition thereof.According to an embodiment, activator is a transition metal.
According to an embodiment, oxidation system comprises the reinforcing agent of promotion/control oxidation.According to an embodiment, reinforcing agent is selected from nitrogenous polycarboxylic acid, nitrogenous polyphosphonic acid, nitrogenous polyalcohol, oxalic acid, oxalates, glycol hydrochlorate, ascorbic acid, citric acid, nitrilo-acetate, gallic acid, fulvic acid, itaconic acid, hemoglobin, hydroxy benzenes, catechol (catecholate), quinoline, dimethoxybenzoic acid, dihydroxy-benzoic acid, dimethoxy-benzyl alcohol, pyridine, histidyl-glycine, phthalocyanine, acetonitrile, 18-hat-6-ether, mercapto succinic acid, cyclohexadiene, polyoxometallate and combination thereof.
According to an embodiment, reinforcing agent is selected from organic compounds containing nitrogen, contains uncle's nitrogen polycarboxylic acid, nitrogenous polyphosphonic acid, nitrogenous polyalcohol and composition thereof.According to an embodiment, reinforcing agent is selected from diethylene-triamine pentaacetic acid (DTPA), ethylenediamine tetra-acetic acid (EDTA), nitrilotriacetic acid(NTA) (NTA) and combination thereof.According to an embodiment, reinforcing agent is selected from compound, polyphosphonic acid salt or polyphosphonic acid, hydroxycarboxylate, hydroxycarboxylic acid, dithiocar-bamate, oxalic acid, imino-diacetic butanedioic acid, [S, S ']-EDDS, glycol hydrochlorate, ascorbic acid, citric acid, nitrilo-acetate, gallic acid, fulvic acid, the itaconic acid based on other aminopolycanboxylic acid.According to an embodiment; reinforcing agent is selected from oxalates; hemoglobin; dihydroxy benzenes (as hydroquinones); trihydroxy benzene; catechol is (as 4; 5-dimethoxy catechol; 2; the 3-dihydroxy benzenes; the 4-methyl pyrocatechol); quinoline; oxyquinoline (as oxine); dihydroxy-benzoic acid is (as 3; the 4-dihydroxy-benzoic acid; 2; the 3-dihydroxy-benzoic acid); 3; the 4-dimethoxy-benzyl alcohol; 3; the 4-dimethoxybenzoic acid; 3; the 4-dimethoxy-p; pyridine; the histidyl-glycine; phthalocyanine; acetonitrile; 18-is preced with-6 ethers; mercapto succinic acid; 1, the 3-cyclohexadiene; polyoxometallate.According to an embodiment, oxidation system comprises at least a enzyme as reinforcing agent.
According to an embodiment, lignocellulose-containing materials was handled about 1 second to about 10 hours with oxidation system.According to an embodiment, lignocellulose-containing materials was handled about 5 seconds to about 5 hours with oxidation system.According to an embodiment, lignocellulose-containing materials was handled about 10 seconds to about 3 hours with oxidation system.
According to an embodiment, to about 200 ℃ temperature, handle lignocellulose-containing materials at about 30 ℃.According to an embodiment, to about 180 ℃ temperature, handle lignocellulose-containing materials at about 50 ℃.According to an embodiment, to about 180 ℃ temperature, handle lignocellulose-containing materials at about 80 ℃.
According to an embodiment, the addition of non-enzymatic catalysis oxidant (calculating with 100%) is that about 0.1 weight % is to about 5 weight % based on the weight of lignocellulose-containing materials.According to an embodiment, the addition of non-enzymatic catalysis oxidant (calculating with 100%) is that about 0.2 weight % is to about 3 weight % based on the weight of lignocellulose-containing materials.According to an embodiment, the addition of non-enzymatic catalysis oxidant (calculating with 100%) is that about 0.3 weight % is to about 2 weight % based on the weight of lignocellulose-containing materials.
According to an embodiment, the addition of activator (calculating with 100%) is about 0.0001 to about 1 weight % based on the weight of lignocellulose-containing materials.According to an embodiment, the addition of activator (calculating with 100%) is that about 0.001 weight % is to about 0.5 weight % based on the weight of lignocellulose-containing materials.According to an embodiment, the addition of activator (calculating with 100%) is that about 0.0025 weight % is to about 0.1 weight % based on the weight of lignocellulose-containing materials.According to an embodiment, activator before any mechanical treatment section or among, separate with the non-enzymatic catalysis oxidant or add simultaneously.Therefore, activator can be before adding the non-enzymatic catalysis oxidant, add simultaneously or afterwards.Activator add the non-enzymatic catalysis oxidant can be close to before mechanical treatment section such as the fiberizer reinforced before, but also can be for example before main fiberizer, but not the enzymatic oxidation agent is after main fiberizer but added before second fiberizer.
Mechanical treatment can carry out in one or several section.Usually, mechanical treatment can carry out in two or more comprise the section of screening reject mechanical treatment section, and the lignocellulose-containing materials that wherein can make 60 weight % at the most is by this screening reject mechanical treatment section.The mechanical treatment section is usually by making lignocellulose-containing materials be undertaken by wood grinder and/or fiberizer.Yet other mechanical treatment also can be such as plunger screw rod (as impressafiner), ring-roller mill (as the Szego grinding machine), biaxial extruder (double screw extruder), back and forth movement equipment, RT Fiberizer TM, disperser or its any combination device in carry out.
According to an embodiment, the non-enzymatic catalysis oxidant is selected from inorganic peroxy compounds such as hydrogen peroxide, or produces the compound such as the percarbonate of hydrogen peroxide, perborate, persulfate, superphosphate, persilicate or corresponding weak acid.
According to an embodiment, the non-enzymatic catalysis oxidant is selected from organic peroxy compound such as percarboxylic acids, as peracetic acid and benzylhydroperoxide.
According to an embodiment, oxidation system comprises the Halogen oxidant, as the chlorine sodium salt of chlorite, hypochlorite, cyanuric acid.According to an embodiment, oxidation system comprises oxygen and/or nitrogen oxide such as NO or NO 2According to an embodiment, oxidation system comprises the combination of different oxidants, and it can or re-use by the step adding that produces the non-enzymatic catalysis oxidant.
According to an embodiment, oxidation system further comprises activator such as metal ion, as Fe, Mn, Co, Cu, W or Mo, or TAED, cyanamide or its combination.According to an embodiment, metal ion such as transition metal ions can acid or the form of salt, or use with the complex form of conventional organic or inorganic compound.
According to an embodiment, ultraviolet irradiation or other irradiation can be applied to the non-enzymatic catalysis oxidant or be applied to the lignocellulose-containing materials of choosing the non-enzymatic catalysis oxidizer treatment that makes up with reinforcing agent wantonly using.
According to an embodiment, reinforcing agent such as complexant, chelating agent or part are included in the oxidation system.The addition that depends on these reinforcing agents, they can promote and/or control oxidation.
According to an embodiment, reinforcing agent and activator all are included in the oxidation system.
Following embodiment has set forth and how to carry out described invention rather than limit its scope.
Except as otherwise noted, all umbers and percentage refer to bone-dry weight portion and percetage by weight.Chemicals calculates with 100%.
Embodiment 1
Picea mariana (Picea mariana) timber is used to produce hot method mechanical pulp (TMP).Before preheating (4.14 crust steam pressures, the 40s time of staying) and defibrination operation, with log peeling and chopping and washing.Use three sections defibrination devices, in the end the defibrination section changes the input energy to obtain having the paper pulp of different free (defibrination) levels.Use single-deck 36 in the first defibrination section " pressurized refiner (the 36-1CP type is operated under 1800rpm), use double plate 36 at second and the 3rd section " the atmospheric pressure fiberizer (401 types, 1200rpm).The energy input is that about 500kWh/ utmost point dry metric ton (bdmt) is at the about 1000kWh/bdmt of the second defibrination Duan Zhongwei in main fiberizer.In most of the cases, have 400,800 and three kind of the 3rd defibrination section of the target energy of 1200kWh/bdmt input.All tests are carried out under controlled condition, this means that concrete energy consumption varies and paper pulp and paper performance are the results of the chemicals of adding in the test.For reference, the energy consumption (TMP that in flight formula device, measures Ref1And TMP Ref2, referring to following table and figure) and suitable with industrial operation.
Each defibrination series of describing in following embodiment produces according to said procedure.
TMP reference (the TMP in figure below and the table Ref1) do not add chemicals and produce.Can find out from the intensity of the gained paper pulp of Fig. 1 and table 1 and 2 as the beating degree (free value) of the function of particular energy consumption (SEC).Fig. 2 has shown fiber length distribution, and Fig. 3 is the fiber width distribution (the free value of about 100ml CSF) of gained paper pulp.
Also provide the TMP reference of under acid condition more, producing (to be labeled as TMP Ref2), it is the effect of result of the method for the invention rather than pH reduction in the defibrination process that the energy that is obtained to guarantee reduces.By add 0.19 weight % sulfuric acid (H based on utmost point desiccated wood weight 2SO 4) to the fiberizer eye (inlet) of main fiberizer and reduction pH.The pH of gained paper pulp is 3.8.The TMP performance of the paper pulp of producing can find among the 1-2 with showing by Fig. 1-3 below.
Acid hydrogen peroxide (H used according to the invention 2O 2) preparation TMP by add the ferric sulfate (FeSO of 0.08 weight % based on utmost point desiccated wood weight 4* 7H 2O) the fiberizer eye of extremely main fiberizer, and the hydrogen peroxide (H that adds 1.0 weight % based on utmost point desiccated wood weight 2O 2) produce to the blow line of main fiberizer.The pH of gained paper pulp is 3.6.This paper pulp is labeled as TMP in figure below and the table HP1Fe
Acid hydrogen peroxide (H used according to the invention 2O 2) the 2nd TMP of preparation is by adding the ferric sulfate (FeSO of (utmost point desiccated wood) 0.15 weight % 4* 7H 2O) the fiberizer eye of extremely main fiberizer, and the hydrogen peroxide (H that adds (utmost point desiccated wood) 1.1 weight % 2O 2) produce to the blow line of main fiberizer.The pH of gained paper pulp is 3.4.This paper pulp is labeled as TMP among Fig. 1 below-3 and the table 1-2 HP2Fe
The beating degree of measuring as the free value of paper pulp is the most important parameters that influences paper pulp and paper performance such as intensity and light scattering ability.Therefore must under constant free value, compare paper pulp.Measure and in value of pushing away (to free value 100ml CSF) so provide hereinafter.
Fig. 1 is to reference (TMP Ref1And TMP Ref2) and paper pulp (TMP produced according to the invention HP1FeAnd TMP HP2Fe) the free value as the function of particular energy consumption (SEC) described.Obtained significant energy saving for paper pulp produced according to the invention as can be seen from Figure 1, and consumed TMP for energy Ref1And TMP Ref2Between not obviously difference.For constant free level (100ml CSF), paper pulp consumption rate reference (TMP produced according to the invention Ref1And TMP Ref2, see Table 2) and few 20% (TMP HP1Fe) and 25% (TMP HP2Fe) energy.For TMP HP1FeAnd TMP HP2FeUse 1.0 weight % and 1.1 weight % (based on utmost point desiccated wood) H respectively 2O 2Obtained energy saving.
In addition, the strength character similar (seeing Table 1 and 2) of the strength character of paper pulp produced according to the invention clearly (stretching and burst index, TEA) and TMP reference also.
Table 1: the feature of the paper pulp of producing and energy consumption
Free value (mlCSF) Energy consumes (kWh/bdt) Tensile figure (Nm/g) Burst index (kPam 2/g) TEA (J/m 2) Fibre length 1 (mm)
TMP Ref1 119 2687 42.4 2.6 30.4 1.6
TMP Ref2 ?91 2825 54.0 3.2 54.0 1.5
TMP HP1Fe 2 ?109 2250 44.3 2.9 34.3 1.6
TMP HP2Fe 2 ?75 2265 54.2 3.0 46.0 1.5
1Measure average (length weighting) fibre length with Kajaani FS-100 fiber size analyzer.
2Produced according to the invention.
Table 2: the paper pulp feature of the paper pulp of producing and in be pushed into the energy saving of constant free value (100ml CSF)
Energy saving 1 (％) Tensile figure (Nm/g) Burst index (kPam 2/g) TEA (J/m 2) Fibre length 2?(mm)
TMP Ref1 49.5 2.7 32.3 ?1.6
TMP Ref2 54.3 3.2 54.0 ?1.6
TMP HP1Fe 3 20 50.7 3.0 40.3 ?1.6
TMP HP2Fe 3 25 51.1 2.8 42.6 ?1.5
1Based on TMP reference (TMP Ref1And TMP Ref2) energy consume resulting energy saving.
2Measure average (length weighting) fibre length with Kajaani FS-100 fiber size analyzer.
3Produced according to the invention.
A kind of mode that reduces energy consumption is a cutting fiber in the defibrination process.Yet a most important characteristics in the process of producing chemi-mechanical pulp or mechanical pulp such as TMP is to keep fibre length on possible extent.Usually, high average fiber length generation has the paper pulp of good advantage to produce firm paper.Can find out reference (TMP from table 1 and 2 Ref1And TMP Ref2) and paper pulp (TMP produced according to the invention HP1FeAnd TMP HP2Fe) average fiber length be maintained.This is showing TMP Ref1, TMP Ref2In Fig. 2 of the fiber length distribution of the paper pulp that is selected from embodiment 1-3 produced according to the invention, and in the Fig. 3 that shows with the fiber width distribution of the identical paper pulp of FibreMaster apparatus measures, further specified.The free value of paper pulp provides in table 1,3 and 5.Therefore, the inventive method makes and can produce high-yield pulp and not destroy pulp property with very low energy consumption.
Embodiment 2
According to the program of the foregoing description 1 with the hot method mechanical pulp of Picea mariana (TMP) peeling, chopping, preheating and defibrination.
(be labeled as TMP under the situation that does not add chemicals, to produce the TMP reference with embodiment 1 described identical mode Ref1).
With with mode identical described in the embodiment 1 by add the sulfuric acid (H of 0.19 weight % based on utmost point desiccated wood weight 2SO 4) the reference TMP that produces under more acid condition to fiberizer eye (inlet) production of main fiberizer (is labeled as TMP Ref2).
Acid hydrogen peroxide (H used according to the invention 2O 2) TMP of preparation be by will being the Na of 0.12 weight % based on utmost point desiccated wood weight 4EDTA be the ferric sulfate (FeSO of 0.08 weight % based on utmost point desiccated wood weight 4* 7H 2O) mix, then mixture is added in the fiberizer eye of main fiberizer and produce.With hydrogen peroxide (H 2O 2, be 1.1 weight % based on utmost point desiccated wood weight) and add the blow line of main fiberizer.The pH of gained paper pulp is 3.7.This paper pulp Fig. 2-4 below and table 3-4 are labeled as TMP HP1FeEDTA
The beating degree of measuring as the free value of paper pulp is the most important parameters that influences paper pulp and paper performance such as intensity and light scattering ability.Therefore must under constant free value, compare paper pulp.Measure and in the value of pushing away (to free value 100ml CSF) therefore in scheming and showing, provide.
Fig. 4 is to reference (TMP Ref1And TMP Ref2) and TMP produced according to the invention HP1FeEDTAFree value as the function of particular energy consumption (SEC) has been described.For constant free value (100mlCSF), TMP HP1FeEDTAThan reference TMP (TMP Ref1And TMP Ref2, see Table 4) and 19% energy consumption less.
Table 3: the feature and the energy saving of the paper pulp of producing
Free value (mlCSF) Energy consumes (kWh/bdt) Tensile figure (Nm/g) Burst index (kPam 2/g) TEA (J/m 2) Fibre length 1 (mm) Light scattering coefficient (m 2/kg)
TMP Ref1 ?119 2687 42.4 2.6 30.4 1.6 53.2
TMP Ref2 ?91 2825 54.0 3.2 54.0 1.5 53.1
TMP HP1FeEDTA 2 ?118 2173 52.0 2.9 51.6 1.6 54.4
TMP HP1Fe 2，3 ?109 2250 44.3 2.9 34.3 1.6 49.4
1Measure average (length weighting) fibre length with Kajaani FS-100 fiber size analyzer.
2Produced according to the invention.
3Take from the data of table 1.
Table 4: the paper pulp feature of the paper pulp of producing and in be pushed into the energy saving of constant free value (100ml CSF)
Energy saving 1 (％) Tensile figure (Nm/g) Burst index (kPam 2/g) TEA (J/m 2) Fibre length 2?(mm) Light scattering coefficient (m 2/kg)
TMP Ref1 49.5 2.7 32.3 ?1.6 54
TMP Ref2 54.3 3.2 54.0 ?1.6 52
TMP HP1FeEDTA 3 19 53.5 2.9 49.1 1.6 55
TMP HP1Fe 3，4 20 50.7 3.0 40.3 1.6 49
1Based on TMP reference (TMP Ref1And TMP Ref2) energy consume resulting energy saving.
2Measure average (length weighting) fibre length with Kajaani FS-100 fiber size analyzer.
3Produced according to the invention.
4Take from the data of table 2.
TMP HP1FeEDTAEnergy saving level and TMP HP1FeIdentical, promptly with reference (TMP Ref1And TMP Ref2) energy consumption be about 20% when comparing.Yet, at TMP HP1FeEDTAIn the test, strength character (being tensile figure and TEA) and TMP Ref1Compare and improved or improve forcefully, with TMP HP1FeCompare also and improved (referring to table 3 and 4).Light scattering ability is the important parameter of printing sheets, with reference (TMP Ref1And TMP Ref2) compare, it maintains par.Fibre length and width distribution are similar to TMP reference (TMP Ref1And TMP Ref2, referring to Fig. 2-3).The light scattering ability that this explanation the present invention has improved the strength character of energy effect and gained paper pulp forcefully and kept paper pulp.
Embodiment 3
According to the program of the foregoing description 1 with the hot method mechanical pulp of Picea mariana (TMP) peeling, chopping, preheating and defibrination.
(be labeled as TMP under the situation that does not add chemicals, to produce the TMP reference with embodiment 1 described identical mode Ref1).
With with mode identical described in the embodiment 1 by adding the sulfuric acid (H of (utmost point desiccated wood) 0.19 weight % 2SO 4) the reference TMP that produces under more acid condition to fiberizer eye (inlet) production of main fiberizer (is labeled as TMP Ref2).
Acid hydrogen peroxide (H used according to the invention 2O 2) preparation TMP by add the ferric sulfate (FeSO of 0.08 weight % based on utmost point desiccated wood weight 4* 7H 2O) the fiberizer eye of extremely main fiberizer, and the hydrogen peroxide (H that adds 2.2 weight % based on utmost point desiccated wood weight 2O 2) produce to the blow line of main fiberizer.The pH of gained paper pulp is 3.3.This paper pulp Fig. 5 and Biao 5-6 below is labeled as TMP HP3Fe
Acid hydrogen peroxide (H used according to the invention 2O 2) preparation TMP by add the ferric sulfate (FeSO of 0.14 weight % based on utmost point desiccated wood weight 4* 7H 2O) the fiberizer eye of extremely main fiberizer, and the hydrogen peroxide (H that adds 2.1 weight % based on utmost point desiccated wood weight 2O 2) produce to the blow line of main fiberizer.The pH of gained paper pulp is 3.2.Below Fig. 2 of this paper pulp, 3 and 5 and table 5-6 be labeled as TMP HP4Fe
The beating degree of measuring as the free value of paper pulp is the most important parameters that influences paper pulp and paper performance such as intensity and light scattering ability.Therefore must under constant free value, compare paper pulp.Measure and in the value of pushing away (to free value 100ml CSF) so figure below and show in provide.
Fig. 5 is to TMP Ref1And TMP Ref2, and paper pulp (TMP produced according to the invention HP3FeAnd TMP HP4Fe) the free value as the function of particular energy consumption (SEC) described.For constant free level (100ml CSF), the paper pulp of producing according to described invention is than reference (TMP Ref1And TMP Ref2) few 33% (TMP HP3Fe) and 37% (TMP HP4Fe) energy consumption.
Table 5: the feature and the energy saving of the paper pulp of producing
Free value (ml CSF) Energy consumes (kWh/bdt) Tensile figure (Nm/g) Burst index (kPam 2/g) TEA (J/m 2) Fibre length 1 (mm)
TMP Ref1 119 2687 42.4 ?2.6 30.4 1.6
TMP Ref2 91 2825 54.0 ?3.2 54.0 1.5
TMP HP3Fe 2 116 1885 47.1 ?2.4 40.3 1.6
TMP HP4Fe 2 109 1810 47.8 ?2.4 41.1 1.5
1Measure average (length weighting) fibre length with Kajaani FS-100 fiber size analyzer.
2Produced according to the invention.
Table 6: the paper pulp feature of the paper pulp of producing and in be pushed into the energy saving of constant free value (100ml CSF)
Energy saving 1 (％) Tensile figure (Nm/g) Burst index (kPam 2/g) TEA (J/m 2) Fibre length 2?(mm)
TMP Ref1 49.5 2.7 32.3 ?1.6
TMP Ref2 54.3 3.2 54.0 ?1.6
TMP HP3Fe 3 33 48.0 2.5 40.6 ?1.5
TMP HP4Fe 3 37 49.2 2.6 41.1 ?1.5
1Based on TMP reference (TMP Ref1And TMP Ref2) energy consume resulting energy saving.
2Measure average (length weighting) fibre length with Kajaani FS-100 fiber size analyzer.
3Produced according to the invention.
According to program of the present invention, use just to be higher than 2 weight % hydrogen peroxide as can be seen from Figure 5, can save energy in a large number up to 37% (under the free level of 100ml CSF).(tensile figure TEA) is better than or equals TMP the strength character of gained paper pulp Ref1The strength character of (referring to table 5-6) does not obtain the fibre length and the fiber width (referring to Fig. 2-3) of variation.It is significant saving the possibility that the strength character of the electric energy of this amount and gained paper pulp do not lose.
Embodiment 4
Norway spruce (Picea abies) timber is used to produce hot method mechanical pulp (TMP).Preheat with defibrination operation before, with log peeling and chopping and washing.Use 20 inches pressurized refiner (the OVP-MEC type is operated under 1500rpm) to produce high free value paper pulp (about 540ml CSF).Energy is input as about 1150kWh/ utmost point dry metric ton (bdmt) in fiberizer.Activator and oxidant are added in the defibrated pulp in the blender (Electrolux BM 10S), immediately further defibrination in wing formula fiberizer.In paper pulp, at first add activator, add oxidant subsequently.The incorporation time of activator and oxidant is 30 seconds.Handle reference paper pulp (TMP in an identical manner Ref3), difference is deionized water is added in the blender to obtain the identical pulp thickness with the paper pulp of handling according to the present invention.The reason of doing like this is that well-known is that pulp thickness influences gained pulp property and the consumption of defibrination energy.Then paper pulp is transferred to wing formula fiberizer with further processing.
Wing formula fiberizer is a laboratory installation, for fixing free level, compares with industrial fiberizer, because its less size, energy consumes higher.
Each defibrination series of describing in following embodiment produces according to said procedure.
TMP reference (the TMP in figure below and the table Ref3) do not add chemicals and generation as mentioned above.Beating degree (free value) as the function of particular energy consumption (SEC) can be as can be seen from Figure 6.
Acid hydrogen peroxide (H used according to the invention 2O 2) preparation TMP by add the copper sulphate (CuSO of 0.13 weight % based on utmost point desiccated wood weight 4* 5H 2O) and the hydrogen peroxide (H of 2.0 weight % 2O 2) paramount free value paper pulp and producing.The pH of gained paper pulp is 3.5.This paper pulp is labeled as TMP in Fig. 6 HP5Cu
Fig. 6 is to reference (TMP Ref3) and paper pulp (TMP produced according to the invention HP5Cu) the free value as the function of particular energy consumption (SEC) described.Obtained significant energy saving for paper pulp produced according to the invention as can be seen from Figure 6.For constant free level (175ml CSF), TMP HP5CuThan reference paper pulp (TMP Ref3) the energy of consuming little energy 37%.For TMP HP5CuWith 2.0 weight % (based on utmost point desiccated wood) H 2O 2With 0.13 weight % (based on utmost point desiccated wood) CuSO 4* 5H 2O has obtained energy saving.
Reference (TMP Ref3) and paper pulp (TMP produced according to the invention HP5Cu) average fiber length (under 175ml CSF) with pulp quality controller PQM1000 apparatus measures be respectively 1.7mm and 1.8mm, the reduction of fibre length does not promptly take place.
Embodiment 4 shows by using copper sulphate to obtain significant energy saving as activator and hydrogen peroxide as oxidant according to method of the present invention.
Embodiment 5
Picea mariana timber is used to produce hot method mechanical pulp (TMP).Before preheating (4.14 crust steam pressures, the 40s time of staying) and defibrination operation, with log peeling and chopping and washing.Use single-deck 36 " the high free value paper pulp (about 750mlCSF) of pressurized refiner (the 36-1CP type is operated under 1800rpm) production.Energy is input as about 500kWh/ utmost point dry metric ton (bdmt) in fiberizer.Then, activator and oxidant are added in the defibrated pulp in the blender (Electrolux BM 10S), immediately further defibrination in wing formula fiberizer.In paper pulp, at first add activator, add oxidant subsequently.The incorporation time of activator and oxidant is 30 seconds.Handle reference paper pulp (TMP in an identical manner Ref4), difference is deionized water is added in the blender to obtain the identical pulp thickness with the paper pulp of handling according to the present invention.The reason of doing like this is that well-known is that pulp thickness influences gained pulp property and the consumption of defibrination energy.Then paper pulp is transferred to wing formula fiberizer with further processing.
Wing formula fiberizer is a laboratory installation, for fixing free level, compares with industrial fiberizer, because its less size, energy consumes higher.Well-knownly be, compare that less fiberizer has higher energy consumption with bigger fiberizer.
Each defibrination series of describing in following embodiment produces according to said procedure.
TMP reference (TMP Ref4) do not add chemicals and generation as mentioned above.Beating degree (free value) as the function of particular energy consumption (SEC) can be as can be seen from Figure 7.
Only add oxidant (H 2O 2) and the TMP that do not add activator or reinforcing agent production by add the hydrogen peroxide (H of 1.0 weight % based on utmost point desiccated wood weight 2O 2) paramount free value paper pulp and producing.The pH of gained paper pulp is 4.0.This paper pulp is labeled as TMP in Fig. 7 HPref
Acid hydrogen peroxide (H used according to the invention 2O 2) preparation TMP by add the ferric sulfate (FeSO of 0.02 weight % based on utmost point desiccated wood weight 4* 7H 2O) and the hydrogen peroxide (H of 1.0 weight % 2O 2) paramount free value paper pulp and producing.The pH of gained paper pulp is 3.9.This paper pulp is labeled as TMP in Fig. 7 HP6Fe
Acid hydrogen peroxide (H used according to the invention 2O 2) preparation TMP by add the ferric sulfate (FeSO of 0.08 weight % based on utmost point desiccated wood weight 4* 7H 2O) and the hydrogen peroxide (H of 1.0 weight % 2O 2) paramount free value paper pulp and producing.The pH of gained paper pulp is 3.8.This paper pulp is labeled as TMP in Fig. 7 HP7Fe
Acid hydrogen peroxide (H used according to the invention 2O 2) preparation TMP by add the ferric sulfate (FeSO of 0.14 weight % based on utmost point desiccated wood weight 4* 7H 2O) and the hydrogen peroxide (H of 1.0 weight % 2O 2) paramount free value paper pulp and producing.The pH of gained paper pulp is 3.7.This paper pulp is labeled as TMP in Fig. 7 HP8Fe
Fig. 7 is to reference paper pulp (TMP Ref4And TMP HPref) and paper pulp (TMP produced according to the invention HP6Fe, TMP HP7FeAnd TMP HP8Fe) the free value as the function of particular energy consumption (SEC) described.Obtained significant energy saving for paper pulp produced according to the invention as can be seen from Figure 7, and when only having hydrogen peroxide (oxidant) (TMP HPref), do not obtain energy saving.For constant free level (175ml CSF), paper pulp produced according to the invention is than reference paper pulp (TMP Ref4And TMP HPref) consuming little energy 10% (TMP HP6Fe), 15% (TMP HP7Fe) and 33% (TMP HP8Fe) energy.For TMP HP6Fe, with 1.0 weight % (based on utmost point desiccated wood) H 2O 2With 0.02 weight % (based on utmost point desiccated wood) FeSO 4* 7H 2O has obtained energy saving.For TMP HP7FeAnd TMP HP8Fe, the reinforced 1.0 weight %H that are respectively of corresponding chemicals 2O 2/ 0.08 weight %FeSO 4* 7H 2O and 1.0 weight %H 2O 2/ 0.14 weight %FeSO 4* 7H 2O.
Reference paper pulp TMP Ref4Average fiber length (under 175ml CSF, measuring) with KajaaniFS-100 fiber size analyzer be 1.7mm, be 1.7mm (TMP for paper pulp produced according to the invention HP6Fe), 1.7mm (TMP HP7Fe) and 1.6mm (TMP HP8Fe).Obviously because of chemical treatment of the present invention significant fiber not taking place shortens.
Can obviously find out from Fig. 7 and data above and only to add oxidant such as H 2O 2Be not enough to reduce the consumption of defibrination energy.Therefore must add activator, this makes the method for the invention be guaranteed.
Embodiment 6
Poplar (Populus tremula) timber is used for production preheating method wood chip chemi-mechanical pulp (CTMP).Preheat with defibrination operation before, with log peeling and chopping and washing.Use 20 inches pressurized refiner (the OVP-MEC type is operated under 1500rpm) to produce high free value paper pulp (about 42ml CSF).Energy is input as about 1450kWh/ utmost point dry metric ton (bdmt) in fiberizer.Then activator and oxidant are added in the defibrated pulp in the blender (Electrolux BM 10S), immediately further defibrination in wing formula fiberizer.In paper pulp, at first add activator, add oxidant subsequently.The incorporation time of activator and oxidant is 30 seconds.Handle reference paper pulp (CTMP in an identical manner Ref), difference is deionized water is added in the blender to obtain the identical pulp thickness with the paper pulp of handling according to the present invention.The reason of doing like this is that well-known is that pulp thickness influences gained pulp property and the consumption of defibrination energy.Then paper pulp is transferred to wing formula fiberizer with further processing.
Wing formula fiberizer is a laboratory installation, for fixing free level, compares with industrial fiberizer, because its less size, energy consumes higher.Well-knownly be, compare that less fiberizer has higher energy consumption with bigger fiberizer.
Each defibrination series of describing in following embodiment produces according to said procedure.
TMP reference (CTMP Ref) do not add chemicals and generation as mentioned above.Beating degree (free value) as the function of particular energy consumption (SEC) can be as can be seen from Figure 8.
Acid hydrogen peroxide (H used according to the invention 2O 2) preparation CTMP by add the ferric sulfate (FeSO of 0.14 weight % based on utmost point desiccated wood weight 4* 7H 2O) and the hydrogen peroxide (H of 2.0 weight % 2O 2) paramount free value paper pulp and producing.The pH of gained paper pulp is 3.8.This paper pulp is labeled as CTMP in Fig. 8 HPFe
Fig. 8 is to reference paper pulp (CTMP Ref) and paper pulp (CTMP produced according to the invention HPFe) the free value as the function of particular energy consumption (SEC) described.Obtained significant energy saving for paper pulp produced according to the invention as can be seen from Figure 8.For constant free level (175mlCSF), CTMP HPFeConsumption rate reference paper pulp (CTMP Ref) the energy of consuming little energy 32%.For CTMP HPFe, with 2.0 weight % (based on utmost point desiccated wood) H 2O 2With 0.14 weight % (based on utmost point desiccated wood) FeSO 4* 7H 2O has obtained energy saving.
Reference paper pulp (CTMP Ref) average fiber length (under 175ml CSF) with pulp quality controller PQM 1000 apparatus measures be 0.95mm, for paper pulp (CTMP produced according to the invention HPFe) be 0.94mm.Obviously because of chemical treatment of the present invention significant fiber not taking place shortens.
Can find out obviously that from embodiment 6 described results for poplar preheating method wood chip chemi-mechanical pulp, the inventive method has also produced significant energy saving and do not had cut staple in the defibrination process.
Reference numeral
In the accompanying drawings, use following unit and term:
Fig. 1,4-8: on vertical Y-axis, be the free value that provides with ml CSF (Canadian Standard Freeness), the SEC on the X-axis of level (particular energy consumption) measures with kWh/bdt.
Fig. 2 and 3: the total length ratio is 1/1000 on vertical Y-axis, and on the X-axis of level, fibre length is represented (Fig. 2) with mm; Fiber width is represented (Fig. 3) with μ m.

Claims (12)

1. prepare the method for high-yield pulp, it comprises:
A) by comprising at least a non-enzymatic catalysis oxidant and activator and not containing oxidation system chemical treatment lignocellulose-containing materials under 2 to 6.5 pH of ozone and chlorine dioxide substantially, wherein said non-enzymatic catalysis oxidant is selected from peralcohol, Halogen oxidant, oxygen, nitrogen oxide or its combination, and described activator is selected from metal ion, TAED, cyanamide or its combination; With
B) the lignocellulose-containing materials mechanical treatment is enough to produce time of high-yield pulp, wherein before any mechanical treatment section and/or among the chemical treatment lignocellulose-containing materials, and wherein not with lignocellulose-containing materials section a) and b) between chemical treatment under 11.5 to 14 pH.
2. according to the process of claim 1 wherein that pH is 2.5 to 6.
3. according to the method for claim 1 or 2, wherein pH is 3 to 5.5.
4. according to the method for claim 1 or 2, wherein said high-yield pulp is mechanical pulp, RMP, ground wood pulp, chemi-mechanical pulp, semi-chemical pulp, hot method mechanical pulp and/or preheating method wood chip chemi-mechanical pulp.
5. according to the method for claim 1 or 2, wherein said lignocellulose-containing materials comprises not defibrated wood.
6. according to the method for claim 1 or 2, wherein said lignocellulose-containing materials comprises the lignocellulose-containing materials of mechanical treatment.
7. according to the method for claim 1 or 2, wherein this method comprises two or three mechanical treatment sections and described oxidation system is applied between two mechanical treatment sections.
8. according to the method for claim 1 or 2, wherein said lignocellulose-containing materials comprises cork and/or hardwood.
9. according to the method for claim 1 or 2, wherein said non-enzymatic catalysis oxidant is a hydrogen peroxide.
10. according to the method for claim 1 or 2, wherein said metal ion is selected from transition metal ions.
11. according to the method for claim 1 or 2, wherein said oxidation system further comprises and is selected from nitrogenous polycarboxylic acid; nitrogenous polyphosphonic acid; nitrogenous polyalcohol; oxalic acid; oxalates; the glycol hydrochlorate; ascorbic acid; citric acid; the nitrilo-acetate; gallic acid; fulvic acid; itaconic acid; hemoglobin; hydroxy benzenes; catechol; quinoline; dimethoxybenzoic acid; dihydroxy-benzoic acid; dimethoxy-benzyl alcohol; pyridine; the histidyl-glycine; phthalocyanine; acetonitrile; 18-hat-6-ether; mercapto succinic acid; cyclohexadiene; the reinforcing agent of polyoxometallate and combination thereof.
12. according to the method for claim 1 or 2, wherein said oxidation system further comprises the reinforcing agent that is selected from EDTA, DTPA, NTA or its combination.
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