CN101548046A - A method of preparing bleached pulp with high yield by free radical cleanness kraft process - Google Patents
A method of preparing bleached pulp with high yield by free radical cleanness kraft process Download PDFInfo
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- CN101548046A CN101548046A CN200680054907A CN200680054907A CN101548046A CN 101548046 A CN101548046 A CN 101548046A CN 200680054907 A CN200680054907 A CN 200680054907A CN 200680054907 A CN200680054907 A CN 200680054907A CN 101548046 A CN101548046 A CN 101548046A
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- Prior art keywords
- free radical
- acid
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- bleached pulp
- oxygen
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- 150000003254 radicals Chemical class 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 59
- 230000008569 process Effects 0.000 title abstract description 26
- 239000002655 kraft paper Substances 0.000 title abstract description 5
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- 238000003487 electrochemical reaction Methods 0.000 claims description 21
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- 238000004537 pulping Methods 0.000 claims description 19
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Classifications
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- 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
- D21C3/00—Pulping cellulose-containing materials
- D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
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Abstract
A method of preparing bleached pulp with high yield by free radical cleanness kraft process, which includes providing electrons to the reactive medium in the electrochemical vessel by electrodes as the pH is subacidity. And put oxygen and/or nitrogen into the reactive vessel, and at the same time add chelating agent, cellulose protectant and free radical stabilizer to the reactive vessel. So as to field a great variety of free radical and to separate the lignin from it, thus bleached pulp is obtained.
Description
A kind of method invention field of preparing bleached pulp with high yield by free radical cleanness kraft process
The method that oar technology processed prepares high yield pulp1 bleached pulp is cleaned the invention discloses a kind of free radical.More specifically understand a kind of without alkali, chlorine, sulphur and anthraquinone, a kind of free radical only formed with oxygen through electrochemical reaction appts is the method that the mechanism of action prepares cleaning and bleaching paper pulp.Background of invention
It is well known that world today's pulping and paper-making industry faces three major issues：Raw material is in short supply, technique falls behind, seriously polluted, and this is the urgent problem that global whole paper industry is faced.
Paper making raw material is in short supply for a long time, not it is a certain area and refer to the whole world and make Paper industries.Forest is the lung of life on earth, the water source that shows self restraint, prevent erosion, regulate the climate, absorbing carbon dioxide manufactures the effect of oxygen, forest not only has the ecological value and with economic value.But former world area of woods according to statistics report just with annual Ι δ Ο Ο Ο Ο Km by data2Speed reduce, tropical rain forest is with 0.5 Km per minute2Speed reduce.
China belongs to the country of serious scarce material Shaolin, and area of woods only has 1/5th of world average level per capita（0.128 hm2), forest reserves is only 1/8th (9.05 m of world average level per capita3) .China Forest statistical yearbook 1999 was compared with 2000, forest rate of descent：Ten big ecological projects related to the forestry industry -12.9%, natural forest reserve engineering -
10.07%, area -6.33% of closing hillsides to facilitate afforestation, shelter-forest -24.75%, economic forest -3.82%, Timber stands -14.07%.
Non-wood fibrous raw material, as rice wheat straw, cotton stalk, hybrid giant napier, banana stem, bast fiber etc., utilization rate is not enough or not make full use of be also a major reason for causing raw material in short supply.
Published according in July, 1998《Chinese biological matter resource availability is evaluated》The latest data of one book shows that China's agricultural crop straw yield was in 19956.04 hundred million tons, wherein 1.40 hundred million tons of wheat-straw, 1.15 hundred million tons of straw, ten thousand tons of Cotton Stalk 1^0,6,450,000 tons of bagasse.In addition to straw directly returning to field and collection loss account for 15.0%, stalk availability is 5.134 hundred million tons, account for total amount 2.3% for papermaking.
Counted according to 1997, rice wheat straw, reed, bagasse, bamboo account for paper grade (stock) non-timber
The 90% of raw material total amount.The ratio such as following table of annual production and the slurrying of main non-wood material：Raw material type gross annual output amount（Million tons）Ratio for slurrying（%) wheat straw 102 17
Straw 200 2
Reed 2.83 70
Bagasse 16 4
10/China of bamboo is that a large agricultural country is a Ge Chan cottons big country again, about 1.6 hundred million tonnes of the year production-goods source that can be compared favourably with timber.China " 15;, planning period, national emphasis cotton growing area cultivated area is stable at 6,000,000 hectares within 2010; annual high-quality 34,200,000 tons of cotton stalk; calculated by the data in book of teaching, only one 2428.2 ten thousand tons of paper pulp of annual output of cotton stalk, and such as utilization rate is up to 30%; can produce more than 740 ten thousand tons every year; the summation of quite annual pulp inlet, this annual resource similar to leaf wood, and utilization rate is less than 1 % so far.
China Light Industry Press, publishes for 2001《Plant Fiber Chemistry》Teaching material, discloses cotton stalk raw material chemical analysis（Weight %) and average fiber it is long（Mm data), its result see the table below：
Novel material hybrid giant napier, is grass that is perennial, uprightly growing thickly, and English name Hybrid Giant Napier, scientific name Ponnisetum hydridum are formed by South America napier grass and Chinese pennisetum selection cross, because yield height is occupied first of herbage.China is successively
Introduced in 1980s from Colombia, plant after reed must succeed, progressively promote from south to north, successively in the provinces and cities such as Sichuan, Hunan, Jiangsu, Tianjin, Guizhou, Shaanxi introduction of plant in Hainan.It is demonstrated experimentally that hybrid giant napier has the features such as strong adaptability, plantation are simple, yield is high, content of cellulose is high.The chemical constituent of hybrid giant napier is analyzed and compares such as following table with the composition of wheat straw, reed, Fast growth poplar（%)：
Note：* it is contrast cellulose.
The harvest area of World banana in 2003 is 454.47 ten thousand hectares, and 439.27 ten thousand hectares than 2002 add 15.20 ten thousand hectares.The maximum country of banana harvest area is India, is 62.00 ten thousand hectares, accounts for the 13.64% of the whole world harvest gross area;Next to that 51.32 ten thousand hectares of Brazil, accounts for 11.29%;The harvest area of other major producing countries is respectively：40.00 ten thousand hectares of Philippine；Indonesia34.500000 hectares；China23.500000 hectares；21.87 ten thousand hectares of Ecuador；13.90 ten thousand hectares of Thailand；Ten thousand hectares of Vietnam 9.ST7；7.26 ten thousand hectares of Mexico；6.20 ten thousand hectares of Papua New Guinea；The public item of Madagascar 5.00 ten thousand.
China is one of major country of world banana production, and Guangdong, Guangxi, Fujian, Hainan, Yunnan, Taiwan are main producing region, the public affairs of 2000 Annual planting area 24.9 ten thousand Are.Wherein Guangdong accounts for the national mat woven of fine bamboo strips one, reaches 10.1 ten thousand hectares, Gaozhou county and middle mountain are its famous banana place of production；Guangxi second, is 5.97 ten thousand hectares, is mainly distributed on the ground such as Nanning Suburb, Pubei, the Lingshan, Tianyang County, Longan, Tiandong County, Longzhou, based on fragrant tooth any of several broadleaf plants and dwarf banana；Fujian the 3rd, is 3.5 ten thousand hectares, is distributed mainly on ZhangZhou and Longhai City, based on any of several broadleaf plants of Tian Bao；Hainan mat woven of fine bamboo strips four, is 3.3 ten thousand hectares, is mainly distributed on Danzhou, east, happy east etc.
Ground, based on fragrant tooth any of several broadleaf plants；^ south is mainly distributed on the ground such as river mouth, Yuanyang and Xishuangbanna, based on fragrant tooth any of several broadleaf plants.
Bast fiber raw material includes two classes, is bark first, because containing more fiber in the cortex of part trees, there is good papermaking value, such as ramulus mori bast fiber accounts for the 26% ~ 30% of full stalk gross weight, is a kind of high-quality paper making raw material, ramulus mori bast fiber portion lignin content is relatively low.Another kind of is crudefiber crop.This kind of raw material by many factors due to being restricted, and the utilization rate in terms of pulping and paper-making is extremely low.
Paper industry is still using the traditional paper-making process before more than 100 years, largely using strong acid, highly basic, strong chlorine, strong sulphur and anthraquinone, discharges black liquor, CODCrUp to 180000 mg/L, and technological process is long, process equipment falls behind relatively, and equipment investment is big, expenses of environmental protection is high.
At the beginning of oxidation bleaching can trace back to for the 50's.The Soviet Union wood woods chemist Nikieih and ARim have found that oxygen can be bleached first within 1952.After 12 years, French scientist Rebeve in 1964 et al. can protect cellulose not oxidative degradation with magnesium salts.U.S., method, auspicious three state successively set up laboratory within 1970, the same year South Africa Enstrd sets up first ClO 2 bleaching workshop in the world, the U.S. in 1972 sets up 12 tons of oxygen bleaching workshops of daily output, and apply for chlorine-free bleaching patent, after do not enter industrialization because of factors such as cellulose loss is big, power consumption, water consumption height, product costs.After 27 years, French George's rood company in 1999, Pu Weisaier companies of the U.S. in 2001 successively start with chlorine dioxide with ozone and with bleaching again, still do not break away from the pollution of chlorine, and the true bright chlorine of scold can form carcinogenic substance (such as through heated：Chloroform, carbon tetrachloride, chloroform etc.）.End in March, 2002, global paper industry does not leave alkali, chlorine, sulphur, the spherical digester of anthraquinone severe contamination, bleaching tower process all the time；Processing to lignin chromophore was still rested on before more than 100 years in the traditional handicraft for separating xylogen degradation.Even there are many national developments in recent years to soda-aq cooking is used without restraint, because of the condensed-nuclei aromatics in anthracene system arene, all condensed-nuclei aromatics have been identified carcinogenesis at present, are included in carcinogenic substance by environmental protection organization of the world already.Therefore, global papermaking had turned into the target that environmental protection organization pays close attention to already.
Conventional process flow is long, uses：Get the raw materials ready → immersion → add the drift → bis- of → bis- mill of the mill of decoction → boiling → pulp washing → mono--mono- to float → tri- drifts → secondary washing slagging-off alkali collection water process screening purification-into slurry, which results in traditional process equipment investment is big.
Countries in the world is mitigate the pollution of pulping industry, and the patent declared over more than 30 years has tens, such as：Paper pulp multistage bleaching alkali process singlet oxygen reinforcing bleaching formulation and work that CN1142555A Nanjing of China Forestry University disclosed in 2 months 1997 12 EJ is invented
Skill, 19993The ozone of the French L'air Liquide Service Brevets ＆ Marques's inventions of CN1212310A disclosed in the moon 31 and the method for ClO 2 bleaching paper pulp,The double-reactor Oxygen Delignification of Fast-Growing of the Sweden Gruvon factories invention of autumn in 1999,Say the method that activated ozone is applied in association with pulp bleaching of Placer Technology Co., Ltd of disclosed CN1297085A U.S. invention in May 30 in 2001,Found the use maize straw of university's invention and the pulping process of other non-wood-fiber materials in CN1371439A North Carolinas disclosed in September in 2002 25 days,DE10126988A1 disclosed in 12 days December in 2002,What CN1407172A Amada Co., Ltd.s disclosed in 2 days April in 2003 were apt to greatly invention is raw material production paper pulp and preparation system device with timber,A kind of free of contamination papermaking paste-making method of Chinese disclosed CN1198492 Shandong Changwei Normal Vocational School invention,The pulping process and CN1458075 of CN1229155-kind of alkali-free-kind more than metal acid-salt electrochemical bleaching pulp technology,The APMP preparation method of the disclosed CN1554827 Shandong Huatai Group Co Ltd invention of EI China December 15 in 2004,The production method of disclosed CN1563564-kind of the chemical wood pulp of China's on January 12nd, 2005,May 4 in 2005 the disclosed CN16116 of EI China73 journeys clean pulping catalyst and its technique for applying that mutually force is invented, disclosed CN1718919-kind of the method that bleach chemical pulp is prepared by cotton stalk of China's on January 11st, 2006, the disclosed CN1737255 paper oar cleaning and bleaching process of the China of the same year 2 month 22 etc..
Above-mentioned all patents of invention have plenty of chlorine-free bleaching through reading carefully, have plenty of reduction alkali, chlorine, the consumption of sulphur, have plenty of and substitute chlorine with ozone, have plenty of and use caustic soda and anthraquinone, peroxy acid, and what is had simply improves technical process.Cut-off is said only April 30 in 2006, and the whole world does not have any one without acid, alkali, chlorine, sulphur, anthraquinone delignification, and thoroughly Parties acid, alkali, chlorine, sulphur, anthraquinone pulping process are taken without any one.Want the pollution of the elimination pulping and paper-making industry from source, must just break away from alkali-free not into the theory constraint of slurry, find new slurrying theoretical.
German scholar K.Freudenberg etc. draws a conclusion on the Research foundation of Phytochemistry and phytotomy：Lignin originates from the parent of lignin, and this lignin parent is present in the glucoside form of body propane.This parent separates out glucose under enzyme effect, and remaining loose primary alconol etc. passes through polymerization, a kind of adhesivity material being deposited in cell membrane and intercellular layer is formed, here it is lignin.
Polymerisation between lignin building unit, mainly combines to form the methylene quinone structure of dimer by being formed between free radical, free radical, then added into methylene quinone
H20th, the addition reaction such as lignin building unit, sugar is completed.That is, in the presence of the hydrogen peroxide and peroxidase that are generated first on cell membrane, lignin building unit is dehydrogenated, generation phenol free radical and its resonating body, is be combined with each other between these free radicals, is formed dimer.These dimers also further dehydrogenation turn into free radical, and then with other free radical combine, repeatedly enter water-filling and the addition reaction of lignin building unit, lignin is converted into macromolecule.
The biosynthetic process of I Π ffl IV V lignins compares with the biosynthetic process of other natural polymers, its outstanding feature is, in its final stage, after free radical is formed, effect just with enzyme is unrelated, any combination between free radical and form lignin macromolecule.It is known that chemical reaction is understood with the origin that invertibity has understood lignin biological synthesis, lignin macromolecule degraded or chain grafting is set to be only optimised process using free-radical theory.
Therefore, only start it is new from source without acid, alkali, chlorine, sulphur, anthraquinone delignification pulping process, severe contamination of the pulping and paper-making industry to environment could be solved.The present invention is for the purpose of solving the above problems.The content of the invention
One aspect of the present invention provides a kind of method that high yield pulp1 bleached pulp is prepared with free radical clean technologies, comprises the following steps：Add organic solvents into the electrochemical reaction kettle containing reaction mass and water, the pH for making the reaction medium in the electrochemical reaction kettle is faintly acid；Electronics is provided by reaction medium of the electrode into be confused electrochemical reaction kettle；Oxygen and/or nitrogen are passed through into the electrochemical reaction kettle, and adds the plain protective agent of chelating agent, Yu dimensions and free radical stabilizer, the lignin in the reaction mass is separated with producing various free radicals；It is derived from bleached pulp.
According to a preferred embodiment of the invention, nitrogen and oxygen in the reaction medium
The concentration of gas is respectively 1 ~ 15 mg/m3。
According to another preferred embodiment of the present invention, the pH values of the reaction medium are between 3 ~ 6.9, preferably between 3.8-5.8.
According to another preferred embodiment of the present invention, the organic solvent is selected from the group being made up of following member：Dimethyl sulfoxide (DMSO), acetic acid, ethyl acetate, ether, Peracetic acid, benzoyl peroxide, nitric acid, oxalic acid and the mixture of two or more in them.
According to another preferred embodiment of the present invention, the free radical stabilizer is selected from the group being made up of following member：Ethylene oxide, dimethyl diepoxy second protective embankment, acetone and ethanol class.Particularly preferred free radical stabilizer is FRS, Na4P207、 Na5P30le、 3MgO · 4Si02 · H20、 H2Si2Os、 Mg2And DMD.
According to another preferred embodiment of the present invention, described free radical is selected from the group being made up of following member：Ultra-oxygen anion free radical（OJ ultra-oxygen anion free radical), is protonated（HOO), hydroxyl radical free radical（OH), NO free radical（NO ' 、 N02), methyl free radicals（ · CH3), quinones free radical（Q), alkanes free radical（R), alkoxy free group（)) and Lipid Free Radicals IX（LOO · ) .
According to another preferred embodiment of the present invention, described reaction mass is from needlebush, leaf wood, grass family stalk fiber, bast fiber, leaf fibre or kind hide fiber.
According to another preferred embodiment of the present invention, described cellulose protective agent is selected from the group being made up of following member：Magnesium sulfate, magnesium carbonate, magnesia, sodium pyrophosphate, sodium dihydrogen phosphate and the mixture of two or more in them.
According to another preferred embodiment of the present invention, described chelating agent is selected from the group being made up of following member：The ammonium pentaacetic acid of divinyl three（DTPA), b diammonium edta (EDTA), sodium citrate, opal, zeolite, sodium tripolyphosphate, polyoxyethylene alkyl ether and the mixture of two or more in them.Particularly preferred chelating agent is opal or sodium tripolyphosphate.
Another aspect of the present invention provides the bleached pulp obtained by the above method.
The essence that the present inventor synthesizes from lignin biological, has invented a kind of method of use free radical slurrying, and ultra-oxygen anion free radical is protonated through description of test（HOO carbohydrate cellulose) is not damaged under mildly acidic conditions, so as to greatly improve pulping yield.The success of the experiment will bring new theory to pulping and paper-making industry, so as to finish alkali-free not into the history of slurry, break traditions spherical digester, bleaching tower, the alkali collection of pulping process, three big workshop sections, the disposable manufacture bleached pulp in bleaching integrated electric reactor is taken off.
Through national departments concerned, the detection present invention is no pollution industrial wastewater CODCrThan the mg/L of traditional chemical sizing process 14 ~ 180,000 compared to 60 ~ 90 times of reduction, 80% water is capable of self-circulating to be reused, economize on electricity 40%, reduces investment outlay 40 ~ 50%.Pulping and paper-making is solved because technology backwardness causes the matter of great urgency that raw material is in short supply, seriously polluted, environmental protection pressure is big so as to effect a radical cure pollution.Embodiment
The invention discloses a kind of method of use preparing bleached pulp with high yield by free radical cleanness kraft process, this method oxygen（02) in the presence of organic solution, receive to electronically form the ultra-oxygen anion free radical of first atom centered on oxygen in electrochemical reaction kettle（Of), the free radical has unique physicochemical properties, and the free radical of various groups can be generated under different reaction conditions, and it is considered as an alkali in water, receives the protonation ultra-oxygen anion free radical of a H+formation（HOO) be Ο free radicals conjugate acid, the equilibrium valve Ρ Κ of water are 4.8.Of/HOO concentration can be changed by changing ρ Η values.Traditional pulping process will but go to obtain the 0 of damage cellulose in alkalescence, because their nature differences of C^/HOO are very big, Of negatively charged is hydrophilic radical, it is impossible to penetration cell interbed, is a kind of reducing agent under the conditions of a lot.And Η Ο Ο neutrals are hydrophobic groupings, can be with penetration cell interbed, and gathered in hydrophobic region, it is a kind of strong oxidizer, it can be broken the big pi bond on lignin phenyl ring and side chain, and lignin degradation dissolution is further oxidized to colourless dicarboxylic acids dissolution, high whiteness cellulose is obtained, carbohydrate is not damaged in faintly acid --- cellulose.Occurs disproportionated reaction when two free radicals meet, such as in free radical stabilizer such as FRS, Na4P207 、 Na5P3O10 、 3MgO · 4Si02 · H20、 H2Si205、 Mg2With in the presence of DMD etc., electronics is under the conduction of metal ion, and electron donor can accelerate 10 ~ 40 times of transmission speed, and electron donor is faster, and free radical yield is higher, and stability is better.
Here be reaction medium obtain formed after electronics free radical, in electrochemical reaction kettle free radical and phenyl ring and chromophore reaction mechanism：
+e
02 HOO,
+e
2¾0 ' H20+ + Η20· +2e 0· Η· + ·ΟΗ
Η + Η20—— ^ Η30+ + ·ΟΗ
·ΟΗ +Η202 ► ΗΟΟ· + Η20
Ο^· +。3 02 + 03:
03 + Η+ ► Η03·
Ν2 + 0; +e
♦ 2NO'
It can react to form new reaction medium and freedom simultaneously between above-mentioned various free radicals, free radical also may occur from the disproportionated reaction of hair property each other, such as：
Free radical delignification mechanism（By taking Η Ο Ο as an example）It is as follows:
The electrode that protonation ultra-oxygen anion free radical takes off used in the reaction mechanism present invention of non-phenolic lignin in faintly acid can be conventional electrode familiar to those skilled in the art.Particularly preferred electrode is the compound electrodes such as nano active carbon electrode, enzyme electrode, mercury electrode, rare earth element electrode, high score sub-electrode, miscellaneous many metal salt electrodes, nickel, titanium, neodymium, lithium, platinum, cobalt, bismuth, lead.
Free radical stabilizer of the present invention is the material for referring to stablize the free radical produced in course of reaction, such as, but not limited to, alkylene oxides（FRS), dimethyl ethylene oxide, acetone, ethanol class；Particularly preferred free radical stabilizer is FRS, Na4P207、 Na5P3O10、 3MgO · 4Si02 H20、 H2Si2Os、 Mg2With DMD etc..
Cellulose protective agent of the present invention is to refer to protect cellulose to be allowed to the material not being damaged during the course of the reaction; for example; but be not limited to, magnesium sulfate, magnesium carbonate, magnesia, sodium pyrophosphate, sodium dihydrogen phosphate, and two or more in them mixture.Particularly preferably carbonic acid Mo.
Chelating agent of the present invention is：The ammonium pentaacetic acid of divinyl three（DTPA), b diammonium edta（EDTA), sodium citrate, opal, zeolite, trimerization upright stone tablet sour sodium, polyoxyethylene alkyl ether and the mixture of two or more in them.Particularly preferred chelating agent is opal and sodium tripolyphosphate.
Reaction medium of the present invention refers to Jie's shield reacted in a kettle., for example, can include water, organic solvent, free radical stabilizer, reaction mass（Pulping raw material）
Deng.
Organic solvent of the present invention refers to liquid organic material, such as, but not limited to, dimethyl sulfoxide (DMSO), acetic acid, ethyl acetate, ether, Peracetic acid, benzoyl peroxide, nitric acid, oxalic acid and the mixture of two or more in them.
Reaction mass of the present invention refers to the biomass fiber materials containing fiber for having pending bleaching, and it can come from, for example：Needlebush（Dragon spruce, masson pine, larch etc.）, leaf wood（Poplar, Eucalyptus, willow, mulberry etc.）, grass family stalk fiber（Straw, wheat straw, reed, bamboo etc.）, bast fiber（Hemp, banana fiber crops, pineapple fibre etc.）, leaf fibre（Chinese alpine rush, pineapple leaves etc.）, plant hide fiber（Cotton, cotton linter etc.）Deng.
Faintly acid of the present invention refers to pH value between 3 ~ 6.9, preferably 3.8 ~
5.8。
Holocellulose of the present invention refers to the fiber and hemicellulose of raw material.
According to the specific embodiment of the present invention, this method includes following process：Get the raw materials ready, rubbing sub-wire cleans material, pretreatment；Material is inputted by electrochemical reaction kettle by conveying worm, connection power supply in kettle is started；Nitrogen 5min is inputted into kettle, the min of oxygen 10 ~ 25 is inputted, reaction is situated between mediocre middle nitrogen, oxygen concentration for 1 ~ 15mg/m3, plus cellulose protective agent, chelating agent, free radical stabilizer；Free radical is 40 ~ 60min with material reaction total time;Spurt discharging, slurry qi leel from；Frequent regulation slurry fine grinding, remove the gred, Qian, Return choosing that disappears, into slurry；All workshop section's waste water enter water treatment system and used again through handling Posterior circle.
The rubbing sub-wire of getting the raw materials ready refers to that raw material is through conventional microtome（Wood chip length and width are respectively 18 ~ 25mm, 3 ~ 6mm of thickness), clean in input rubbing devillicate machine, material is twisted into after velvet shape, into preheating infuser, pretreatment condition is pressure 0.3MPa, temperature 60 ~ 80, pH value 38 ~ 5.8.
Oxalic acid, nitric acid, Peracetic acid for adjusting acid used in pH value to prepare etc., consumption is defined by pH value faintly acids, and dip time is 15 ~ 30min, dehydration Hou Ruxia workshop sections.
Upper workshop section's material is inputted into electrochemical reaction kettle with feeding screw, it is reaction medium that kettle inner anode, which be connected organic solvent in electric discharge, water and water, material with kettle external power, and still shell body is negative electrode.
The min of nitrogen 5 is inputted to stop；It is 1 ~ 15 mg/m to input nitrogen, oxygen concentration in oxygen, reaction medium again3, free radical stabilizer, reaction temperature are inputted under equal pressure
During to 140, compression pump input H202, while inputting Mg2+、 Na5P3O10It is used as H202Stabilizer, first set reaction condition be nitrogen, oxygen input after, 90 ~ 120 °C of temperature, 0.3 ~ 0.6MPa of pressure, pH value 3.8 ~ 48.Second is that pressure rises to 0.8 ~ 1.2 MPa in the Mpa of oxygen pressure 0.8 ~ 1.2 input 10-25 min, kettle.Free radical cleaning pulping test knot is bright
The pilot product Chinese alpine rush once produced only is reacted using free radical electrochemical reaction kettle（3And wheat straw 0%)（70%) mixing slurry, cotton stalk bleaching pulp, poplar bleached pulp etc. have entrusted the authoritative unit detection such as national paper quality Supervision Test Center, University Of Science and Technology Of Tianjin, the results detailed in test report.Illustrate from test data, oxidizing process slurrying is applied not only to timber and is also applied for non-timber, such as agricultural wastes whole-cotton stalk, wheat straw are all available pulping raw materials.
The blunt announcement of test 4 and national bleached sulfite chemical wood pulp contrast table that national paper quality Supervision Test Center, University Of Science and Technology Of Tianjin provided in 2004 to 2005 years：
The invention provides a kind of method that high yield pulp1 bleached pulp is prepared with free radical clean technologies, its raw material is needlebush（Dragon spruce, masson pine, larch etc.）, leaf wood (poplar, by wood, willow, mulberry etc.）, grass family stalk fiber（Straw, wheat
Grass, reed, bamboo etc.）, bast fiber（Hemp, banana fiber crops, pineapple fibre etc.）, leaf fibre（Chinese alpine rush, pineapple leaves etc.）, plant hide fiber（Cotton, cotton linter etc.）, like wooden non-wood fiber raw material whole-cotton stalk.
The present invention is more specifically described below in conjunction with embodiment.Embodiment 1
Take the g (oven-dry weights of dragon spruce piece 100）, velvet shape is twisted into rubbing devillicate machine, wind-force removes impurity, after the purification of 60 circulating hot waters, conveyer belt feeding preheating infuser, 80, the MPa of pressure 0.3, pH=4.8, pre-process 30 min, and electrochemical reaction kettle is inputted with conveying worm after dehydration（Reactor model：Μ-Ο Ρ-Π Ι types, factory：Tianjin Machinery Plant of Light Industry）, stirring line style rotating speed is 0.8 ~ 1.2 m/s, and temperature is that 140, pH is to use conventional electrodes under 3.8 reaction conditions, constantly makes to produce electronics in kettle, opens after the min of nitrogen 5, oxygen pressure valve is opened, makes reaction medium（Including water, oxalic acid, material）Middle nitrogen, oxygen concentration are the mg/m of l ~ 153;Add cellulose protective agent magnesia, 0.002 g chelating agent EDTA, 0.15 g free radical stabilizer Na that concentration is 0.008 g under 0.3MPa pressure5P30lc, barrier gate valve boosts to 0.8 MPa, and the reaction time is 45 min, and 10 min are reacted in voltage stabilizing, are decompressed to 0.15 MPa, opens discharging gate valve；Gas separating dewatering apparatus is starched into spurting；Hot gas is discharged into cyclic water tank by the air valve that begins to rehearse, after circular treatment, is reused；With spiral wash engine in 60 deionized waters cyclic washing twice, dehydration, fine grinding, except saving, disappear it is latent after, produce 68 ~ 78% bleached pulp ISO.The whiteness is disposably takes off bleaching integrated reaction whiteness, and holocellulose yield is 62 ~ 75%.Embodiment 2
Be the same as Example 1, difference is that raw material is fallen leaves loose pieces, and velvet shape is twisted into rubbing devillicate machine, wind-force removes impurity, after the purification of 60 circulating hot waters, conveyer belt feeding preheating infuser, machine is sent to input in electrochemical reaction kettle with spiral is pleased after dehydration, it is 0.8 ~ 1.2 m/s to stir line style rotating speed, and how temperature uses conventional electrodes under part for 3.9 reactions if being 120, pH, constantly make to produce electronics in kettle, open after the min of nitrogen 5, oxygen pressure valve is opened, makes reaction medium（Including water, Peracetic acid, material）Middle nitrogen, oxygen concentration are 1 ~ 15 mg/m3;Add cellulose protective agent magnesium carbonate, 0.0015 g chelating agent DTPA, 0.1 g free radical stabilizer FRS that concentration is 0.005 g under 0.4 MPa pressure; barrier gate valve, boosts to 0.8 MPa, and the anti-village time is 30 min; 10 min, decompression are reacted in voltage stabilizing
To 015MPa, opens discharging gate valve；Gas separating dewatering apparatus is starched into spurting；Hot gas is discharged into cyclic water tank by the air valve that begins to rehearse, after circular treatment, is reused；With spiral wash engine in 60 deionized waters cyclic washing twice, dehydration, fine grinding, except saving, disappear it is latent after, produce 68 ~ 76% bleached pulp ISO.The whiteness is disposably takes off bleaching integrated reaction whiteness, and holocellulose yield is 65 ~ 78%.Embodiment 3
Be the same as Example 1, difference is that raw material is poplar piece, velvet shape is twisted into rubbing devillicate machine, wind-force removes impurity, after the purification of 60 C circulating hot waters, conveyer belt feeding preheating infuser, inputted after dehydration with conveying worm in electrochemical reaction kettle, it is 0.8-1.2 m/s to stir line style rotating speed, and temperature is 140TC, and pH is to use conventional electrodes under 4.0 reaction conditions, constantly make to produce electronics in kettle, open after the min of nitrogen 5, oxygen pressure valve is opened, makes reaction medium（Including water, acetic acid, material）Middle nitrogen, oxygen concentration are the mg/m of l ~ 153;Add cellulose protective agent magnesia, 0.002 g chelator acid citrate sodium, 0.12 g free radical stabilizer DMD that concentration is 0.007 g under 0.4 MPa pressure; barrier gate valve; boost to 0.8 MPa; reaction time is 30 min; 10 min are reacted in voltage stabilizing; 0.15 MPa is decompressed to, discharging gate valve is opened；Gas separating dewatering apparatus is starched into spurting；Hot gas is discharged into cyclic water tank by the air valve that begins to rehearse, after circular treatment, is reused；With spiral wash engine in 60 deionized waters cyclic washing twice, dehydration, fine grinding, except saving, disappear it is latent after, produce the ISO of bleached pulp 76 ~ 84.5%.The whiteness is disposably takes off bleaching integrated reaction whiteness, and holocellulose yield is 60 ~ 76%.Embodiment 4
Be the same as Example 1, difference is that raw material is whole-cotton stalk, and velvet shape is twisted into rubbing devillicate machine, wind-force removes impurity, after circulating hot water purification, conveyer belt feeding preheating infuser, inputted after dehydration with conveying worm in electrochemical reaction kettle, it is 0.8 ~ 1.2 m/s to stir line style rotating speed, and temperature be 130, and " C, pH be to use conventional electrodes under 4.8 reaction conditions; constantly make generation electronics in kettle; after opening nitrogen 5 min, oxygen pressure valve is opened, makes reaction Jie's shield（Including water, acetic acid, material）Middle nitrogen, oxygen concentration are 1-15 mg/m3;Add cellulose protective agent sodium dihydrogen phosphate, 0.002 g chelating agent zeolite, 0.1 g free radical stabilizer H that concentration is 0.005 under 0.4 MPa pressure2Si2Os, barrier gate valve boosts to 0.8 MPa, and the reaction time is 40 min, and voltage stabilizing is anti-
10 min are answered, 0.15 MPa is decompressed to, discharging gate valve is opened；Gas separating dewatering apparatus is starched into spurting；Hot gas is discharged into cyclic water tank by the air valve that begins to rehearse, after circular treatment, is reused；With spiral wash engine in 60 deionized waters cyclic washing twice, dehydration, fine grinding, except saving, disappear it is latent after, produce 72 ~ 79% bleached pulp ISO.The whiteness is disposably takes off bleaching integrated reaction whiteness, and holocellulose yield is 68 ~ 77%.Embodiment 5
Take the g (oven-dry weights of straw 100）Velvet shape is twisted into rubbing devillicate machine, wind-force removes impurity, after 60 °C of circulating hot water purifications, conveyer belt feeding preheating infuser, 80, the MPa of pressure 0.3, pH=4.8,30 min are pre-processed, are inputted after dehydration with conveying worm in electrochemical reaction kettle, stirring line style rotating speed is 0.8 ~ 1.2 m/s, temperature is 140, pH constantly makes to produce electronics in kettle, opened after the min of nitrogen 5 to use conventional electrodes under 3.8 reaction conditions, oxygen pressure valve is opened, makes reaction medium（Including water, Peracetic acid, material）Middle nitrogen, oxygen concentration are 1 ~ 15 mg/m3;Add cellulose protective agent magnesium sulfate, 0.002 g chelating agent opal, 0.15 g free radical stabilizer 3MgO 4Si0 that concentration is 0.008 g under 0.3 MPa pressure2 ' H20, barrier gate valve boosts to 0.8 MPa, and the anti-disease time is 45 min, and 10 min are reacted in voltage stabilizing, are decompressed to 0.15 MPa, opens discharging gate valve；Gas separating dewatering apparatus is starched into spurting；Hot gas is discharged into cyclic water tank by the air valve that begins to rehearse, after circular treatment, is reused；With spiral wash engine in 60 C deionized waters cyclic washing twice, dehydration, fine grinding, except saving, disappear it is latent after, produce 68 ~ 75% bleached pulp ISO.The whiteness is disposably takes off bleaching integrated reaction whiteness, and holocellulose yield is 52 ~ 68%.Embodiment 6
Be the same as Example 5, difference is that raw material is wheat straw, produces 70 ~ 82% bleached pulp ISO.The whiteness is disposably takes off bleaching integrated reaction whiteness, and holocellulose yield is 55 ~ 70%.Embodiment 7
Be the same as Example 5, difference is that raw material is banana fiber crops, and velvet shape is twisted into rubbing devillicate machine, wind-force removes impurity, after the purification of 60 circulating hot waters, conveyer belt feeding preheating infuser, inputted after dehydration with conveying worm in electrochemical reaction kettle, stirring line style rotating speed is
0.8-1.2 m/s, temperature is 140, pH, to use conventional electrodes under 4.0 reaction conditions, constantly makes to produce electronics in kettle, opens after the min of nitrogen 5, oxygen pressure valve is opened, makes reaction medium（Including water, dimethyl sulfoxide, material）Middle nitrogen, oxygen concentration are 1 ~ 15 mg/m3;0.4Add the burnt bony sour sodium of cellulose protective agent, 0.00 that concentration is 0.007 g under MPa pressure2G chelating agent sodium tripolyphosphate, 0.12 g free radical stabilizer Na4P207, barrier gate valve boosts to 0.8 MPa, and the reaction time is 30 min, and 10 mm are reacted in voltage stabilizing, are decompressed to 0.15 MPa, opens discharging gate valve；Gas separating dewatering apparatus is starched into spurting；Hot gas is discharged into cyclic water tank by the air valve that begins to rehearse, after circular treatment, is reused；With spiral wash engine in 60 deionized waters cyclic washing twice, dehydration, fine grinding, except saving, disappear it is latent after, produce the ISO of bleached pulp 78 ~ 86%.The whiteness is disposably takes off bleaching integrated reaction whiteness, and holocellulose yield is 60 ~ 72%.Embodiment 8
Be the same as Example 5, difference is that raw material is Chinese alpine rush, velvet shape is twisted into rubbing devillicate machine, wind-force removes impurity, after the purification of 60 C circulating hot waters, conveyer belt feeding preheating infuser is inputted in electrochemical reaction kettle after dehydration with conveying worm, it is 0.8 ~ 1.2 m/s to stir line style rotating speed, and temperature is 130.C, pH constantly make to produce electronics in kettle, open after the min of nitrogen 5, oxygen pressure valve is opened, makes reaction medium to use conventional electrodes under 4.8 reaction conditions（Including water, ethyl acetate, material）Middle nitrogen, oxygen concentration are 1 ~ 15 mg/m3;Add cellulose protective agent phosphoric acid Mo, 0.002 g chelating agent zeolite, 0.1 g free radical stabilizer Na that concentration is 0.005 g under 0.4 MPa pressure4P207, barrier gate valve boosts to 0.8 MPa, and the reaction time is 40 min, and 10 min are reacted in voltage stabilizing, are decompressed to 0.15 MPa, opens discharging gate valve；Gas separating dewatering apparatus is starched into spurting；Hot gas is discharged into cyclic water tank by the air valve that begins to rehearse, after circular treatment, is reused；With spiral wash engine in 60 deionized waters cyclic washing twice, dehydration, fine grinding, except saving, disappear it is latent after, produce 74 ~ 83% bleached pulp ISO.The whiteness is disposably takes off bleaching integrated reaction whiteness, and holocellulose yield is 68 ~ 79%.
Claims (13)
- Claim1. a kind of method for preparing bleached pulp with free radical cleaning pulping technology, comprises the following steps：Add organic solvents into the electrochemical reaction kettle containing reaction mass and water, the pH for making the reaction medium in the electrochemical reaction kettle is faintly acid；Electronics is provided by reaction medium of the electrode into the electrochemical reaction kettle；Oxygen and/or nitrogen are passed through into the electrochemical reaction kettle, and adds chelating agent, cellulose protective agent and free radical stabilizer, to produce various free radicals so that the lignin in the reaction mass is separated；It is derived from bleached pulp.2. according to the method for claim 1, wherein the concentration of nitrogen and oxygen is respectively 1 ~ 15 mg/m in the reaction medium3。3. method according to claim 1, wherein the pH value of be confused reaction medium is between 3 ~ 6.9.4. method according to claim 3, wherein the pH value of the reaction medium is between 3.8 ~ 5.8.5. according to the method for claim 1, wherein the organic solvent is selected from the group being made up of following member：Two Yue bases sulfoxides, acetic acid, ethyl acetate, ether, Peracetic acid, benzoyl peroxide, nitric acid, oxalic acid and the mixture of two or more in them.6. method according to claim 1, wherein the free radical stabilizer is selected from the group being made up of following member：Ethylene oxide, dimethyl ethylene oxide, acetone and ethanol class.7. method according to claim 6, wherein the free radical stabilizer is selected from the group being made up of following member： FRS、 Na5P3O10, 3MgO · 4Si02 · H20、 H2Si205、 Mg2 +And DMD.8. method according to claim 1, wherein described free radical is selected from the group being made up of following member：Ultra-oxygen anion free radical（Ο), ultra-oxygen anion free radical is protonated（Η Ο Ο '), hydroxyl radical free radical（' Ο Η), NO free radical（NO ·、 Ν02), methyl free radicals（ . CH3), quinones free radical（' Q), alkanes free radical（' R), alkoxy free group（LO ') and Lipid Free Radicals（LOO · ) .9. method according to claim 1, wherein described reaction mass from needlebush, Leaf wood, grass family stalk fiber, bast fiber, leaf fibre plant hide fiber.10. according to the method for claim 1, wherein described cellulose protective agent is selected from the group being made up of following member：Magnesium sulfate, magnesium carbonate, magnesia, sodium pyrophosphate, sodium dihydrogen phosphate and the mixture of two or more in them.11. according to the method for claim 1, wherein described chelating agent is selected from the group being made up of following member：The ammonium pentaacetic acid of divinyl three（DT A), b diammonium edta (EDTA), sodium citrate, opal, zeolite, sodium tripolyphosphate, polyoxyethylene alkyl ether and the mixture of two or more in them.12. according to the method for claim 11, wherein described chelating agent is opal or sodium tripolyphosphate.13. the bleached pulp obtained according to the method for any one of claim 1-12.
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| PCT/CN2006/001262 WO2007143877A1 (en) | 2006-06-09 | 2006-06-09 | A method of preparing bleached pulp with high yield by free radical cleanness kraft process |
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| CN2661301Y (en) * | 2003-11-24 | 2004-12-08 | 梅秀泉 | Kraft processing device by lignin removing by oxygen and bleaching |
| CN1621609A (en) * | 2003-11-24 | 2005-06-01 | 梅秀泉 | Integral slurrying method including oxygen delignify and bleaching and apparatus thereof |
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