CN1878909A - Full-closed zero discharge oxidizing pulping process and its preparation method - Google Patents
Full-closed zero discharge oxidizing pulping process and its preparation method Download PDFInfo
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- CN1878909A CN1878909A CNA2003801108070A CN200380110807A CN1878909A CN 1878909 A CN1878909 A CN 1878909A CN A2003801108070 A CNA2003801108070 A CN A2003801108070A CN 200380110807 A CN200380110807 A CN 200380110807A CN 1878909 A CN1878909 A CN 1878909A
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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
- 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
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/004—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives inorganic compounds
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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
- D21C3/22—Other features of pulping processes
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Abstract
The object of the present invention is to provide a fully-closed, zero discharging and clean oxidizing pulping process and the preparation method thereof. In accordance with the present invention, it employs active oxygen free radicals generated by electron reduction reaction of molecular oxygen in an ion reactor to transform and separate lignin, to change chromophoric groups in the intercellular space and to obtain paper pulp. The conventional pulping technologies which use harmful polluting chemicals such as acid, alkaline, chlorine, anthraquinone and so on are basically changed in the present invention. The cooking and bleaching process, which generate severe pollution, can be avoided. The abundant annually grown fiber materials can be utilized in this process, and water and energy can be saved. The present invention can reduce production cost and have excellent social, economic and environmental benefits.
Description
Full-closed zero discharge oxidizing pulping process and preparation method thereof invention field
The present invention disclose a kind of full-closed zero discharge oxidizing pulping process and preparation method thereof, more specifically to a kind of totally-enclosed self-loopa without it is sour, without alkali, without chlorine, without anthraquinone, non-evaporating boil, exempt from bleaching, zero-emission, pollution-free cleaning papermaking paste-making method.Background of invention
Current paper making raw material is in short supply for a long time, not some area and refer to global paper industry.Forest is the lung of life on earth, except water conservation, is prevented erosion, and the effect of regulating the climate etc. is outer, can release oxygen with absorbing carbon dioxide, and forest not only the meat and fish dishes ecological value and has economic value.But the world is just with annual 700 x l 0 at presentsm2Decrease of speed, tropical rain forest is with 50 x 10 per minute4m2Speed reduce, such as strictly control continue disorderly is intended to cut down trees at random, after 40 years, world population is continuously increased, the mankind will face no oxygen for breathe predicament.
China Forest statistical yearbook 1999 is compared with 2000, forest rate of descent：The ten big % of ecological projects related to the forestry industry -12. 9, natural forest reserve engineering -10. 7%, area -6. 33% of closing hillsides to facilitate afforestation, shelter-forest -24. 75%, economic forest -3. 82%, Timber stands -14. 07%.
Non-wood-fiber element raw material divides in Plant Fiber Chemistry：1. grass family fibrous raw material；2. bast fiber raw material；3. seed wool fibre raw material；4. leaf fiber raw material, wherein Zong He Yu dimension hplcs are between 48% ~ 84%, non-wood-fiber length majority compares fibre length, cellulose is mainly used in papermaking, the cellulose either extracted with wood or with grass, all it can all make high, middle-grade paper pulp as the framework material in slurrying.Research confirms that various chemical analysis are similar with broadleaf, softwood in non-wood material cotton stalk fiber.
China 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（t ) .China " 15, planning period, national emphasis cotton growing area cultivated area is stable in 6,000,000 hm within 20102, year the high-quality t of cotton stalk 34,200,000 is given birth to, is calculated by the data in textbook, only one annual output t of pulp material 2428. 2 ten thousand of cotton stalk, such as utilization rate can produce 485. 6 ten thousand t every year up to 20%, this year production-goods source similar to leaf wood, utilization rate is less than 1% so far.Corn stalk, wheat straw, straw（T) can extract non-wood fibrous raw material up to 4. 7 hundred million according to Yearbook of Agricultural Statistics three in 2000 is 2. 35 hundred million t, this batch of huge year coins paper material now with rate less than 5%, the U.S. will be referred to as agriculture green waste in production-goods source these years, and China is referred to as green year production-goods source.
China Light Industry Press, publishes for 2000《Pulping process and equipment》In, the integrated fiber cellulose content of each raw material is determined with sodium chlorite method, its data is shown in Table 1.
The unit of table 1：Weight %
Sweet slag Guangdong 75. 6,73. 0 wheat straw Hebei, 71. 3 Korean pine Daxing'an Mountainrange, the places of origin of raw materials holocellulose places of origin of raw materials holocellulose fish Open dragon spruces Xiaoxinanlin Mountains 69. 6
、
The Ba Maoshi of 66. 4 67. 2 cornstalk Hebei, 84. 9 reed Hubei, 75. 4 splendid achnatherum Ningxia, 79. 8 Chinese silvergrass Hubei, 76. 6 leaflet camphor Heilungkiang, 74. 9 cotton stalk Jiangsu, red bamboo Guangdong, the Chinese alpine rush factory of high point poplar Henan 81. 6 west 76. 7 green bamboo Zhejiang, 69. 5 sorghum stalk Hebei 75. 1
The superfluous China Light Industry Press of 84. 3 straw Hebei, Sichuan 64. 0, publishes for 2001《Plant Fiber Chemistry teaching material》, disclose cotton stalk raw material chemical analysis（Weight %) and average fiber it is long（Leg）Data, it the results are shown in Table 2.
Table 2
The current paper-making industry whole world is known to use the traditional paper-making process before more than 100 years, and without restraint using strong acid, highly basic, strong chlorine, Heisui River is discharged without restraint, natural environment for the survival of mankind is had a strong impact on.The state such as Japan, India, Canada, which develops into, in recent years uses anthraquinone, is the condensed-nuclei aromatics in aromatic hydrocarbon because of anthracene, and all condensed-nuclei aromatics have had confirmed that carcinogenesis material, such as known carcinogenic structural formula being made up of anthracene at present：
10-methyl-1,2 benzanthracene or ethylidene-1,2 Benzanthracenes ClO 2 bleaching, Environmental Protection Agency have issued the order on prohibitting the use of chlorine in filling bleaching in papermaking in April, 2000.Sight is invested chlorine dioxide as bleaching agent by 54% paper mill again in the world at present, but the dioxane compound of chlorine dioxide 91% and other organic matter chemical combination, and the 9% chlorine discharge of remaininging still endangers environment for human survival.
Oxidation bleaching can trace back to the beginning of the fifties, nineteen fifty-two, the Soviet Union's wood woods chemist Nikieih and ARim had found that oxygen can be bleached first, after 12 years, French scientist Rebeve in 1964 et al., cellulose not oxidative degradation can be protected with magnesium salts, U.S. in 1970, method, auspicious three state successively sets up laboratory, the same year South Africa Ens trd sets up first ClO 2 bleaching workshop in the world, the U.S. in 1972, which is set up, says production 12t oxygen bleachings workshop, and apply for chlorine-free bleaching patent, afterwards because cellulose loss is big, power consumption, water consumption is high, the factors such as product cost do not enter industrialization.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.Cut-off is retrieved in various countries' Patent data in March, 2002, and global paper-making industry does not leave acid, alkali, the digesting technoloy of chlorine severe contamination all the time, and the chlorine bleaching technique of severe contamination is not left all the time yet；Processing to lignin chromophore was still rested on before more than 100 years in the traditional handicraft for separating xylogen degradation, therefore, global papermaking had turned into the target that environmental protection organization pays close attention to already.
The method of the ozone of L'air Liquide Service Brevets ＆ Marques of CN1212310A France invention and ClO 2 bleaching paper pulp disclosed in 31 days March in 1999, the open CN1371439A dish methods made in U.S.A on the 25th of September in 2002, CN1407172A Amada Co., Ltd.s disclosed in 2 days April in 2003 are apt to greatly a kind of free of contamination papermaking paste-making method invented with the disclosed CN1198492 Shandong Wei Chang normal universities of preparation method and preparation system device and China that non-timber is raw material production paper pulp of invention, a kind of methods of alkali-free slurrying of CN1229155, CN1458075-kind of polyoxometallate electrochemical bleaching pulp technology etc..
Above-mentioned all patents of invention have plenty of chlorine-free bleaching through reading carefully, have plenty of reduction acid, alkali,
Chlorine consumption, has plenty of and substitutes chlorine with ozone, there is the use alkali and anthraquinone, peroxy acid for being.Cut-off in March, 2002 whole world does not have any one without acid, alkali delignification, thoroughly takes Parties soda acid chlorine without any one, illustrates the foregoing invention not pollution administration from source.The present invention is that pollution is eradicated from the source of the sector, from slurrying delignification anthraquinone is less used into bleaching overall process without strong acid, highly basic and chloride, all paper wastes are not outwards discharged, totally-enclosed self-loopa zero-emission is formed, fundamentally solves that pulping industry raw material is in short supply and with serious pollution two big world problem.The content of the invention
The technical problems to be solved by the invention are to overcome shortcoming of the prior art there is provided a kind of totally-enclosed, self-loopa, zero-emission, pollution-free, oxidizing pulping process and preparation method thereof.
Clean pulping process of the present invention and preparation method thereof, is achieved by following technical proposals, it is characterised in that the clean pulping process and preparation method thereof is, using non-timber or timber as raw material, to be prepared from by following technical process：
(A) pretreated feedstock；
(B) the above-mentioned pretreated material of oxidation dipping in the presence of active oxygen A and the cellulose being made up of metal ion and metallic ion coordination body are protectant；
(C) first ground with active oxygen A, then impregnated material is aoxidized with active oxygen B grindings；
(D) concentrate, mashing,
Wherein above-mentioned active oxygen A is selected from 02、 H202One or both of free radical generated with it, active oxygen B is selected from 03、 02(singlet oxygen）, (the ultra-oxygen anion free radicals of 0/Η 00）The one or more of its free radical generated in water in the presence of organic solvent.
The organic solvent is, for example, dimethyl sulfoxide (DMSO), oxalic acid class.
A kind of paper pulp obtained in aforementioned manners.
In a kind of method of cleaning pulping as described above, the non-timber such as whole-cotton stalk include that cotton bast, cotton stalk, cotton stalk root and whole-cotton stalk integrated fiber, stiff valve cotton and cotton linter, cotton be hasty and careless, the mixture of cellulose contained in cottonseed, hemicellulose, one kind in lignin or they two or more.The timber includes softwood, broadleaf such as kahikatea, masson pine, pesudotsuga taxifolia, aspen wood, Fast growth poplar, birch etc..
The metal ion is selected from Mg++、 Fe++、 Mn++、 Cu++、 Α ++、 Zn++、 Si++In one kind or their mixtures of two or more；The metallic ion coordination body is selected from two Yue bases two and corrects page（The 91st article of detailed rules and regulations)
Oxirane（DMD), diethylenetriamine pentaacetic acid（DTPA), ethylenediamine tetra-acetic acid（EDTA), the mixture of the sour sodium of protective embankment base, one kind in polyoxyethylene alkyl ether or they two or more.
The metal ion consumption is by weight between 1-l OOOppm.
The oxidation impregnation process is carried out under the acid condition between pH value is 1-4, and preferably described radon impregnation process is carried out in the case where pH value is 1. 5-2. 5 acid condition.
The milled processed is carried out under the acid condition between pH value is 1-4, and preferably described milled processed is carried out in the case where pH value is 2. 5-3. 8 acid condition.
The acid condition can pass through active oxygen of the invention（Such as H00) reach, i plus pH adjusting agent can also be led to reach.
Concentration of the active oxygen Α in handled material is 0. 01-2. Owt%, and molar concentrations of the active oxygen B in handled material is 0. 1-50umol/L.
A kind of method of cleaning pulping as previously discussed, this method has following feature and advantage：（A) active oxygen is added drop-wise to the rotation heat by mill in disc mill, produces energy transmission reaction, cellulose is separated from cell interbed；（B) utilization active oxygen A, B collective effect, by the chromophore in lignin " ,-aldehyde ketone base class are converted into carboxylic acid or the colourless group of dicarboxylic acids class；(C) from misfortune ring：Oxidizing reactor system, all use moisture two parts reflux cycle in oneself factory in technological process are sent into after pretreatment of raw material：Part I is the water after purification of raw materials processing, solid slag is transported after centrifugal clarification, the conventional beater floor of slurry feeding, produced clear water enters recirculating water purification pond, clarifier-tank built with 0. 1% -0. 15% three base oxygen or ozone generator（03Generator）, clear water is produced in decoloring reaction, water and containing micro oxygen radical, system is used into recirculated water by pump；Part II is the water after oxidation processes, handled after centrifugal clarification with conventional thickeners, slurry feeding reserve pit enters machine room, produced water filtration enters oneself factory's interior circulation water purifying tank, by the purified water pumping purification of raw materials system after processing, Gasization dipping systems, oxygen grinding system, screening system, used repeatedly in oneself factory's interior circulation.
This method is to produce electronic reduction reaction generation active oxygen radical to convert isolated lignin in ion reactor with molecular oxygen, the chromophore in plant cell interbed is changed, obtains paper dress.This method fundamentally changes the traditional handicraft chemicals pulping process such as with serious pollution acid, alkali, chlorine, anthraquinone, not only remove with serious pollution boiling, the third big workshop section of tradition bleaching from using the present invention, and using abundant year production-goods source, also can save energy water saving reduction product cost.
This method is to be added to active oxygen in material, and mill heating power is produced with highly concentrated defibrator mix grinding
Reaction, to change the chromophore of lignin in plant cell interbed, the strong attack and intramolecular nucleophilic attack power of hydroxyl radical free radical are formed with 3 oxygen atoms in molecular oxygen and electrophilic reaction occurs for lignin, it is broken the big pi bond of lignin building unit phenyl ring and side chain, its dissolution of degrading, chromophore converts or is decomposed into low molecule in lignin, generates colourless monocarboxylic acid or dicarboxylic acids class.
Reaction equation is as follows：
Particularly method of the invention is as follows：
A kind of oxidizing pulping process and preparation method thereof, it is characterised in that the clean pulping process is, using non-timber or timber as raw material, to be prepared from by following technical process：
(Α) pretreated feedstock；
(Β) above-mentioned pretreated material of oxidation dipping in the presence of active oxygen Α and the cellulose being made up of metal ion and metallic ion coordination body are protectant；
(C) first ground with active oxygen A, then impregnated material is aoxidized with active oxygen B grindings；
(D) concentrate, mashing,
Wherein above-mentioned active oxygen A is selected from 02、 H202One or both of free radical generated with it, active oxygen B is selected from 03、 02(singlet oxygen）, (the ultra-oxygen anion free radicals of 0/Books 0）The one or more of the free radical generated in water in the presence of organic solvent.
' molecular oxygen through ionizing radiation device produce redox reaction when result in active oxygen, energy is provided, ultimately produce water, in 4 electronic processes received altogether, often receive one and be electronically generated an oxygen radical, such as electron reduction generation ultra-oxygen anion free radical, its reaction equation is 02+ e → 0^/H00 ■, two-electron reduction generates hydrogen peroxide, and its reaction equation is： 02 + 2e + 2H+→
6
Correct page（The 91st article of detailed rules and regulations）
H202, three electron reductions generation hydroxyl radical free radical, ferrous iron and hydroperoxidation generation free radical, its reaction equation is： 02 + 3e + 3H+ → H20 + · 0H、 Fe2 + + H202→ Fe3 ++ 0 Η+0H-it is the special free radical of water process.
Metal ion is selected from such as Mg++、 Fe++、 Mn++、 Cu++、 Α ++、 Zn++、 S i++In one kind, or they two or more mixture.The metal ion is typically provided in a salt form, for example ferrous sulfate, magnesium carbonate etc..The metallic ion coordination body is selected from such as dimethyl ethylene oxide（DMD), diethylenetriamine pentaacetic acid（DTPA), ethylenediamine tetra-acetic acid（EDTA one kind), in sodium alkyl sulfonate, polyoxyethylene alkyl ether or the mixture of they two or more.Both of which and ultra-oxygen anion free radical（O2" HOO), hydrogen peroxide（H202) respectively with the plain protection system of the functional fiber of different components composition, not only protected cellulose but also can reach except silicon purpose.
Pretreatment generally includes the removal of impurity, cuts off, sub-wire, and cleaned depending on concrete condition.Wherein oxidation impregnation process is preferably carried out in acid condition, and such as pH value is between 1-4, preferably 1. 5-2. 5 or so.
Wherein milled processed is preferably carried out in acid condition, and such as pH value is between 1-4, preferably 2. 5-3. 8 or so.
Acid condition can pass through active oxygen of the invention（Such as H00) reach, in addition it can be reached by adding pH adjusting agent.
Metal ion is generally used in a salt form, and its consumption is usually between 1-l OOOppm, between preferably 10-l OOppm based on metal ion weight.
It is of the present invention non-evaporating to boil：Finger removes cooking section from, and the rotation heat by mill in disc mill is added drop-wise to active oxygen, energy transmission reaction is produced, cellulose is separated from cell interbed.
It is of the present invention to exempt from traditional bleaching：Refer to without bleachery, with the collective effect of active oxygen people, B, the chromophore in lignin is converted into colourless group, such as will " ,-butyrone base class change into carboxylic acid or dicarboxylic acids class.
According to a preferred embodiment of the invention, method of the invention includes：
Feedstock pre-processing system：Refer to the workshop section of a coordinating operation; feedstock pre-processing system; it is to be removed material hulling after calyx with shredder, is cut into that the 5cm of 5cm length 1. is thick, material of the ratio of briquetting up to 98%; velvet shape is cracked into roller press type shredder; wind-force dedusting removes marrow core, and clarifier washes away debris, and clarifier is oneself totally-enclosed factory's interior circulation water with water; micro active oxygen radical, micro cellulose protective agent are remained in the water（Commercially it is commercially available）, therefore corrigendum page（The 91st article of detailed rules and regulations)
It is not necessary to during pretreatment plus active oxygen, is polluted with recirculated water washing material without discharge opeing, change the pollution technique of traditional handicraft pickling, alkali cleaning.
Oxidizing reactor system（See Chinese invention patent application 200310103895. 3)：Major function be material is infiltrated, softened, degumming, pH value 1-4 in kettle, active oxygen generates ultra-oxygen anion free radical in slightly acidic water（(/ Η 00), with strong permeability, can be directed through plant cell interbed and occur oxidation reaction.Agitator is provided with oxidizing reactor, the agitator at the top of the oxidizing reactor with external motor by being connected and being driven by it, the stirring slurry of the agitator is at least three layers, rotating speed controllable, start agitator, make the cation that electrode is produced in water in kettle, shearing force in pressure and agitator, under the collective effect of water temperature, soften material.Active oxygen makes linking layer, pectin, poly-pentose while decomposing generation decoloring reaction in high-speed stirred in oxidizing reactor.Through inventor's repetition test; preferably; pH value 1. 5-2. 5 in kettle; plus 0. 02-0. 1% cellulose protective agents prepared in advance; speed of agitator is up to 40-80 beats/min; in 40-60 minutes, material chromophore is by the deep yellow white that shoals in kettle, and cyclic washing is simultaneously extracted.
Grinding system：It is preferred to use disc mill system：It is made up of RL50S types disc mill or highly concentrated defibrator with oxidizing reactor two large divisions.There is point of a mill, two mills in technique, mill active oxygen Α, two mills use active oxygen Β.Material is exported by oxidation dipping systems, uniformly sent into by screw feeder after grinding machine, infiltrated with molar concentration for 1-15umol/L ozone, wet weight percentage concentration is 30,11 values 2. 5,600-1200 beats/min of mix grinding rotating speed, grinding machine gap is 0. 2-0. 15mm;Constantly add weight percentage concentration is 0 1-1. 5 active oxygen A and material mix grinding in shower water during-mill, softening material is reached by mix grinding, the cellulose coated in separation cell interbed, the heating power reaction major function that rubs is by active oxygen and material mix grinding, the friction of mill speed is set to produce heating power transfer reaction, by ultra-oxygen anion free radical, molecular oxygen and hydrogen peroxide, to aoxidize the chromophore in phenyl-propane, plus lignin, the difference of respective softening temperature between hemicellulose and cellulose three, it is hydrophilic group after fiber fines oxidation, it can be connected in cellulosic backbone, increase yield 8-12%, key of the present invention is process conditions（The content that the present invention such as the order of technique, pH value, temperature, active oxygen consumption, time, rotating speed, pressure, slurry be dense is discussed in detail）.
There is the mill slag after point Return choosings of a mill, bis- Return repeatedly to regrind, sieve again in the process system, it is transferred to after clarifier processing, add after the edible Grade citric acid waters that concentration expressed in percentage by weight is 0. 12 and the azanol spray that concentration expressed in percentage by weight is 0. 01, to prevent paper defects and oxidation stain, routinely technique mashing, the slurry is original slurry, yield 76 %, ISO whiteness are 52-65..
This workshop section can build thick slurry machining production line in aboundresources raw material area of concentration, centered on enterprise raw material be provided ensured.
Original slurry is hooked with screw feeder and is continuously introduced into grinding machine, be added dropwise that the concentration expressed in percentage by weight that first prepares is 0.1 in a grinding process 02And/or the H that concentration expressed in percentage by weight is 1.5202, dripping quantity and slurry ratio by weight 1:0.12-0.15, with slurry mix grinding, 1300 beats/min of mill speed, 0.15-0.1 Yan are transferred in grinding machine gap, and temperature is 60-80, starch dense up to 12-15%, 11 value 2.5-3.8, observation pulp brightness is 65-75.；The singlet oxygen that the ultra-oxygen anion free radical (0^/HOO ■) and/or molar concentration that the ozone and/or molar concentration that dropwise addition molar concentration is about 10umol/L in two grinding process are about 10umol/L are about 10umol/L), actuating pressure 0.3- 0.6MPa, 1300 beats/min of rotating speed, it is transferred to 0.15- 0 in grinding machine gap, 1 Let, (the TC of temperature 80- 10, starch dense 12-15%, 8 value 2.5-3.8, with slurry mix grinding 0.5- lh, ISO whiteness should be 75-86 °, into conventional fine screen, purification, cylinder is concentrated, mashing, store sizing process system, if need to brighten again, can be by operating procedure again repeatedly once, slurry yield is 75%.
Method of the present invention has the advantages that compared with prior art：The present invention can be achieved totally-enclosed, zero-emission, self-loopa, without acid, without alkali, without chlorine, without anthraquinone, it is non-evaporating boil, exempt from bleaching, it is pollution-free cleaning papermaking paste-making method; the characteristics of with energy-conservation, water saving, cleaning pulping; fundamentally solve the pollution of pulping and paper-making industry; promote agricultural resource reutilization, preserve the ecological environment.The totally-enclosed self-loopa zero-emission：Refer to the feeding oxidation impregnation system after pretreatment of raw material, the useful moisture two parts backflow of institute is in oneself factory's interior circulation in technological process, a part is that solid slag is transported after centrifugal clarification, the conventional beater floor of slurry feeding, produced clear water enters oneself factory's interior circulation water purifying tank, three base oxygen or ozone generator of the clarifier-tank built with 0.1%- 0.15%（03Generator）, clear water is produced in decoloring reaction, water and containing micro oxygen radical, system is used into recirculated water by pump；Another part is handled with conventional thickeners after centrifugal clarification, slurry feeding reserve pit enters machine room, produced water filtration enters oneself factory's interior circulation water purifying tank, by the purified water pumping purification of raw materials system after processing, oxidation dipping systems, oxygen grinding system, screening system, used repeatedly in oneself factory's interior circulation.Present invention process is discharged without gas, no black water discharge, and the percentage that discharge solid slag accounts for gross weight is 12% -22%, and free from environmental pollution, waste residue can send into biological treatment tank and separately use it for anything else.Brief description of the drawings
Fig. 1 is the full-closed zero discharge oxidizing pulping process flow chart of the present invention.
9
Correct page（The 91st article of detailed rules and regulations）
Embodiment
It is just blunt below that according to embodiment, the invention will be further described.It should be understood that the purpose that these embodiments are merely to illustrate, is not intended to limit the scope of the invention.Embodiment one
Whole-cotton stalk 100kg is taken to be removed with shredder hulling after calyx, the thick ratio of briquetting of the long 1.5cm of 5cm is cut into up to 98% material, velvet shape is cracked into roller press type shredder, wind-force dedusting, except marrow core, weed out impurity, after recirculated water is cleaned, inputted with conveying worm in the oxidizing reactor with automatic stirring, reaction temperature is 60 °C, pH value 2.5 in kettle, plus Tan Suan Magnesium 0.02kg and dimethyl ethylene oxide 0.01kg (DMD), 60 beats/min of speed of agitator, adds H after 0.5h202Solution, its concentration expressed in percentage by weight is controlled 0.2, stirring accelerates 80 beats/min after addition, temperature is 80, and " C; the soft rate of material immersion swollen is observed in kettle after lh up to 98%; material is shoaled white by buff in kettle, meeting international standard ISO 48-52 ° of whiteness, (following cylinder is referred to as whiteness or ISO whiteness）Material, the material cyclic washing is extracted after concentration, aqueous concentration expressed in percentage by weight is 30, by clean material dropping H202Solution, its concentration expressed in percentage by weight in material is 0.2, input grinding machine is hooked with screw feeder and carries out mix grinding, 600-1200 beats/min of rotating speed, grinding machine gap is adjusted to 0.2mm- 0.15mm, mill slag after screening can repeatedly be regrinded, sieved again, it is transferred to after clarifier processing, add weight percentage concentration is that after the azanol that 0.12 food grade citric acid water and concentration expressed in percentage by weight are 0.01 embathes, routinely pulping process is beaten, this slurry is original slurry, yield 76./., ISO whiteness is 52-65..This workshop section can generally set up thick slurry machining production line in raw material area of concentration, centered on manufacturing enterprise original slurry is provided.
Embodiment two
With the original slurry 100kg in embodiment 1, grinding machine is sent into screw feeder uniformly continuous, the H that the concentration expressed in percentage by weight first prepared is 1.5 is added dropwise in a grinding process202, dripping quantity and slurry ratio by weight is 1：0.12, with slurry mix grinding, 1300 beats/min of mill speed, 0.15-0.1 legs are transferred in grinding machine gap, and temperature is 60 °C, starch dense 12-15% by weight, H values 3.8, observation pulp brightness is 65-75 °；The ozone that molar concentration is about 10umol/L, actuating pressure 0.4MPa, 1300 beats/min of rotating speed is added dropwise in two mills, it is transferred to 0.1mm in grinding machine gap, temperature 80, starches dense 12-15% by weight, pH value 3.8, with the slurry-lh of mix grinding 0.5, whiteness should be 75-86 °, into conventional fine screen, purification, cylinder concentration, mashing, storage sizing process system, if need to brighten again, can be by operating procedure again repeatedly once, slurry yield is
10
Correct page（The 91st article of detailed rules and regulations）
75%。
Embodiment three
Repetition and the identical program of embodiment one, simply replace magnesium carbonate with the sour magnesium of same weight bowl, obtain original slurry.
Example IV
Repeat and the identical program of embodiment two, the ultra-oxygen anion free radical for being simply 10umol/L with molar concentration（0^/HOO) replace the ozone that molar concentration is about 10umol/L.Embodiment five
Poplar piece 100kg is taken to crack into velvet shape with roller press type shredder, wind-force dedusting removes impurity, after recirculated water is cleaned, inputted with conveying worm in the oxidizing reactor with automatic stirring, reaction temperature is 60 °C, pH value 2.5 in kettle, plus magnesium sulfate 0.015kg and dimethyl ethylene oxide are G.01kg (DMD), 60 beats/min of speed of agitator, adds H after 0.5h202Solution, controls its concentration expressed in percentage by weight to stir 80 beats/min of acceleration after 0.2, addition, and temperature is that the soft rate of material immersion swollen is up to 98% in observation kettle after 100, lh, and material is shoaled white by buff in kettle, and raw material slightly starches ISO whiteness 48-52., the material cyclic washing is extracted after concentration, water content is 30%, by clean material dropping 02And H202Solution, its concentration expressed in percentage by weight in material is 0.25, input grinding machine is hooked with screw feeder and carries out mix grinding, 600-1200 beats/min of rotating speed, grinding machine gap is adjusted to 0.2mm- 0.15mm, mill slag after screening can again be regrinded, sieved again, it is transferred to after clarifier processing, the N that the food grade citric acid water and concentration expressed in percentage by weight that add weight percentage concentration is 0.12 are 0.01, after N- dialkylhydroxyamines embathe, routinely pulping process is beaten, and this slurry is original slurry, yield 76%, ISO whiteness is 52-65..
Embodiment six
With the original slurry 100kg in embodiment five, grinding machine is sent into screw feeder uniformly continuous, be added dropwise that the concentration expressed in percentage by weight first prepared is 0.1 in a grinding process 02With 1.5 H202The composite oxygen of composition, by weight dripping quantity and slurry ratio are 1：0.15, with slurry mix grinding, 1300 beats/min of mill speed, 0.15- 0.1mm are transferred in grinding machine gap, and temperature is 60, and " C starches dense 12-15% by weight, pH value 3.8, observation pulp brightness is 65-75.；The ultra-oxygen anion free radical (0/HOO) that molar concentration is about 10umol/L is added dropwise in two mills, actuating pressure 0.4MPa, 1300 beats/min of rotating speed, it is transferred to 0. lmm in grinding machine gap, 80 °C of temperature, starches dense 12-15% by weight, 3 values 3.8, with slurry mix grinding 0.5- lh
11
Correct page（The 91st article of detailed rules and regulations）
I SO whiteness should be 75-86.,, can be by operating procedure again repeatedly once if need to brighten again into conventional fine screen, purification, cylinder concentration, mashing, storage sizing process system, slurry yield is 75%.
Embodiment seven
Repetition and the identical program of embodiment five, simply replace dimethyl ethylene oxide with the diethylenetriamine pentaacetic acid (DTPA) of same weight, obtain original slurry.
Embodiment eight
Repeat and the identical program of embodiment six, the singlet oxygen θ for being simply 10umol/L with molar concentration2) and molar concentration be l Oumol/L ozone（03) volume gram point is replaced in the ultra-oxygen anion free radical that concentration is 10umol/L（ O HOO · ) .
The present invention is non-evaporating to boil, exempt from bleaching, totally-enclosed self-loopa, active oxygen mix grinding technique, and without adding the chemicals such as strong acid, highly basic, chloride again, enterprise can manufacture various types of medium and high classes paper pulp according to the market demand.
Oxidizing process cleaning pulping test result
Inventor is detected pilot product whole-cotton stalk, mulberry, poplar slurry and whole-cotton stalk screened stock commission University Of Science and Technology Of Tianjin, the results detailed in test report（Table 3).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 is a kind of available pulping raw material.
Test report and national bleached sulfite slurry contrast table that University Of Science and Technology Of Tianjin provided on November 12nd, 2003, are shown in Table 3.
Table 3
Bleach sulfurous acid
Index name cotton scale, which slightly starches cotton stalk screened stock mulberry and slightly starches poplar, slightly starches salt slurry standard
Fibre length（The equal mm of weight) 0. 50 0. 51 0. 65 0. 47 0. 55 beating degrees（° SR) 45 59 51. 5 58 62 quantitative (g/ m2) 58. 2 58. 2 60. 0 59. 0 57. 5 tightness (g/cm3) 3. 3 0. 33 0. 32 0. 33 0. 32 fracture lengths（Km) 3. 2 3. 81 3. 44 3. 44 3. 07 tear index（RaNmVg) the whiteness of 2. 8 2. 9 3. 4 2. 9 2. 5 burst index (KPamVg) 1. 5 1. 9 1. 5 1. 7 1. 4 (% IS0) 82. 0 68. 69 71. 58 70. 87 75. 17 opacities（%) 88. 1 95. 91 93. 91 96. 05 94. 07
Claims (9)
- Claim1st, the present invention relates to a kind of full-closed zero discharge oxidizing pulping process and preparation method thereof, it is characterised in that the clean pulping process and preparation method thereof is, using non-timber or timber as raw material, to be prepared from by following technical process：(A) pretreated feedstock；(B) the above-mentioned pretreated material of oxidation dipping in the presence of active oxygen A and the cellulose being made up of metal ion and metallic ion coordination body are protectant；(C) first ground with active oxygen A, then impregnated material is aoxidized with active oxygen B grindings；(D) concentrate, mashing,Wherein above-mentioned active oxygen A is selected from 02、 H202One or both of free radical generated with it, active oxygen B is selected from 03、 C singlet oxygens）, O HOO (ultra-oxygen anion free radicals）The one or more of its free radical generated in water in the presence of organic solvent.2nd, according to the method described in claim 1, it is characterised in that the non-timber such as whole-cotton stalk include cellulose contained in cotton bast, cotton stalk, cotton stalk root and whole-cotton stalk integrated fiber, stiff valve cotton and cotton linter, cotton slag, cottonseed；The mixture of one kind or they two or more in hemicellulose, lignin；The timber includes softwood, broadleaf such as kahikatea, masson pine, pesudotsuga taxifolia, aspen wood, Fast growth poplar, birch etc..3rd, the method according to claim 1, it is characterised in that the metal ion is selected from Mg++、 FeH、 Mn++、 Cu++、 ΑΓ++、 Zn++, one kind in Si^ or their two or more mixtures, the metallic ion coordination body is selected from dimethyl ethylene oxide（D), diethylenetriamine pentaacetic acid（DTPA), ethylenediamine tetra-acetic acid（EDTA one kind), in sodium alkyl sulfonate, polyoxyethylene alkyl ether or the mixture of they two or more.4th, according to the method described in claim 1, it is characterised in that the metal ion consumption is by weight between 1-lOOOppm.5th, according to the method described in claim 1, it is characterised in that the oxidation impregnation process is carried out under the acid condition between pH value is 1-4,.6th, method according to claim 5, it is characterised in that the oxidation impregnation process preferable ph is progress under 1.5-2.5 acid condition.7th, the method according to claim 1, it is characterised in that the milled processed is carried out under the acid condition between pH values is 1-4.8th, method according to claim 7, it is characterised in that the preferred pH of milled processed13Correct page（The 91st article of detailed rules and regulations） It is worth under the acid condition for 2.5-3.8 and carries out.9th, 1 according to the method described in claim 1, it is characterised in that concentration of the active oxygen A in handled material is that the molar concentration in handled material is 0.1-50umol/L in 0.01- 2. Owt%, the active oxygen B.10th, the blunt method according to described in claim 1 of, this method has following feature and advantage：(A) in grinding, active oxygen is added drop-wise to the rotation heat in disc mill by mill, energy transmission reaction is produced, cellulose is separated from cell interbed；(B) utilization active oxygen A, B collective effect, by the chromophore in lignin ", β-aldehyde ketone base class are converted into carboxylic acid or the colourless group of dicarboxylic acids class；(C) self-loopa：Feeding oxidation impregnation system after pretreatment of raw material, all used moisture two parts backflows are in oneself factory's interior circulation in technological process：Part I is the water after purification of raw materials processing, solid slag is transported after centrifugal clarification, the conventional beater floor of slurry feeding, produced clear water enters oneself factory's interior circulation water purifying tank, clarifier-tank built with 0.1% -0.15% three base oxygen or ozone generator, clear water is produced in decoloring reaction, water and containing micro oxygen radical, system is used into recirculated water by pump；Part II is the water after oxidation processes, handled after centrifugal clarification with conventional thickeners, slurry feeding reserve pit enters machine room, produced water filtration enters oneself factory's interior circulation water purifying tank, by the purified water pumping purification of raw materials system after processing, oxidation dipping systems, oxygen grinding system, screening system, used repeatedly in oneself factory's interior circulation.11st, the Paper slurries that any method is obtained in a kind of use claim 1-10.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2003/001121 WO2005064076A1 (en) | 2003-12-25 | 2003-12-25 | Closed cycle zero discharge oxidizing pulping process |
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| CN1878909A true CN1878909A (en) | 2006-12-13 |
| CN100420789C CN100420789C (en) | 2008-09-24 |
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| US (1) | US20070272377A1 (en) |
| EP (1) | EP1707668A1 (en) |
| CN (1) | CN100420789C (en) |
| AU (1) | AU2003292884A1 (en) |
| WO (1) | WO2005064076A1 (en) |
| ZA (1) | ZA200605196B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108547079A (en) * | 2018-06-08 | 2018-09-18 | 北京鹏盛天纤科技有限公司 | A kind of absorbent cotton green continous way production integrating device and technique |
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| CN101381970B (en) * | 2007-09-05 | 2011-06-15 | 中国科学院过程工程研究所 | Method for co-producing paper pulp and fuel ethanol by wild grass on forest land |
| US20090090478A1 (en) * | 2007-10-05 | 2009-04-09 | Hollomon Martha G | Selectivity improvement in oxygen delignification and bleaching of lignocellulose pulp using singlet oxygen |
| US9512237B2 (en) | 2009-05-28 | 2016-12-06 | Gp Cellulose Gmbh | Method for inhibiting the growth of microbes with a modified cellulose fiber |
| US9511167B2 (en) | 2009-05-28 | 2016-12-06 | Gp Cellulose Gmbh | Modified cellulose from chemical kraft fiber and methods of making and using the same |
| US9512563B2 (en) | 2009-05-28 | 2016-12-06 | Gp Cellulose Gmbh | Surface treated modified cellulose from chemical kraft fiber and methods of making and using same |
| CA2949518C (en) | 2009-05-28 | 2019-01-08 | Gp Cellulose Gmbh | Modified cellulose from chemical kraft fiber and methods of making and using the same |
| AU2012268700B2 (en) | 2011-05-23 | 2017-02-02 | Gp Cellulose Gmbh | Softwood kraft fiber having improved whiteness and brightness and methods of making and using the same |
| TWI628331B (en) | 2012-01-12 | 2018-07-01 | Ｇｐ纖維股份有限公司 | A low viscosity kraft fiber having reduced yellowing properties and methods of making and using the same |
| EP3495550A1 (en) | 2012-04-18 | 2019-06-12 | GP Cellulose GmbH | The use of surfactant to treat pulp and improve the incorporation of kraft pulp into fiber for the production of viscose and other secondary fiber products |
| WO2014122533A2 (en) | 2013-02-08 | 2014-08-14 | Gp Cellulose Gmbh | Softwood kraft fiber having an improved a-cellulose content and its use in the production of chemical cellulose products |
| RU2671653C2 (en) | 2013-03-14 | 2018-11-06 | ДжиПи СЕЛЛЬЮЛОУС ГМБХ | Method for manufacturing high functional low-viscosity kraft fibers with use of acid bleaching sequence and fiber produced therewith |
| CN105143547B (en) | 2013-03-15 | 2018-05-01 | Gp 纤维素股份有限公司 | With low viscosity kraft fibers for increasing carboxyl-content and production and preparation method thereof |
| KR102421357B1 (en) * | 2013-12-19 | 2022-07-18 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Using recycled waste water to make nonwoven fibrous materials suitable for use in a pollution control device or in a firestop |
| CN104153228A (en) * | 2014-07-31 | 2014-11-19 | 广西三威林产工业有限公司 | Wood chip washing and conveying device |
| CN105483936B (en) * | 2016-01-26 | 2017-11-21 | 天津鸿胜嘉德科技有限公司 | A kind of production method of spunlace non-woven cloth |
| CA3040734A1 (en) | 2016-11-16 | 2018-05-24 | Gp Cellulose Gmbh | Modified cellulose from chemical fiber and methods of making and using the same |
| CN110295507A (en) * | 2019-06-06 | 2019-10-01 | 安徽盛林环保科技有限公司 | Stalk extracts fibre technology |
| CN114808519B (en) * | 2022-04-22 | 2023-03-03 | 山东大汶河农业发展集团有限公司 | High-value utilization method of ginger straws |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE3881676D1 (en) * | 1988-01-25 | 1993-07-15 | Acetocell Gmbh & Co Kg | METHOD FOR TREATING LIGNINE-CONTAINING CELLULOSE MASS WITH OZONE. |
| AU5104593A (en) * | 1992-10-23 | 1994-05-24 | Macmillan Bloedel Limited | Improved ozone bleaching |
| CN1055737C (en) * | 1996-01-15 | 2000-08-23 | 南京林业大学 | Prescription and process for intensively bleaching pulp using singlet state oxygen in alkali bleaching stage of multi-stage process |
| DE19612194A1 (en) * | 1996-03-27 | 1997-10-02 | Consortium Elektrochem Ind | Multi-component system for changing, breaking down or bleaching lignin, lignin-containing materials or similar substances as well as methods for their use |
| CN1297085A (en) * | 1999-11-19 | 2001-05-30 | 普拉塞尔技术有限公司 | Method for use of activated ozone in bleaching paper pulp |
| DE10126988A1 (en) * | 2001-06-05 | 2002-12-12 | Call Krimhild | Systems for oxidation or bleaching, especially of pulp, comprise a component enzymatically generating peroxide, superoxide or other reactive oxygen species, and a precursor formed enzymatically, or is oxidizably reactive |
| US7396974B2 (en) * | 2002-02-08 | 2008-07-08 | University Of Maine | Oxidation using a non-enzymatic free radical system mediated by redox cycling chelators |
-
2003
- 2003-12-25 AU AU2003292884A patent/AU2003292884A1/en not_active Abandoned
- 2003-12-25 CN CNB2003801108070A patent/CN100420789C/en not_active Expired - Fee Related
- 2003-12-25 EP EP03767376A patent/EP1707668A1/en not_active Withdrawn
- 2003-12-25 US US10/583,763 patent/US20070272377A1/en not_active Abandoned
- 2003-12-25 WO PCT/CN2003/001121 patent/WO2005064076A1/en active Application Filing
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108547079A (en) * | 2018-06-08 | 2018-09-18 | 北京鹏盛天纤科技有限公司 | A kind of absorbent cotton green continous way production integrating device and technique |
| CN108547079B (en) * | 2018-06-08 | 2023-10-10 | 北京鹏盛天纤科技有限公司 | Green continuous production integrated device and process for absorbent cotton |
Also Published As
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| ZA200605196B (en) | 2008-01-08 |
| WO2005064076A1 (en) | 2005-07-14 |
| EP1707668A1 (en) | 2006-10-04 |
| AU2003292884A1 (en) | 2005-07-21 |
| US20070272377A1 (en) | 2007-11-29 |
| CN100420789C (en) | 2008-09-24 |
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