CN101305127B - A new pulp and process for pulping - Google Patents
A new pulp and process for pulping Download PDFInfo
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- CN101305127B CN101305127B CN2006800418482A CN200680041848A CN101305127B CN 101305127 B CN101305127 B CN 101305127B CN 2006800418482 A CN2006800418482 A CN 2006800418482A CN 200680041848 A CN200680041848 A CN 200680041848A CN 101305127 B CN101305127 B CN 101305127B
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- Prior art keywords
- ligno
- cellulosic materials
- salt
- paper pulp
- tetraalkylammonium salt
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Classifications
-
- 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
- D21C9/007—Modification of pulp properties by mechanical or physical means
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C1/00—Pretreatment of the finely-divided materials before digesting
- D21C1/06—Pretreatment of the finely-divided materials before digesting with alkaline reacting compounds
Abstract
The invention relates to a new pulp, which is derived from lignocellulosic material subjected for agitation in aqueous tetra-alkylammonium salt solution under microwave irradiation. The invention relates also to a process for pulping lignocellulosic material and to a process for softening lignocellulosic material. The treated material is preferably wood, softwood or hardwood.
Description
Invention field
The present invention relates to new paper pulp, it is by the ligno-cellulosic materials that obtains under stirring in the tetra-allkylammonium saline solution under microwave irradiation.The invention still further relates to the method for the pulping process and the softening ligno-cellulosic materials of ligno-cellulosic materials.
Background technology
Paper pulp
Paper pulp is the raw material of producing paper, cardboard, fiberboard and similarly manufacturing a product.Its purified form is the cellulose source of artificial silk, cellulose or other cellulose-derived products.
Obtain paper pulp by string, so it is reproducible resource.Since the earliest Babylon and Egyptian civilization, fibre plant is used as the resource that is used for writing material, for example papyrus always.The origin of papermaking (it is to be bondd by the fiber that separates to form interior poly-sheet material again) is owing to the Cai Lun in 105AD China in period, and it uses bamboo, paper mulberry bark and rag.Up to 1800 mid-nineties 90s, the commercial timber that just uses is as the papermaking resource.The current primary timber pulping process that uses is for example pulverized timber, soda, SO2 or sulphite and sulfate or brown paper method respectively exploitation in 1844,1853,1866 and 1870.Because their development, so fundamental method is modified and changes, and this technology is highly improved.
For most of industry, the environment of nineteen seventies and the worry of energy have influenced the great variety of paper pulp and paper mill operation, and many effort are devoted to develop the production method that energy is the most effective and clean most.In most of the cases, the practice result of short-term becomes the method for increase, for example washer, settling vessel, storage pool (holding pond) etc., the discharging of their minimum stream fluids.Other trend are, pulverize the timber method by modification, improve pulp quality, increase the paper pulp that uses high yield, in harvesting and section, use more trees and eliminate or be minimized in the slurrying huge sulfur-containing compound and from the poisonous and corrosivity chlorine compound of bleaching.
Before pulping process, handle timber by harvesting, peeling, section and screening technology.The section purpose that is used for slurrying is reduction timber permeates and spread and do not have excessively cutting or damaged fiber to the chemicals that allows processing a size.The long fragment of about 20mm flows freely easily and can be pneumatic or transport on belt, and is in heaps then or store in storeroom.Kirk-Othmer, Encyclopedia of Chemical Technology, the 3rd edition, 379-391 page or leaf.
Paper pulp of the present invention can be subdivided into mechanical pulp and chemical pulp.
Described mechanical pulp is subdivided into pulverizes wood pulp, thermomechanical pulp (TMP) and chemical thermo-mechanical pulp (CTMP).By pasting the wetting moistening timber of revolving wheel extruding, wherein the axle of timber is parallel to the axle of wheel, thereby wood pulp is pulverized in preparation.Temperature in the pulverizing district of centre can be 180-190 ℃.Removing of the motion of water and paper pulp controlled and heat dissipation, thereby prevents the timber coking.After this processing, pulverize wood pulp except containing independent fiber, also contain fibre bundle, broken fiber and the particulate of remarkable ratio (70-80wt%).Fiber is the timber with initial complete cell wall lignin basically.Therefore they are very hard and huge, and do not cave in as chemical paper fiber.Because the productive rate with about 95% obtains to pulverize wood pulp, so its cost is low relatively.Except the main direct cost of timber is an electric power, for about 49-75kJ (11,7-17,9kcl)/ton normal paper grade.
By wood chip prewashing is steamed 110-150 ℃, so that make them extending, thus preparation thermomechanical pulp (TMP).During temperature more than it is heated to the glass transition point of wet lignin, the thermoplastification of timber takes place.When these wood chips in fiberizer under high-consistency during fibration, all independent fibers are released; In the thin layer of centre, separate, and produce banded (ribbonlike) material by the S1 layer of cell membrane.Fibration content depends on the defibrination condition and is crucial for pulp property.This material has high light scattering coefficient, but it is lower than pulverizing timber, and has high flexibility, obtains bonding and the surface flatness good with paper.Long stapled increase ratio is improved the tear resistance of TMP paper pulp, but the fiber in this part is hard and bonding is seldom had contribution.Compare with pulverizing wood pulp, the fiber fragmentation is wanted much less.
Prepare chemical thermo-mechanical pulp (CTMP) with the TMP same way as, but the preliminary treatment fragment is handled with sodium sulfite gentleness under pH9-10.In the method, with chemicals dipping fragment, the subsequently defibrination of Steam Heating to 130-170 ℃.Productive rate is 90-92%, than the low 2-3% of TMP.Compare with suitable thermomechanical pulp, CTMP paper pulp has bigger long fiber fraction and lower particulate part.Complete fiber is bigger than TMP fiber flexibility, therefore obtains better shhet and forms and adhesive property.It is reported that CTMP slurrying is particularly suitable for the wooden slurry of high density rigid.
In chemical pulping, the enough lignin of dissolving from middle thin slice allows at the defibre down of mechanism (if any) seldom.Yet a part of cell wall lignin is retained in the fiber, and attempts removing it in digestion process and cause the paper pulp excessive degradation.For this reason, the lignin of about 3-4wt% remains in the hardwood chemical pulp and 4-10wt% remains in the cork chemical pulp usually.If make complete delignified paper pulp, then subsequently by in independent processing, removing delignification.
The delignified speed of concentration affects of the boiling mother liquor that contacts with timber.In the time of in it is penetrated into fragment, because chemicals causes carrying out relatively slowly in fragment center delignification through the required time that exhausts of wood structure diffusion and actual concentrations.Hard cook for the major part that prevents paper pulp stops boiling after the delignification fully at bigger fragment center usually.So gained paper pulp contains some not timber relic of defiber, described timber relic will and turn back to boiling vessel or mechanical fiberization by screening and separating.
Main chemical pulping wood method is brown paper or sulfate process.Alkaline pulp-making mother liquor or cooked solution contain the NaOH and the vulcanized sodium of the 3-1 ratio of having an appointment.Title brown paper is meant German intensity, and it characterizes and compares as if the paper pulp (as in initial soda process) that uses NaOH to obtain separately, the paper pulp by force that produces when comprising vulcanized sodium in the slurrying mother liquor.Another title, promptly sulfate process is derived from and uses sodium sulphate as the supply chemicals in removal process.By organic carbon of deriving, sodium sulphate is reduced into vulcanized sodium in recovery furnace.
Vulcanized sodium and sodium hydroxide solution are in the following balance:
Therefore, moisture vulcanized sodium is the source of hydroxide ion and must pays attention in the adjusting chemicals is reinforced.In the industry of North America, developed a kind of system, wherein based on etc. weight, by the two is expressed as itself and sodium oxide molybdena Na with NaOH and vulcanized sodium
2The equal weight of O is put into NaOH and vulcanized sodium.Work as Na
2S and NaOH all are expressed as Na
2During O, the percentage of the vulcanized sodium in the mixture is called as sulphidity (sulfidity).Reinforced, the mother liquor composition of chemicals, heat time heating time and reaction temperature are to treat the function of wood species or the species mixture and the purposes that paper pulp is planned of boiling.In producing the bleached grade paper pulp that fine paper uses, be active alkali 18% at the typical set condition of southern pine; Sulphidity 25%; Mother liquor is 4: 1 with the ratio of timber; In the thermal treatment zone, top 170 ℃ following 90 minutes and following 90 minutes at 170 ℃ in second district.Hardwood requires so inviolent condition, mainly is because initial content of lignin is lower.
Although the brown paper method by high level of development, be applicable and effective method, it use to exist some problems and shortcoming.Single factory is the requirement of minimization of energy, water and chemicals hardy.In addition, there are two intrinsic problems in chemical method, that is low-carb productive rate and form huge organosulfur compound.
A kind of modification of the brown paper method of commercial employing is the polysulfide method.When elementary sulfur joins in the solution of vulcanized sodium and NaOH, sulphur dissolving and to form general formula be Na
2S
xComplex mixture (wherein x is 2-5, and this depends on equilibrium condition and adds how much sulphur).Sulphur Na
2S
xBe oxidant, under the condition of brown paper slurrying, it changes into mutually alkali stable glycuronic acid with hemiacetal functional group.In the polysulfide method increase of productive rate be directly proportional based on the sulfur content (up to about 10%) that timber added.
A kind of extra pulping process is sulphite slurrying.In initial sodium sulfite process, use SO
2Make pulping wood with the aqueous solution of lime.Calcium sulfite has very limited solubility and excessive SO more than pH2
2Gas remains in the boiling vessel, so that keep pH described below horizontal.Therefore, this method may be opposite with brown paper or soda process, is a kind of acid system.Use alkali and SO except calcium at present
2Solution and sulphite slurrying are meant that wherein whole pH scopes are used for the whole bag of tricks of all or a part of slurrying.Magnesium, sodium and ammonium are as the substitute of calcium.Magnesium sulfide has the solubility of reduction more than pH5, but sodium sulphate and ammonium sulfate are solvable under pH1-14.
Except foregoing pulp-making method, also there is the pulp-making method of some half chemistry.Difference between the chemical method of half chemistry and high yield is very little, and more is this situation of degraded between machinery and full chemical method.Half chemical method is chemical delignification basically, wherein needs mechanical treatment to stop chemical method with the some place of the fragment of defibre and part boiling therein.Can use any known chemical method to produce semichemical wood pulp.Although this paper pulp flexibility is less, compare with mechanical pulp, be similar to chemical pulp, this is because they do not depend on the fracture of fibre wall for bonding.Productive rate is that 60-85% and content of lignin are 15-20%.Lignin concentrates on fiber surface.
Microwave
According to recently known about the document of organic synthesis, when reacting required energy in the system time by using microwave radiation, introducing, the reaction time of organic reaction significantly descends.The conventional frequency of microwave energy is 2.45GHz.In organic synthesis, has obtainable document wide in range and that increase continuously in the field of use microwave technology.Mingos has published example (the D.Michael P.Mingos of survey article of the weak point of this theme in 1994; " Microwaves inchemical synthesis (microwave in the chemical synthesis) ", Chemistry and industry1, in August, 1994,596-599 page or leaf).People such as Loupy published recently about the summary of heterogeneous catalysis under microwave radiation (Loupy, A., Petit, A., Hamelin, J., Texier-Boullet, F., Jachault, P., Mathe, D.; " New solvent-freeorganic synthesis using focused microwave (using the microwave that focuses on, novel not solvent-laden organic synthesis) ", Synthesis 1998, the 1213-1234 pages or leaves).Strauss has published another representative article (C.R.Strauss, " A combinatorialapproach to the development of Environmentaly Benign OrganicChemical Preparations (combined method of development environment close friend's organic chemistry preparation) ", Aust.J.Chem.1999,52, the 83-96 pages or leaves).
Microwave in the machinery pulping
Patent CA2008526 discloses the ligno-cellulosic materials that uses the heating using microwave dipping, makes the method for paper pulp.In the presence of catalyst and chelating agent, at the slurrying mother liquor (Na of prior art
2SO
3Solution) flood in.Follow boiling vessel internal irradiation gained material after the dipping of described chemicals in microwave.Then carry out independent mechanical jordaning step.The major advantage of microwave treatment is digestion time and the energy decreases that is consumed.
People such as Scott (TAPPI Fall Technol.Trade Fair, the 667-676 page or leaf) reported the preliminary treatment of the method for " the improvement paper performance of microwave energy saving daily record and mechanical pulp ", under any dipping situation that does not have extra chemicals, handled as mechanical pulp.For the power level of high use, the energy consumption in machinery pulping subsequently descends maximum 15%.Obviously, by rapid evaporation water, timber is softened, so ligno-cellulosic materials ruptures fast.
Microwave in timber and cellulosic dissolving
FI20031156 discloses the method for the microwave-assisted of dissolving lignocellulose material in ionic liquid.Dissolving is completely, and can be suitable for the ligno-cellulosic materials of any kind of, comprising cork and hardwood.Must under the situation that does not have water basically, dissolve.The dissolved substances component can be separated with the gained ionic liquid solution.
People such as Rogers announced in microwave field in 2002, method (Swatloski, the R.P. of dissolving pure cellulose fiber in ionic liquid; Spear S.K.; Holbrey, J.D.; Rogers, R.D.Journal of American Chemical Society, 2002,124,4974-4975 page or leaf).Also must under the situation that does not have water basically, dissolve herein.
At " Comprehensive Cellulose Chemistry ", the 1st volume, Wiley-VCH discloses widely in the 59-67 page or leaf and has been used for cellulosic other non-organic solvents of deriving.The aqueous solution that proves especially different tetra-alkyl ammonium hydroxides is to be used for cellulosic active solvent.Realize dissolving fully apace.Because water always volume excessively exists, be unpractiaca therefore at solvent described in the cellulosic derivatization.
Summary of the invention
Slurrying is one of important and industry power consumption in the whole world.Because there are huge demand in climate change, the population of sustainable growth and the energy consumption of bringing thus to the effective production technology of new forms of energy in all industrial circles.In slurrying, eliminating or the sulphur compound of stench is reduced minimum is another benefit.
The purpose of this invention is to provide new paper pulp material.
Another purpose of the present invention provides the pulping process of ligno-cellulosic materials.
Further aim of the present invention provides the method for softening ligno-cellulosic materials.
According to following detailed description and claim, further purpose will become apparent.
The known fiber element can be dissolved in the described tetra-alkyl ammonium hydroxide aqueous solution fully.Also knownly do not exist under the situation of water basically, timber may be dissolved in the ionic liquid.
During cellulose when test in the tetra-alkyl ammonium hydroxide aqueous solution dissolving timber in microwave field in, being surprisingly found out that, is not that cellulose but lignin in the timber dissolve in salting liquid.
Unforeseeablely be to finish therein under the mode that basic generation delignification and cellulose be kept perfectly as fine long fiber bundle and can stir.The present invention has realized new a kind of slurrying and preparation method thereof.
By the concentration and the mixing time of fine setting salt, can avoid delignification, and timber is sharply softening simultaneously.
In delignification's (slurrying) and these two processes of softening ligno-cellulosic materials, surprisingly require short processing, so that realize described result.After in microwave field, stirring in 1 minute, ligno-cellulosic materials, for example timber can or delignification or softening.
Detailed Description Of The Invention
According to the invention provides a kind of new paper pulp, described paper pulp is derived from the ligno-cellulosic materials that carried out stirring under microwave radiation in the tetra-allkylammonium saline solution.
Can in described solution, have or not have under the situation that stirs lignocellulose and stir.
Ligno-cellulosic materials can be the ligno-cellulosic materials of any kind of basically.The main source that is used for the fiber of paper pulp is a timber, for example cork and hardwood.Other sources comprise straw, grass and sugarcane.Can be mainly from natural any vacular plant, and non-wood resource, for example straw, grass, for example rice, cogongrass, wheat and sabai; Sugarcane and reed for example mainly are bagasse or sugar cane; Several bamboos; Bast fiber, for example jute, flax, mestha, flax, ramie and hemp; Leaf fibre for example extracts paper pulp fiber in agaba or abaca and the sisal hemp.
Preferably, ligno-cellulosic materials is a timber, for example cork and hardwood.
Ligno-cellulosic materials can be its primitive form of finding at occurring in nature, and perhaps it can partly be processed.In a preferred embodiment of the invention, ligno-cellulosic materials is made up of wood chip, and promptly under microwave radiation, lignocellulose timber carried out peeling and chopping before the described material of stirring in the tetra-allkylammonium saline solution.
Can be by steep water or described tetra-allkylammonium saline solution in ligno-cellulosic materials, preprocessing lignocellulose material.
The content of tetraalkylammonium salt can be 1-75wt% in the tetra-allkylammonium saline solution, preferably 5-60wt% and most preferably 10-40wt%.CATION in the tetraalkylammonium salt is:
R wherein
1, R
2, R
3And R
4Be C independently
1-C
30Alkyl, C
3-C
8Carbocyclic ring or C
3-C
8Anion in heterocyclic radical and this salt can be halogen, pseudohalogen, perchlorate, C
1-C
6Carboxylate radical or hydroxyl.
Preferably, anion is chloride or hydroxyl, and most preferably anion is a hydroxyl.
Preferred preferred especially tetraalkylammonium salt is R wherein
1, R
2, R
3And R
4Be C independently
4Anion in alkyl and this salt is a salt hydroxy.
If stir lignocellulose according to the present invention under microwave radiation, then other organic ion compounds are when when miscible, also can be used as the salt component with water.The variant (being called as ionic liquid) of this ionic compound is disclosed in FI20031156.
Can be under 40 ℃ to 270 ℃ temperature, preferably under 70 ℃ to 210 ℃ the temperature and most preferably stirring under 120 ℃ to 190 ℃.
When under microwave radiation, when ligno-cellulosic materials stirs in the tetra-allkylammonium saline solution, also can exert pressure.When applying, pressure preferably below 20bar, more preferably 2bar to 9bar below the 10bar and most preferably.
Mixing time can change to 24 hours from 1 minute, and this depends on employed salt and concentration thereof, the character of ligno-cellulosic materials and concentration, whipping temp and applied pressure possibly.
Paper pulp of the present invention can be used as to produce paper, cardboard, fiberboard and similarly manufacture a product uses material.
According to the present invention, a kind of pulping process of ligno-cellulosic materials also is provided, in described method, under microwave radiation, in the tetra-allkylammonium saline solution, carry out the stirring of ligno-cellulosic materials, so that set up partially or completely delignification.
In pulping process, can in described solution, have or not have under the situation that stirs ligno-cellulosic materials and stir.
Ligno-cellulosic materials can be the ligno-cellulosic materials of any kind of basically.The fiber main source that is used for paper pulp is a timber, for example cork and hardwood.Other resources comprise straw, grass and sugarcane.Can be mainly from natural any vacular plant, and non-wood resource, for example straw, grass, for example rice, cogongrass, wheat and sabai; Sugarcane and reed for example mainly are bagasse or sugar cane; Several bamboos; Bast fiber, for example jute, flax, mestha, flax, ramie and hemp; Leaf fibre for example extracts paper pulp fiber in agaba or abaca and the sisal hemp.
Preferably, employed ligno-cellulosic materials is a timber, for example cork and hardwood.
Ligno-cellulosic materials can be its primitive form of finding at occurring in nature, and perhaps it can partly be processed.In a preferred embodiment of the invention, ligno-cellulosic materials is made up of wood chip, and promptly under microwave radiation, lignocellulose timber carried out peeling and chopping before the described material of stirring in the tetra-allkylammonium saline solution.
Can be by steep water or described tetra-allkylammonium saline solution in ligno-cellulosic materials, preprocessing lignocellulose material.
In pulping process, the content of tetraalkylammonium salt can be 1-75wt% in the tetra-allkylammonium saline solution, preferably 5-60wt% and most preferably 10-40wt%.CATION in the tetraalkylammonium salt is:
R wherein
1, R
2, R
3And R
4Be C independently
1-C
30Alkyl, C
3-C
8Carbocyclic ring or C
3-C
8Anion in heterocyclic radical and this salt can be halogen, pseudohalogen, perchlorate, C
1-C
6Carboxylate radical or hydroxyl.
Preferably, anion is chloride or hydroxyl, and most preferably anion is a hydroxyl.
In pulping process, preferred preferred especially tetraalkylammonium salt is R wherein
1, R
2, R
3And R
4Be C independently
4Anion in alkyl and this salt is a described salt hydroxy.
In pulping process of the present invention, other organic ion compounds are when when miscible, also can be used as the salt component with water.In FI20031156, exemplified adoptable compound.
In the pulping process of the present invention, can be under 40 ℃ to 270 ℃ temperature, preferably under 70 ℃ to 210 ℃ the temperature and most preferably stirring under 120 ℃ to 190 ℃.
When under microwave radiation, when ligno-cellulosic materials stirs in the tetra-allkylammonium saline solution, also can exert pressure.When applying, pressure preferably below 20bar, more preferably 2bar to 9bar below the 10bar and most preferably.
Mixing time can change to 24 hours from 1 minute, and this depends on employed salt and concentration thereof, the character of ligno-cellulosic materials and concentration, whipping temp and applied pressure possibly.
In pulping process of the present invention, advantageously select described parameter, its mode makes and partially or completely makes ligno-cellulosic materials delignification.
The ligno-cellulosic materials of slurrying can be used as to produce paper, cardboard, fiberboard and similarly manufacture a product uses material.
According to the method that the present invention further provides softening ligno-cellulosic materials, in described method, ligno-cellulosic materials stirs in the tetra-allkylammonium saline solution under microwave radiation.
In softening process, can in described solution, have or not have under the situation that stirs ligno-cellulosic materials and stir.
In described softening process, ligno-cellulosic materials can be the ligno-cellulosic materials of any kind of basically.The fiber main source that is used for paper pulp is a timber, for example cork and hardwood.Other resources comprise straw, grass and sugarcane.Can be mainly from natural any vacular plant, and non-wood resource, for example straw, grass, for example rice, cogongrass, wheat and sabai; Sugarcane and reed for example mainly are bagasse or sugar cane; Several bamboos; Bast fiber, for example jute, flax, mestha, flax, ramie and hemp; Leaf fibre for example extracts paper pulp fiber in agaba or abaca and the sisal hemp.
Preferably, employed ligno-cellulosic materials is a timber, for example cork and hardwood.
Ligno-cellulosic materials can be its primitive form of finding at occurring in nature, and perhaps it can partly be processed.In a preferred embodiment of the invention, ligno-cellulosic materials is made up of wood chip, and promptly under microwave radiation, lignocellulose timber carried out peeling and chopping before the described material of stirring in the tetra-allkylammonium saline solution.
Can be by steep water or described tetra-allkylammonium saline solution in ligno-cellulosic materials, preprocessing lignocellulose material.
In softening process of the present invention, the content of tetraalkylammonium salt can be 1-75wt% in the tetra-allkylammonium saline solution, preferably 5-60wt% and most preferably 10-40wt%.CATION in the tetraalkylammonium salt is:
R wherein
1, R
2, R
3And R
4Be C independently
1-C
30Alkyl, C
3-C
8Carbocyclic ring or C
3-C
8Anion in heterocyclic radical and this salt can be halogen, pseudohalogen, perchlorate, C
1-C
6Carboxylate radical or hydroxyl.
Preferably, anion is chloride or hydroxyl, and most preferably anion is a hydroxyl.
Preferred preferred especially tetraalkylammonium salt is R wherein in softening process
1, R
2, R
3And R
4Be C independently
4Anion in alkyl and this salt is a described salt hydroxy.
In softening process of the present invention, other organic ion compounds are when when miscible, also can be used as the salt component with water.In FI20031156, exemplified adoptable compound.
In the softening process of the present invention, can be under 40 ℃ to 270 ℃ temperature, preferably under 70 ℃ to 210 ℃ the temperature and most preferably stirring under 120 ℃ to 190 ℃.
In softening process of the present invention, also can exert pressure.When applying, pressure preferably below 20bar, more preferably 2bar to 9bar below the 10bar and most preferably.
Mixing time can change to 24 hours from 1 minute, and this depends on employed salt and concentration thereof, the character of ligno-cellulosic materials and concentration, whipping temp and applied pressure possibly.
In softening process of the present invention, advantageously select described parameter, its mode makes does not have slurrying by only softening ligno-cellulosic materials.Therefore, delignification does not take place in softening process process of the present invention significantly.The structural break of ligno-cellulosic materials and with tetra-allkylammonium saline solution dipping, its mode make in procedure of processing process subsequently energy and/or chemical depletion descend.
Softening ligno-cellulosic materials can be used as to produce paper, cardboard, fiberboard and similarly manufacture a product uses material.
The present invention has realized can be according to fast and the new paper pulp made of the mode of Energy Efficient.The quality pulp that delignified degree can be finely tuned and gained paper pulp is made up of fine long fiber.The present invention has also realized the method for softening ligno-cellulosic materials.Described softening, ductile material then can energy more effective and efficient manner further process.Therefore, the present invention causes lower energy consumption and so environmental advantage.In addition, avoid forming huge organosulfur compound.Employed tetraalkylammonium salt is relatively cheap material, and it preferably is recycled.
Embodiment
Following embodiment has described the present invention rather than has limited described the present invention to embodiment.In embodiment 1-10, the ligno-cellulosic materials of handling is the Finnish cork rod that cuts from the long wood chip of 20mm.Be parallel to ply and cut this rod, so that help to form long fiber.The initial reason of cutting rod is the limited size of microwave reactor, that is 5ml.
Embodiment 1
In microwave field, in 40% moisture TBAH, handled cork 5 minutes at 170 ℃
In the reactor tube of the sealing of being furnished with magnetic stirring bar, 4, mix about 750mg cork rod in the aqueous solution of 5ml 40% TBAH, and stirred 5 minutes down at 170 ℃.
Stirring causes containing the solution of the burgundy of long fiber particulate.Wash with water and obtain two bundles oldlace fiber separately and the fiber that separates fully.
Embodiment 2
In microwave field, in the moisture TBAH 20% under 170 ℃, handled cork 5 minutes
In the reactor tube of the sealing of being furnished with magnetic stirring bar, 4, mix about 750mg cork rod in the aqueous solution of 5ml 20% TBAH, and stirred 5 minutes down at 170 ℃.
Stirring causes containing the solution of the burgundy of long fiber particulate.Wash with water and obtain two bundles oldlace fiber separately and the fiber that separates fully.Paper pulp ratio of components embodiment 1 is more complete a little.
Embodiment 3
In microwave field, in the moisture TBAH 10% under 170 ℃, handled cork 5 minutes
In the reactor tube of the sealing of being furnished with magnetic stirring bar, 4, mix about 750mg cork rod in the aqueous solution of 5ml 10% TBAH, and stirred 5 minutes down at 170 ℃.
Stirring causes containing the solution of the burgundy of long fiber particulate.Wash with water and obtain two bundles oldlace fiber separately, and paper pulp ratio of components embodiment 2 is more complete.
Embodiment 4
In microwave field, in the moisture TBAH 10% under 170 ℃, handled cork 30 minutes
In the reactor tube of the sealing of being furnished with magnetic stirring bar, 4, mix about 750mg cork rod in the aqueous solution of 5ml 10% TBAH, and stirred 30 minutes down at 170 ℃.
Stirring causes containing the solution of the burgundy of long fiber particulate.Wash with water and obtain two bundles oldlace fiber separately, and the paper pulp composition is similar to embodiment 1.
Embodiment 5
In microwave field, in the moisture TBAH 40% under 120 ℃, handled cork 5 minutes
In the reactor tube of the sealing of being furnished with magnetic stirring bar, 4, mix about 750mg cork rod in the aqueous solution of 5ml 40% TBAH, and stirred 5 minutes down at 120 ℃.
Stirring causes containing the solution of the burgundy of long fiber particulate.Wash with water and obtain two bundles oldlace fiber separately and the fiber that separates fully.The paper pulp composition is similar to embodiment 2.
Embodiment 6
In microwave field, in the moisture TBAH 5% under 120 ℃, handled cork 5 minutes
In the reactor tube of the sealing of being furnished with magnetic stirring bar, 4, mix about 750mg cork rod in the aqueous solution of 5ml 5% TBAH, and stirred 5 minutes down at 120 ℃.
Stirring causes containing the brown solution of some wooden sticks and long fiber particulate.Wash with water and obtain sharply softening wooden stick, some particulates separate from described rod.
Embodiment 7
In microwave field, in the moisture TBAH 40% under 80 ℃, handled cork 5 minutes
In the reactor tube of the sealing of being furnished with magnetic stirring bar, 4, mix about 750mg cork rod in the aqueous solution of 5ml 40% TBAH, and stirred 5 minutes down at 80 ℃.
Stirring causes containing the brown solution of some wooden sticks and long fiber particulate.Wash with water and obtain the sharply softening wooden stick that separates with part, some particulates also separate from described rod.
Embodiment 8
In microwave field, in the moisture TBAH 10% under 80 ℃, handled cork 30 minutes
In the reactor tube of the sealing of being furnished with magnetic stirring bar, 4, mix about 750mg cork rod in the aqueous solution of 5ml 10% TBAH, and stirred 30 minutes down at 80 ℃.
The same with embodiment 7, stir the brown solution that causes containing some wooden sticks and long fiber particulate.Wash with water and obtain the sharply softening wooden stick that separates with part, some particulates also separate from described rod.
Embodiment 9
In microwave field, in the moisture TBAH 10% under 70 ℃, handled cork 1 hour
In the reactor tube of the sealing of being furnished with magnetic stirring bar, 4, mix about 750mg cork rod in the aqueous solution of 5ml 10% TBAH, and stirred 1 hour down at 70 ℃.
Stir the transparent light brown solution that causes containing some wooden sticks herein.Wash with water and obtain the sharply softening wooden stick that separates with part.
Embodiment 10
In microwave field, in the NaOH (NaOH) 40% under 170 ℃, handled cork 5 minutes
In the reactor tube of the sealing of being furnished with magnetic stirring bar, 4, mix about 750mg cork rod in the aqueous solution of 5ml 40% NaOH (NaOH), and stirred 5 minutes down at 170 ℃.
Stirring herein causes fibrous material to destroy, thus the brown organic material sheet that is not had the viscosity of fibre property.
Embodiment 11
Under the situation that does not have microwave field, in 40% moisture TBAH, handle the contrast of cork
In the reactor tube of the sealing of being furnished with magnetic stirring bar, in 12ml 40% TBAH (NaOH) aqueous solution, mix about 2000mg cork rod, and under 95 ℃, stir and spend the night
Stirring herein causes fibrous material to destroy, thus the brown organic material sheet that is not had the viscosity of fibre property.
Claims (27)
1. a paper pulp is characterized in that this paper pulp is to obtain by ligno-cellulosic materials is stirred in the aqueous solution at tetraalkylammonium salt under the microwave radiation, and wherein the content of tetraalkylammonium salt in the aqueous solution of tetraalkylammonium salt is 1-75wt%.
2. the paper pulp of claim 1 is characterized in that ligno-cellulosic materials is cork or hardwood.
3. the paper pulp of claim 2, the content that it is characterized in that tetraalkylammonium salt in the tetra-allkylammonium saline solution is 5-60wt%.
4. the paper pulp of claim 3, the content that it is characterized in that tetraalkylammonium salt in the tetra-allkylammonium saline solution is 10-40wt%.
5. claim 1 or 2 paper pulp is characterized in that the CATION in the tetraalkylammonium salt is:
R wherein
1, R
2, R
3And R
4Be C independently
1-C
30Alkyl, C
3-C
8Carbocyclic ring or C
3-C
8Anion in heterocyclic radical and this salt is halogen, pseudohalogen, perchlorate, C
1-C
6Carboxylate radical or hydroxyl.
6. the paper pulp of claim 5 is characterized in that R
1, R
2, R
3And R
4Be C independently
4Anion in alkyl and this salt is a hydroxyl.
7. claim 1 or 2 paper pulp is characterized in that stirring under 40 ℃ to 270 ℃ temperature.
8. the paper pulp of claim 7 is characterized in that stirring under 70 ℃ to 210 ℃ temperature.
9. the paper pulp of claim 8 is characterized in that stirring under 120 ℃ to 190 ℃ temperature.
10. the pulping process of ligno-cellulosic materials, it is characterized in that in order to realize partially or completely delignificationization, ligno-cellulosic materials aqueous solution at tetraalkylammonium salt under microwave radiation is stirred, and wherein said tetraalkylammonium salt is 1-75wt% at the content of the aqueous solution of tetraalkylammonium salt.
11. the method for claim 10 is characterized in that ligno-cellulosic materials is cork or hardwood.
12. the method for claim 11, the content that it is characterized in that tetraalkylammonium salt in the tetra-allkylammonium saline solution is 5-60wt%.
13. the method for claim 12, the content that it is characterized in that tetraalkylammonium salt in the tetra-allkylammonium saline solution is 10-40wt%.
14. the method for claim 10 or 11 is characterized in that the CATION in the tetraalkylammonium salt is:
R wherein
1, R
2, R
3And R
4Be C independently
1-C
30Alkyl, C
3-C
8Carbocyclic ring or C
3-C
8Anion in heterocyclic radical and this salt is halogen, pseudohalogen, perchlorate, C
1-C
6Carboxylate radical or hydroxyl.
15. the method for claim 14 is characterized in that R
1, R
2, R
3And R
4Be C independently
4Anion in alkyl and this salt is a hydroxyl.
16. the method for claim 10 or 11 is characterized in that stirring under 40 ℃ to 270 ℃ temperature.
17. the method for claim 16 is characterized in that stirring under 70 ℃ to 210 ℃ temperature.
18. the method for claim 17 is characterized in that stirring under 120 ℃ to 190 ℃ temperature.
19. the method for softening ligno-cellulosic materials is characterized in that ligno-cellulosic materials is being stirred in this tetra-allkylammonium saline solution under the microwave radiation, wherein said tetraalkylammonium salt is 1-75wt% at the content of the aqueous solution of tetraalkylammonium salt.
20. the method for claim 19 is characterized in that ligno-cellulosic materials is cork or hardwood.
21. the method for claim 20, the content that it is characterized in that tetraalkylammonium salt in the tetra-allkylammonium saline solution is 5-60wt%.
22. the method for claim 21, the content that it is characterized in that tetraalkylammonium salt in the tetra-allkylammonium saline solution is 10-40wt%.
23. the method for claim 19 or 20 is characterized in that the CATION in the tetraalkylammonium salt is:
R wherein
1, R
2, R
3And R
4Be C independently
1-C
30Alkyl, C
3-C
8Carbocyclic ring or C
3-C
8Anion in heterocyclic radical and this salt is halogen, pseudohalogen, perchlorate, C
1-C
6Carboxylate radical or hydroxyl.
24. the method for claim 23 is characterized in that R
1, R
2, R
3And R
4Be C independently
4Anion in alkyl and this salt is a hydroxyl.
25. the method for claim 19 or 20 is characterized in that stirring under 40 ℃ to 270 ℃ temperature.
26. the method for claim 25 is characterized in that stirring under 70 ℃ to 210 ℃ temperature.
27. the method for claim 26 is characterized in that stirring under 120 ℃ to 190 ℃ temperature.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI20051145 | 2005-11-11 | ||
| FI20051145A FI20051145A0 (en) | 2005-11-11 | 2005-11-11 | New pulp and process for pulping |
| PCT/FI2006/000362 WO2007054610A1 (en) | 2005-11-11 | 2006-11-10 | A new pulp and process for pulping |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101305127A CN101305127A (en) | 2008-11-12 |
| CN101305127B true CN101305127B (en) | 2011-10-12 |
Family
ID=35458753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800418482A Expired - Fee Related CN101305127B (en) | 2005-11-11 | 2006-11-10 | A new pulp and process for pulping |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US20100006245A1 (en) |
| EP (1) | EP1954872A1 (en) |
| JP (1) | JP2009516086A (en) |
| KR (1) | KR20080083114A (en) |
| CN (1) | CN101305127B (en) |
| BR (1) | BRPI0618527A2 (en) |
| CA (1) | CA2627265A1 (en) |
| FI (1) | FI20051145A0 (en) |
| NO (1) | NO20082535L (en) |
| RU (1) | RU2401352C2 (en) |
| WO (1) | WO2007054610A1 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2033974A1 (en) * | 2007-09-06 | 2009-03-11 | The Queens University of Belfast | Conversion method |
| JP5301237B2 (en) * | 2007-10-17 | 2013-09-25 | 新日鉄住金化学株式会社 | Method for producing solubilized lignin, saccharide raw material and monosaccharide raw material |
| RU2480547C2 (en) * | 2008-01-30 | 2013-04-27 | Курасики Босеки Кабусики Кайся | Method of treatment with flame retardant and fire-hardened material of cellulose fibers |
| JP5410060B2 (en) * | 2008-10-02 | 2014-02-05 | 株式会社Ｋｒｉ | Separation of lignocellulosic biomass from cellulose and lignin using ionic liquid |
| NZ599844A (en) | 2009-02-11 | 2013-12-20 | Xyleco Inc | Processing biomass |
| CN101806007B (en) * | 2010-04-09 | 2011-09-07 | 山东轻工业学院 | Method for treating paper pulp by using 1-allyl-3-methylimidazole chloride |
| PT105422A (en) * | 2010-12-09 | 2012-06-11 | Univ Aveiro | MODIFIED CELLULOSE PULP, PREPARATION METHOD BY PROCESSING BY HIGH PRESSURE AND THEIR APPLICATIONS |
| AU2013329146B2 (en) | 2012-10-10 | 2017-03-09 | Xyleco, Inc. | Processing materials |
| JP6502257B2 (en) | 2012-10-10 | 2019-04-17 | ザイレコ，インコーポレイテッド | Processing of biomass |
| NZ706072A (en) | 2013-03-08 | 2018-12-21 | Xyleco Inc | Equipment protecting enclosures |
| GB201304872D0 (en) * | 2013-03-15 | 2013-05-01 | Imp Innovations Ltd | Treatment |
| US11118308B2 (en) | 2013-03-15 | 2021-09-14 | Ip2Ipo Innovations Limited | Treatment of lignocellulosic biomass with ionic liquid |
| CN103498375B (en) * | 2013-09-24 | 2015-06-03 | 昆明理工大学 | Method for pulping by broussonetia papyrifera white-bark |
| GB201520453D0 (en) | 2015-11-20 | 2016-01-06 | Imp Innovations Ltd | Process |
| CN112359634B (en) * | 2020-10-26 | 2022-10-21 | 顾理富 | New technology of traditional culture paper |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679146A (en) * | 1993-09-14 | 1997-10-21 | Lenzing Aktiengesellschaft | Moulding materials and spinning materials containing cellulose |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1943176A (en) * | 1930-09-27 | 1934-01-09 | Chem Ind Basel | Cellulose solution |
| SE385027B (en) * | 1974-09-27 | 1976-05-31 | Mo Och Domsjoe Ab | PROCEDURE FOR RELEASING CELLULOSIAN FIBERS |
| JPS5522067A (en) * | 1978-08-03 | 1980-02-16 | Toyo Pulp Co Ltd | Bleaching of broadleaf tree unbleached kraft pulp |
| US4548675A (en) * | 1983-05-16 | 1985-10-22 | New Fibers International | Nonsulfur chemimechanical pulping process |
| FR2552125B1 (en) * | 1983-09-16 | 1986-03-21 | Interox | PROCESS FOR THE TREATMENT OF CELLULOSIC MATERIALS BY OXIDIZING AGENTS |
| JPS60144332A (en) * | 1983-12-26 | 1985-07-30 | Tachikawa Kenkyusho | Dissolution of cellulose in organic solvent |
| SE508227C2 (en) * | 1997-05-30 | 1998-09-14 | Hampshire Chemical Ab | Extraction agents included essential oils and process for using them |
| US6146494A (en) * | 1997-06-12 | 2000-11-14 | The Procter & Gamble Company | Modified cellulosic fibers and fibrous webs containing these fibers |
| JP3989153B2 (en) * | 1999-06-25 | 2007-10-10 | 王子製紙株式会社 | Lignocellulosic cooking aid and pulp production method |
| JP2002105882A (en) * | 2000-09-25 | 2002-04-10 | Rengo Co Ltd | Method for producing cellulosic single fiber by fibrillation |
| US6824599B2 (en) * | 2001-10-03 | 2004-11-30 | The University Of Alabama | Dissolution and processing of cellulose using ionic liquids |
| JP2004285534A (en) * | 2003-03-25 | 2004-10-14 | Nippon Paper Industries Co Ltd | Method for bleaching chemithermomechanical pulp |
| JP2004285531A (en) * | 2003-03-25 | 2004-10-14 | Nippon Paper Industries Co Ltd | Method for digestion of chemical pulp |
| JP2004285532A (en) * | 2003-03-25 | 2004-10-14 | Nippon Paper Industries Co Ltd | Method for acid treatment of kraft pulp |
| EP2257669B1 (en) * | 2008-02-19 | 2017-03-22 | The Board Of Trustees Of The University Of Alabama | Ionic liquid systems for the processing of biomass, their components and/or derivatives, and mixtures thereof |
-
2005
- 2005-11-11 FI FI20051145A patent/FI20051145A0/en not_active IP Right Cessation
-
2006
- 2006-11-10 BR BRPI0618527-4A patent/BRPI0618527A2/en not_active IP Right Cessation
- 2006-11-10 KR KR1020087013967A patent/KR20080083114A/en not_active Application Discontinuation
- 2006-11-10 JP JP2008539461A patent/JP2009516086A/en active Pending
- 2006-11-10 WO PCT/FI2006/000362 patent/WO2007054610A1/en active Application Filing
- 2006-11-10 US US12/092,317 patent/US20100006245A1/en not_active Abandoned
- 2006-11-10 RU RU2008120137/12A patent/RU2401352C2/en not_active IP Right Cessation
- 2006-11-10 CA CA002627265A patent/CA2627265A1/en not_active Abandoned
- 2006-11-10 CN CN2006800418482A patent/CN101305127B/en not_active Expired - Fee Related
- 2006-11-10 EP EP06807988A patent/EP1954872A1/en not_active Withdrawn
-
2008
- 2008-06-06 NO NO20082535A patent/NO20082535L/en not_active Application Discontinuation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679146A (en) * | 1993-09-14 | 1997-10-21 | Lenzing Aktiengesellschaft | Moulding materials and spinning materials containing cellulose |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20080083114A (en) | 2008-09-16 |
| EP1954872A1 (en) | 2008-08-13 |
| NO20082535L (en) | 2008-06-06 |
| BRPI0618527A2 (en) | 2011-09-06 |
| FI20051145A0 (en) | 2005-11-11 |
| WO2007054610A1 (en) | 2007-05-18 |
| US20100006245A1 (en) | 2010-01-14 |
| CA2627265A1 (en) | 2007-05-18 |
| JP2009516086A (en) | 2009-04-16 |
| RU2401352C2 (en) | 2010-10-10 |
| CN101305127A (en) | 2008-11-12 |
| RU2008120137A (en) | 2009-12-20 |
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