CN103619922A

CN103619922A - Process

Info

Publication number: CN103619922A
Application number: CN201280030025.5A
Authority: CN
Inventors: 马丁·理查德·科克罗夫特; 卢克·费希尔
Original assignee: Innovia Films Ltd
Current assignee: Innovia Films Ltd
Priority date: 2011-05-20
Filing date: 2012-05-18
Publication date: 2014-03-05
Also published as: GB201108530D0; GB2493490A; WO2012160363A1; EP2710053A1

Abstract

Disclosed herein is a method of producing cellulose shaped articles comprising the steps of exposing non-dissolving cellulose-containing pulp to electron beam radiation originating from a plurality of locations, forming a solution or dope comprising the cellulose-containing pulp, and casting a cellulose shaped article from the solution. Products of the method and systems for implementing the method are also disclosed.

Description

Method

Invention field

The invention provides the method for processing of cellulose, wherein the paper pulp of non-solubility cellulose is processed so that it is suitable for the cellulose forming product of preparation such as fiber.Also provide for implementing the system of such method.

Background technology

Except the practicality in the industrial production of paper, the paper pulp of cellulose has a lot of other application, comprises the industry manufacture such as the cellulose forming product of fiber.

The source that has the paper pulp of a lot of cellulose, for example timber (particularly soft wood), cotton, flax, hemp and bamboo class.Paper pulp is prepared by these starting material conventionally, and described starting material also remove delignification and hemicellulose by processing with separation, thereby the content of cellulose of paper pulp is maximized.

Those skilled in the art are known two kinds of general pulping techniques.First, by grind or the starting material of milling with physically separated fiber cellulose fiber and hemicellulose and xylogen, can mechanically prepare paper pulp.

Alternatively, can chemically process starting material with dissolved lignin and hemicellulose, ideally not destroy and be derived from raw-material cellulosic fibre.The example of chemical pulping method comprises sulphate cook method (Kraft process) and sulphite process.

Also have a large amount of mixed pulp methods, wherein in mechanical pulp-making method, use chemical process step, vice versa.The example of such method comprises thermomechanical method, and wherein, except mechanical disintegration, wood chip or other starting material also will be exposed to heat; With chemi thermo mechanical method, wherein, before pulverizing and heat exposure, first wood chip is exposed to chemicals used in chemical pulping method.

For the technician in cellulose regenerated field, two class paper pulp from chemical pulping method, have been obtained.First-selection is ' dissolving pulp ' or ' dissolving grade paper pulp ', and it is as the raw material of viscose process.Dissolving pulp is characterised in that high cellulose content, approximately more than 90%.As shown in their title, they are soluble in commercial fibres element reclaiming process solvent used or jelly (dopes).

The another kind of of paper pulp is ' non-dissolving pulp ', and the example comprises ' commercial pulp ' or ' fluff pulp '.These have limited practicality in viscose process and other methods for the production of cellulose forming product, because as shown in their titles, they are insoluble in conventional process solutions or jelly.Therefore, they are mainly used in the application except cellulose regenerated.For example, in all fluff pulps of manufacturing, surpass 80% for the production of baby diaper.

Compare with dissolving pulp, due to the lower cost of non-dissolving pulp, previously in viscose process, utilized the trial of non-dissolving pulp.Yet, due to they deleterious effects to the character of gained viscose solution, so they only can use with low ratio, as packing material, be no more than approximately 5% to 10% of total paper pulp used.

The example of commercially available non-dissolving pulp comprises purchased from the Pearl429 of Fibria, UPM and ENCE (Weyerhauser), Peach (Weyerhauser), Fluff416 (Weyerhauser), Port Wentworth SBSK (Weyerhauser) and Bleached Eucalyptus paper pulp.

Except their solvability, non-dissolving pulp is different in many aspects from dissolving pulp.For example, they have the hemicellulose level higher than dissolving pulp, lower alpha-cellulose content conventionally, for what more do not refine, have the higher polymerization degree (DP) and/or have lower quality control.

Those skilled in the art will know, conventionally the viscose process of implementing comprises step: paper pulp is dissolved or slurrying in caustic soda in caustic soda, in caustic solution, flood, with dithiocarbonic anhydride yellow Mierocrystalline cellulose, and in caustic-alkali aqueous solution, dissolve again to form viscose glue.

Viscose glue is conventionally filtered and refilters so that the purity of material maximizes, thereby improves product quality.Then adopt technology well known by persons skilled in the art to make it form desired shape, for example, by spinning nozzle, extrude to form fibrous material, contact with acidity casting liquid subsequently with by viscose glue regenerated cellulose.

In some applications, between dipping and yellow step, cellulose slurry or the solution of dipping can alkalize, and wherein remove the alkali cellulose that a part of caustic alkali liquid (for example, by compacting) obtains having target Mierocrystalline cellulose and sodium carbonate (soda) content.The object of this step is to improve cellulosic character, main by reducing its polymerization degree (DP).

If make non-dissolving pulp carry out these conventional steps of implementing, the viscose solution of gained will have unacceptable low filterableness for the application that is shaped.Even if this detrimentally affect to the filterableness of viscose solution, hindered non-dissolving pulp with higher than slurry approximately 5 % by weight to 10 % by weight ratio and for viscose process.

On the other hand, be optimized to can be used for producing the viscose liquid with high-level filterableness for the dissolving pulp of viscose process.

Can adopt a lot of different testing method to measure filterableness.By obtaining the slope of a curve of being mapped and generated by the viscose glue weight of filter cloth in the interval with five minutes, calculate obstruction constant (Rv).

TVW is the measurement to the total amount of the viscose glue of 30 minutes inner filtrations.

Conventionally, Rv and TVW value are higher, and viscose glue quality is higher, because it can not block or stop up filter cloth.

With the ball settling velocity (BFV) of measuring second, be that the steel ball of counterweight 0.13g+/-0.02g sinks down into the measurement that the degree of depth is time of spending of the bottom of the viscose solution sample of 205mm.

As the substitute technology for quantitative viscose solution quality, can use Counting of fibers method, wherein measure the quantity of residual fiber in solution.

Except viscose process, the substitute technology of production of cellulose molded article is known.Recently, use ionic liquid to be for example disclosed in EP1458805, EP1893651, EP1805131, US2009/0084509, GB1011446 to form the gluey thing of Mierocrystalline cellulose.

Still need in the art to process non-dissolving pulp so that they are applicable to be produced by Mierocrystalline cellulose the method for molded article.

Summary of the invention

Therefore, according to a first aspect of the invention, provide the method for production of cellulose molded article, it comprises step:

A) make the paper pulp of non-solubility cellulose be exposed to the electron beam irradiation that is derived from a plurality of positions,

B) form solution or the jelly of the paper pulp that comprises cellulose, and

C) by solution casting cellulose forming product.

As mentioned above, technician will appreciate that what thing non-dissolving pulp represents.S/he can be identified to be had such paper pulp and has the one or more character in following character: compare with dissolving pulp, relatively high hemicellulose level (being generally approximately more than 10%), relatively low alpha-cellulose content (be generally approximately below 90%, be more typically approximately 83% to approximately 89%), more refining, the relatively high polymerization degree (DP) (being generally approximately 700 to approximately 1200) and/or there is relatively low quality control.

For avoiding doubt, the other treatment step of appearance can and be most likely at step a) before and/or step a)-c) between carry out.Such step will discuss in more detail below.Will appreciate that, such step, especially these step a) and b) between the step of carrying out, can change outward appearance or the performance of paper pulp.Therefore, when with reference to step b) when forming the solution of the paper pulp that comprises cellulose or jelly, will be understood that paper pulp needs not to be the form of paper pulp itself, and can be that paper pulp for example, through the variant of processing, slurries, solution or the chip prepared by the non-dissolving pulp of processing.

The molded article that the method according to this invention is produced most preferably is fiber.Other products that can also form comprise rope (ropes), yarn, cloth or cigaratte filter.These other products can directly be formed by cellulose solution, or can be formed by the fiber being spun into cellulose solution.

For avoiding doubt, term " molded article " should not comprise cellulose tablet, film or laminate etc.

The paper pulp of processing cellulose with electron beam irradiation is known, and for commercial process for many years.Conventionally for example, by pulp layer or sheet being sent to (using handling machinery) near stationary electron beams source, use the pulp processing of electron beam irradiation.Yet such technology is from failing that non-dissolving pulp is applicable to producing method of cellulose forming product, viscose process especially.

In fact, contriver has observed when making non-dissolving pulp carry out conventional electron beam treatment step, has in fact reduced the solvent of they conventional uses in producing method of cellulose forming product and the solubleness in jelly.Do not wish to be limited to theory, it is believed that when conventional electrical bundle treatment process (it generally includes and uses from high-voltage electron radiation single, Fixed Emitter (common about 10meV) pulp treatment) is applied to non-dissolving pulp, this has and solidifies or the treat surface of closed paper pulp, reduce the deliquescent effect that it has weakened.

Yet, unexpectedly determine that non-dissolving pulp is exposed to by the ejected electron bundle radiation of a plurality of positions makes these paper pulp be suitable for use as the raw material of viscose process.

Electron beam irradiation can be from the transmitting of any amount of position, for example, from two, three, four, five or six position transmittings.Yet, aspect the present invention is preferred in, electron beam irradiation is launched from two positions, most preferably, from the above and below transmitting of paper pulp.Electron beam irradiation can be from single, movably electron beam source transmitting, or from a plurality of can be that fixed or movable electron beam source is launched independently.From the transmitting of the electron beam irradiation of a plurality of positions can be simultaneously or order.

The voltage of the electron beam irradiation that preferably, non-dissolving pulp exposes is by lower than conventional electrical bundle treatment process voltage used.For example, from one, the ejected electron bundle radiation of some or all of positions will be for below about 1.5meV, below about 1.0meV, below about 800keV, below about 600keV, below about 500keV, below about 400keV, below about 300keV, below about 250keV or below even about 200keV.

Well known by persons skilled in the artly anyly can launch the voltage of required radiation and the electron beam evaporation equipment of dosage may be used in method of the present invention.

For example, can use and can under the voltage of 750keV to 1.5meV, send the middle pressure device of doses of electron beam radiation.Use the processing service of such device to be provided by many companies, for example AquaMed.Such equipment is favourable, because paper pulp process velocity (being processing speed) is for high.Yet, consider the more transmitting of high-pressure electronic bundle radiation, at electron beam source, need more shielding around, this makes operating equipment and/or paper pulp is challenging with the radiation realizing from least two positions in some cases.

These difficulties can be by using low-voltage device to improve, the device for example using in coating curing system.The example of such equipment is at least provided by PCT Engineering Systems at UK.This equipment can be at height to the curtain formula beam dose of sending electron beam irradiation under the voltage of 300keV.Beamwidth is adjustable, depends on paper pulp area to be processed, and realizes processing with the consistence of acceptable level.Transmitting due to the electron beam irradiation of relatively low pressure, so need minimal shielding, make equipment more operationally for from a plurality of positions pulp treatment and/or for simultaneously and/or sequentially carry out pulp treatment with a plurality of described device of different positions, and to user's the health any risk of tool not.

In certain embodiments, preferably, use from the electron beam irradiation of the equivalent of different positions and process non-dissolving pulp.Yet, in optional scheme, being changed to below about 100keV, below about 80keV, below about 60keV, below about 50keV, below about 40keV, below about 30keV, below about 20keV, below about 10keV of the radiation quantity of launching from different positions, or below about 5keV.

The total dose of the electron beam irradiation that paper pulp exposes can change.In preferred aspects of the invention, paper pulp is exposed to the electron beam irradiation of following dosage, described dosage be about about 0.5mRad to about 5.0mRad (about 5kgy to about 50kgy), about 1.0mRad to about 4.0mRad (about 10kgy is to about 40kgy), about 1.5mRad to about 3.5mRad (about 15kgy is to about 35kgy), about 2.0mRad to about 3.0mRad (about 20kgy is to about 30kgy) or about 1.0mRad to about 2.0mRad (about 10kgy is to about 20kgy).Therein paper pulp is supplied with to process electron beam so that paper pulp is exposed in the embodiment of radiation, can be controlled feed speed to guarantee to give target dosage.

The dosage of the radiation that non-dissolving pulp exposes and voltage can change according to the source of paper pulp to be processed, density, area, thickness and/or weight.The thickness of the paper pulp of processing according to the present invention can be for about 0.1mm, about 0.5mm, about 1.0mm, about 5.0mm or 10.0mm be to about 100mm, about 50mm, about 20mm, about 15mm or about 10mm.The weight of handled paper pulp can be about 200g/m in the methods of the invention ², about 400g/m ², about 600g/m ², or about 700g/m ²to about 2000g/m ², about 1500g/m ², about 1200g/m ², about 1000g/m ², or about 800g/m ².

Non-dissolving pulp can be continuously (for example,, by using e Foerderanlage) or be exposed to off and on electron beam irradiation.

Treated paper pulp preferably has below approximately 600, below approximately 500, below approximately 400 or the polymerization degree below 300 most preferably from about.This polymerization degree with respect to untreated non-dissolving pulp (it typically is approximately 800 to 1400) has formed significant improvement.Surprisingly, can obtain these favourable results with voltage and/or the dosage of the radiation significantly lower than the radiation of routine use.

Before paper pulp is exposed to electron beam irradiation, simultaneously or afterwards, can make paper pulp carry out one or more roughing steps.For example, in the situation of fluff pulp, these can be with sheet form supply, and can expect to make their fluffings or broken, for example, use high-shear mixer.Additionally or alternatively, can be before electron beam treatment, simultaneously or make afterwards paper pulp carry out drying step, for example, by being placed on baking oven and being heated to for example temperature of approximately 40 ℃ to 100 ℃.As further possible roughing step, can be by paper pulp layering.

In a preferred embodiment of the invention, the Temperature Treatment that paper pulp is reduced.

Do not wish to be limited to theory, should be sure of that the fiber properties of wood pulp is destroyed by making paper pulp be exposed to low temperature, may destroy hydrogen bonded and cellulosic fibre is more easy to get.

The Temperature Treatment reducing realizes by making paper pulp be exposed to low temperature, for example 0 ℃ following ,-50 ℃ following ,-100 ℃ following ,-150 ℃ following or below-180 ℃.

The Temperature Treatment reducing can for example, by storing paper pulp or remaining on low temperature environment, implement in industrial freezer.Additionally or alternatively, paper pulp can be exposed in low temperature agent, cryogenic liquid for example, as liquid nitrogen, liquid helium, liquid hydrogen, liquid oxygen, liquid neon or their mixture.If use the agent of liquid low temperature, preferably make paper pulp soak into and/or be immersed in wherein.

In preferred version, the time length of the Temperature Treatment of reduction be approximately 60 minutes following, more preferably from about 30 minutes following, approximately 20 minutes following or below approximately 15 minutes.

After the method according to this invention is by electron beam radiotreatment, then can make treated paper pulp carry out one or more steps used in the ordinary method for the production of shaped cellulose goods.For avoiding any doubt, step of the present invention is carried out with (in-line) form in line and is non-essential; They also can use independent equipment, independent processing line, in independent facility etc. and outside line (off-line) carry out.

Treated paper pulp can carry out the one or more steps in the normally used following steps of viscose process: i) dissolving/slurrying; Ii) dipping; And/or iii) yellow.In addition, the cellulosic solution that contains that is formed at step (b) preferably obtains (hereinafter referred to as molten fibre (vissolution) or molten fibre (vissolving)) by dissolving cellulos to form viscose glue.

For step I), it conventionally for example, is undertaken by form solution of paper pulp of cellulose or slurries in alkaline liquid (caustic solution, comprises the alkali metal hydroxide such as sodium hydroxide conventionally).Routinely, the concentration for the caustic solution of dissolving pulp is 18 % by weight to 20 % by weight.In solution or slurries, cellulosic concentration is generally approximately 2 % by weight to 15 % by weight.

Step I i) in, cellulosic solution or slurry for some time in basic solution.This makes basic solution permeable fiber element, causes part to form Mierocrystalline cellulose alkali salt, for example sodium salt.As step I), alkaline liquid is generally caustic solution, conventionally comprises the alkali metal hydroxide such as sodium hydroxide.Routinely, the concentration for the caustic solution of dissolving pulp is 18 % by weight to 20 % by weight.In solution or slurries, cellulosic concentration is generally approximately 2 % by weight to 15 % by weight.Dipping carries out 10 minutes to 120 minutes conventionally, and temperature is equal to or greater than approximately 50 ℃.

If carry out in the method for the invention step I i), can use identical processing condition.Yet, surprisingly, found, when making treated non-dissolving pulp be exposed to the lower time of condition of milder, can obtain favourable result.

Therefore be, in a preferred embodiment of the invention, step I i) to be undertaken by treated non-dissolving pulp being impregnated in the caustic solution of 16% to 18% alkali metal hydroxide.In particularly preferred embodiments, treated paper pulp to be impregnated in to alkali metal hydroxide concn be approximately 16.5 % by weight to approximately 17.5 % by weight, approximately 17.5 % by weight to approximately 18 % by weight, approximately 17 % by weight to approximately 18 % by weight, approximately 16.6 % by weight to approximately 17.0 % by weight or approximately 17.2 % by weight to approximately 17.8 % by weight caustic solution in.The caustic solution of same concentrations can be used for forming step I mentioned above) in slurries or solution.

Also have been surprisingly found that the paper pulp that dipping is processed according to the inventive method at the lower temperature of the temperature than conventional has produced the alkali cellulose that can be used for forming the viscose solution with improvement performance.Therefore, in a preferred embodiment of the invention, impregnation steps is carried out at least in part at the temperature of approximately 30 ℃ to approximately 50 ℃, approximately 35 ℃ to approximately 48 ℃, approximately 35 ℃ to approximately 45 ℃, approximately 38 ℃ to approximately 42 ℃ or approximately 40 ℃ to approximately 48 ℃.

Find, of the present invention can be for the production of the preferred immersion condition with the viscose solution of good filterableness, the conventional immersion condition using together with same dissolving pulp is compared, and can cause removing hemicellulose still less from cellulose pulp.Thought in the past that the hemicellulose that should remove maximum possible from paper pulp was so that the filterableness maximization of the viscose solution of gained.Yet, have been surprisingly found that, although should remove the natural hemicellulose of vast scale from paper pulp, retain the quality of the viscose solution seem on a small quantity in fact to contribute to gained.

Therefore, in a preferred embodiment of the invention, with the weighing scale of the Mierocrystalline cellulose total amount that exists, the cellulosic solution that contains that is formed at step (b) preferably comprises 0.1% to approximately 1.0%, approximately 0.8%, approximately 0.6% or approximately 0.5% hemicellulose.

In the viscose process of implementing in routine, manganese can be added in steeping fluid to reduce the DP of cellulose pulp.It adds with the amount (with the weighing scale of mixture) of 40ppm to 500ppm conventionally.

Although can use in the same manner manganese in the method for the invention, due to the favourable character that the electron beam treatment of non-dissolving pulp produces, the use of manganese is not that to obtain available viscose solution necessary.Therefore, in the preferred embodiment of the invention, at step I i) in dipping solution or slurries in do not add manganese or do not have manganese.

One or more impregnated additive may reside in or be added into containing in cellulosic slurries or solution that method of the present invention used.These play a role by making cellulosic structure keep open, and technician will know such material.The example of operable impregnated additive comprises glycerine and/or alcohol alcoxylates, particularly ethoxylated alcohol.These can be added into solution or slurries in any step of the present invention, most preferably in step I) and/or ii) in.The example of particularly preferred impregnated additive is Berol 388.In use, such as the preferred addition of impregnated additive of Berol 388, with cellulose, count approximately 0.1% to approximately 5.0%, approximately 0.5% to approximately 5%, approximately 1% to approximately 4% or approximately 0.5% to approximately 2%.

Additionally or alternatively, one or more swelling agents may reside in or be added into comprising in treated cellulosic slurries or solution that the present invention processes.Preferably, in step I) and/or ii) in one or more swelling agents are added into slurries or solution.The specific examples of the swelling agent that can use in the methods of the invention comprises propylene glycol, polyoxyethylene glycol, polyvinyl alcohol or polyacrylic ester.

In viscose process, conventional other step of carrying out is yellow (step I ii)).Paper pulp or the slurries that comprise this type of paper pulp or the solution according to the inventive method, processed, can carry out this type of step.

In a preferred embodiment of the invention, starting step I ii) before, can make to comprise treated cellulosic slurries or solution and carry out drain step (to remove excessive alkaline liquid, for example, by compacting), broken and/or aging step.If carried out, drain step and/or broken step will preferably produce Mierocrystalline cellulose fragmentary product.

The alkali cellulose product obtaining from any drain step of carrying out preferably includes the approximately Mierocrystalline cellulose below 32% and/or the approximately alkaline matter below 16% (most preferably being alkali metal hydroxide, for example sodium hydroxide).

Routinely, by the alkali cellulose that makes to be formed by dissolving pulp at the temperature more than 30 ℃, contact to realize yellow with 26% to 29% dithiocarbonic anhydride (with the cellulosic weighing scale existing).For example, alkali cellulose can be added into the whisk (whisk yellow) of introducing gaseous state dithiocarbonic anhydride, liquid carbon disulphide or the dithiocarbonic anhydride aqueous solution.

It is problematic just finding to use the more dithiocarbonic anhydride of volume before, because found that the formation speed of trithiocarbonic acid sodium (it is the less desirable by product reacting between dithiocarbonic anhydride and caustic solution) improves, particularly when carrying out yellow under intensification.

Although treated non-solubility cellulose pulp (or chip, slurries or solution of being formed by this class paper pulp) can experience some conventional machining conditions in yellow step (if carrying out in the method for the invention), have been surprisingly found that and when adjusting conventional machining condition, obtained optimum.

More specifically, if the non-solubility cellulose pulp of the electron beam irradiation that the method according to this invention obtains or chip, slurries or the solution being formed by this class paper pulp carry out yellow step, it is preferably below approximately 30 ℃, more preferably carry out at the temperature approximately 20 ℃ to approximately 30 ℃, approximately 22 ℃ to approximately 28 ℃, approximately 24 ℃ to approximately 26 ℃ or approximately 25 ℃ to approximately 30 ℃.

Additionally or alternatively, described treated paper pulp, chip, slurries or solution preferably with cellulosic weighing scale to exist approximately more than 30% dithiocarbonic anhydride contact, more preferably contact with approximately 30% to approximately 40%, approximately 30% to approximately 35% dithiocarbonic anhydride, approximately 32% to approximately 38% dithiocarbonic anhydride or approximately 34% to approximately 38% dithiocarbonic anhydride.Have been surprisingly found that and be increased in the viscosity that the dithiocarbonic anhydride amount of using during yellow has reduced the viscose solution being formed by yellow Mierocrystalline cellulose.

In preferred version of the present invention, prepared by the paper pulp of the non-solubility cellulose that viscose solution is processed by the method according to this invention, or prepared by the chip being made by described paper pulp, slurries or solution.

This is for example, for example, by the paper pulp of treated cellulose (or chip prepared therefrom, slurries or solution) being dissolved in alkaline liquid (caustic solution, comprises alkali metal hydroxide, sodium hydroxide conventionally) and realize.Liquid is preferably moisture.

Preferably using and can producing content of cellulose (CIV) be approximately 5% to 15%, approximately 5% to 13%, approximately 5% to approximately 10% or approximately 7% to approximately 10% and/or amount and the concentration of the alkaline liquid of caustic alkali content (SIV) viscose solution that is approximately 2% to approximately 10%, approximately 4% to approximately 8%, approximately 5.5% to approximately 7.5% or approximately 6% to approximately 7%.

Molten fibre preferably carries out at the temperature of approximately 10 ℃ to approximately 25 ℃, approximately 15 ℃ to approximately 20 ℃, approximately 18 ℃ to approximately 22 ℃ or approximately 16 ℃ to approximately 18 ℃.

In the method for the invention, can carry out alkalinization step.This will be preferably after dipping and/or carry out before yellow.The object of alkalinization step is to improve cellulosic character contained in paper pulp, for example, and by reducing the cellulosic polymerization degree.

As routine is implemented, alkalinization step comprises that slurries or the solution in alkaline liquid is removed a part of alkaline liquid (and optionally adding fresh alkaline liquid) from disappearing fibre element paper pulp, thereby obtain target content of cellulose and/or target alkali or carbonate content, be generally at least about 33% Mierocrystalline cellulose and/or at least about 16% alkali.Such processing conditions can be in method of the present invention.

Alternatively, in the methods of the invention, different target Mierocrystalline cellulose and/or alkali contents can be preferably.More specifically, in preferred version of the present invention, treated alkali cellulose product the best comprises the approximately Mierocrystalline cellulose below 32% and/or the approximately alkaline matter below 16% (most preferably being alkali metal hydroxide, for example sodium hydroxide).

Yet because paper pulp will preferably obtain and show target DP after according to the electron beam treatment of the inventive method, alkalinization step can be got rid of outside described method.Contain cellulosic slurries or the solution according to the present invention, prepared that in a preferred embodiment of the invention, will carry out impregnation steps (step I i) preferably carry out cooling to prevent that alkalization from occurring.For example, solution or mixture can be cooled to approximately 50 ℃ of following, approximately 40 ℃ of following, approximately 30 ℃ of following temperature or most preferably be cooled to approximately 25 ℃ of following temperature.

As use the replacement scheme of the paper pulp of processing according to the present invention in viscose glue type method (comprising the one or more steps in above-mentioned steps), can in the cellulose regenerated method of ionic liquid, use paper pulp.In such method, paper pulp mixes with the ionic liquid of melting and/or is dissolved in the ionic liquid of melting.Preferred ionic liquid comprises at room temperature for those of liquid, for example 1-ethyl-3-methyl acetic acid imidazoles (1-ethyl-3-methyl-imidazolium acetate) or 1-butyl-3-methyl acetic acid imidazoles (1-butyl-3-methylimidazolium acetate) (being called below EMIM acetate and BMIM acetate), and in EP1458805, EP1893651, EP1805131, US2009/0084509, GB1011446 disclosed other ionic liquids.

For promoting to dissolve, one or more dissolution accelerators may reside in or are added in ionic liquid solution or jelly.Those skilled in the art will know such material.In a preferred embodiment of the invention, the specific examples of operable dissolution accelerator comprises polar protic inert substance, particularly dimethyl sulfoxide (DMSO), N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), dimethyl formamide, methane amide, N-methylmorpholine-N-oxide compound, pyridine, acetone, dioxane, N-Methyl pyrrolidone, pentadiene sulfone (piperyline sulfone) and hexamethylphosphoramide or their mixture and/or nitrogenous alkali, as pyridine, ammonia, morpholine, diethanolamine, trolamine, piperidines, triethylamine, urea or their mixture.

The solution of the cellulose being formed by the paper pulp of processing according to the inventive method preferably has at least 400, more preferably at least 500, at least 600 or at least 700 K value.

Additionally or alternatively, the solution of the cellulose being formed by the paper pulp of processing according to the inventive method preferably has one or more in following characteristic: Rv is more than approximately 200, more preferably from about more than 500, TVW is approximately more than 100, and fibre count be approximately 100 fibers/gram following or more preferably 20 fibers/gram below.

Generally speaking, the processing of carrying out due to paper pulp is a part of the present invention, so can prepare the solution of the cellulose being formed by treated non-dissolving pulp completely.Yet those skilled in the art may still wish to produce solution by the mixture of dissolving and non-dissolving pulp.Therefore, in a preferred method of the invention, the paper pulp using in the inventive method at least about 15%, will be treated non-dissolving pulp.In other words, that in step (ii), in solution dipping and/or that form in step (b) in, exist and/or in step (c), cast exist in cellulose forming product solution used cellulosic and will be obtained by treated non-dissolving pulp at least about 15%.

In a more preferred embodiment, that in step (ii), in solution dipping and/or that form in step (b) in, exist and/or in step (c), cast exist in cellulose forming product solution used cellulosic and will be obtained by treated non-dissolving pulp at least about 25%, approximately 50%, approximately 70%, approximately 90%, approximately 95% or even approximately 98%.

Method of the present invention further comprises by cellulose solution, by viscose solution or by the step of the gluey thing of ionic liquid Mierocrystalline cellulose or solution casting cellulose forming product.Technology for this will be that this area is that technician is known.For example, in preferred embodiments, when molded article is cellulosic fibre, those fibers are preferably extruded cellulose solution by spinning nozzle and are formed with producd fibers shape material.Yet any fiber forms technology and equipment and can use.

Similarly, in embodiments of the invention, when not the cellulose forming product of fiber is prepared by cellulose solution, adopt routine techniques well known by persons skilled in the art, can make this cellulose solution molding, form or be configured as required configuration (arrangement).

In addition, at the Mierocrystalline cellulose by preparing from cellulose solution, form the embodiment of cellulosics, adopt any technology well known by persons skilled in the art, can make cellulosic fibre convert those goods to.

Shaped fibers cellulose solution is preferably transferred to subsequently and comprises in the casting bath of casting liquid.

According to a second aspect of the invention, provide the cellulose forming product obtaining according to the method for first aspect present invention.

According to a third aspect of the invention we, system for processing of cellulose is provided, it comprises at least one electron beam source and for the paper pulp of untreated cellulose is exposed to from the device of at least one electron beam source ejected electron bundle, described at least one electron beam source can be from a plurality of positions divergent bundle.

In first embodiment, system comprises single electron beam source, and it can move or be moved into a plurality of different positionss of the paper pulp divergent bundle radiation of cellulose.In optional embodiment, system comprises a plurality of electron beam sources, and it can maybe cannot move or be moved independently.

For exposing the device of untreated cellulose pulp, preferably include e Foerderanlage, for example conveying belt.In such embodiments, preferably the paper pulp of cellulose is provided on e Foerderanlage with sheet or layer form, and moves to from a plurality of positions ejected electron intrafascicular by e Foerderanlage.Additionally or alternatively, more than one electron beam source can move or be moved with from a plurality of position radiation paper pulp.In such embodiments, at least one location optimization on handling machinery and at least one location optimization under handling machinery.

For avoiding doubt, in appropriate circumstances, the reference of feature to the first aspect of the present invention discussed above is optionally applicable to the product of second aspect present invention and the system of the third aspect.

Now, will in following examples, set forth the present invention.

Embodiment

Embodiment 1: the DP of the paper pulp of the comparison of electron beam treatment method-treated

The conventional technology of using of a series of non-dissolving pulp sample evidence being provided by Weyerhauser is (one-sided, voltage is 1.5meV) and according to the inventive method (bilateral, and electron beam source is placed in paper pulp charging above and below, the voltage delivery from each source with 250-280keV send electron beam irradiation) carry out electron beam irradiation processing.Before processing and evaluate afterwards the polymerization degree (DP), and result below with in Fig. 1 a-1e is providing.

Table 1-is used the result of the electron beam treatment of routine techniques

Table 2-is used the result of the electron beam treatment of the technology of the present invention

Can find out, by using bilateral electron beam treatment, the reduction of observing DP is suitable with the reduction of the DP that uses routine techniques to observe.Yet importantly, these results are used the doses of electron beam radiation of the electron beam irradiation of remarkable more low voltage and significantly reduction to obtain.

This provides a lot of favourable selections for those skilled in the art, comprise by non-dissolving pulp obtain the paper pulp with acceptable DP ability and with energy still less carry out this situation possibility and with dangerous less low dosage equipment replace routine use in the possibility of dosage or high dosage electron beam equipment.

In addition, from Fig. 1 a to 1e (its viewed DP that tested different paper pulp are shown reduces), can find out apparently, all paper pulp is to being used the processing of the technology of the present invention react (this means that technology of the present invention is not limited to for specific non-dissolving pulp type) to a certain extent, and for much paper pulp, degree is larger.

Embodiment 2: the comparison-adhesive properties of electron beam treatment method

The paper pulp of the cellulose that use is processed according to the inventive method, or the paper pulp of processing by conventional, single position electron beam treatment is prepared a series of viscose solutions.With the listed processing conditions of following table, carry out Making viscose solution.

Table 3-viscose glue processing conditions

To the fibre count of gained viscose solution with Rv tests and result provides in following table:

The viscose solution character that table 4-obtains

Can find out, the character of the viscose solution of being prepared by the paper pulp of processing according to the inventive method is better than the paper pulp (adopting identical condition to process) of being prepared by processed conventionally paper pulp.This is surprising especially, because the initial DP of the paper pulp that the present invention processes is a little more than processed conventionally paper pulp.

Embodiment 3: the comparison-adhesive properties of electron beam treatment method

With the paper pulp of the cellulose of processing according to the inventive method or carry out Making viscose solution with untreated paper pulp.Being used for the processing conditions of Making viscose solution is listed in the following table.

Table 5-viscose glue processing conditions

The Rv of gained viscose solution is tested and result provides in following table:

The viscose solution character that table 6-obtains

Experiment numbers	Paper pulp	Viscose glue quality (Rv)
			1	Untreated	285
2	The present invention	850

Institute it is evident that, compare with untreated paper pulp, the viscose glue quality of the solution of being prepared by the paper pulp of processing according to the inventive method significantly improves.

Embodiment 4: electron beam treatment efficiency

Consistence and the distribution of research electron beam treatment.Pearl 429 paper pulp reels are carried out according to electron beam treatment of the present invention.After this, the radius of paper pulp reel is divided into 4 equal portions (paper pulp on sample 1-reel outside, the paper pulp in sample 4-reel core).

At each sample point, cutting fragment is with the DP at test reel both sides (Bei Henan) and center.By the layering of paper pulp sample, and obtain the DP of end face, bottom surface, and the average DP of paper pulp sample.Before test DP, in high-shear mixer, shred each sample and make it fluff to increase surface-area, and be stored in baking oven at 60 ℃.

Then by the sample of the every part in four parts of the reel from electron beam treatment for the preparation of viscose solution.Processing conditions for the preparation of viscose solution is listed in the following table.

Table 7-viscose processing conditions

Carbonate content (SiV) in content of cellulose (CiV) and viscose glue in the Rv of gained viscose solution, ball settling velocity (BFV), fibre count, viscose glue is tested and result provides in following table.

Table 8-DP and viscose SOLUTION PROPERTIES

Fig. 2 shows the viscose glue quality (Rv) of each sample and the relation between standard deviation.

The common Rv value apparently higher than identical industrial viscose glue (plant-manufactured) of Rv value of laboratory viscose glue.It has been generally acknowledged that it is acceptable for industrial processes that Rv value is greater than 100 laboratory viscose glue.

The best DP that has before found Pearl 429 is approximately 380 to 400, because this has guaranteed good workability and the good quality of the finished product.

From DP and standard deviation result, can find out, the electron beam treatment of whole reel is quite even.In addition,

sample

1,2 and 4 DP are in desired scope.

Sample 3 has lower slightly DP, and this shows that the paper pulp of reel in this part crosses processing.Yet it is 129.4 Rv value that paper pulp has acceptable, it is not also very disadvantageous representing to process.

Do not wish to be limited to theory, be sure of, as long as by electron beam treatment pulp treatment equably, even if there be crossing and process slightly, the quality of the viscose glue of producing is also acceptable.

Claims

1. the method for production of cellulose molded article, it comprises step:

B) form solution or the jelly of the paper pulp that comprises cellulose, and

C) by described solution casting cellulose forming product.

2. the method for claim 1, wherein electron beam irradiation is launched from two positions.

3. method as claimed in claim 1 or 2, wherein electron beam irradiation on described paper pulp and under position transmitting.

4. method as claimed any one in claims 1 to 3, wherein the voltage of the one or more positions ejected electron bundle radiation in described a plurality of positions is below about 1.5meV.

5. the method as described in any one in claim 1 to 4, wherein the voltage of the one or more positions ejected electron bundle radiation in described a plurality of positions is below about 500keV.

6. the method as described in any one in claim 1 to 5, wherein the voltage of ejected electron bundle radiation is changed to below about 50keV.

7. the method as described in any one in claim 1 to 6, the dosage of the electron beam irradiation that wherein said paper pulp exposes is that about 0.5mRad is to about 5.0mRad.

8. the method as described in any one in claim 1 to 7, the dosage of the electron beam irradiation that wherein said paper pulp exposes is that about 1.5mRad is to about 3.5mRad.

9. the method as described in any one in claim 1 to 8, the thickness of wherein said paper pulp is that about 0.1mm is to about 100mm.

10. method as claimed in any one of claims 1-9 wherein, the weight of wherein said paper pulp is about 200g/m ²to about 1200g/m ².

11. methods as described in any one in claim 1 to 10, wherein, after step is exposed to electron beam irradiation in a), the mean polymerisation degree of described paper pulp is approximately below 500.

12. methods as described in any one in claim 1 to 11, wherein, after step is exposed to electron beam irradiation in a), the mean polymerisation degree of described paper pulp is approximately below 400.

13. methods as described in any one in claim 1 to 12, wherein at step b) before, make described paper pulp be selected from the one or more other treatment step of the Temperature Treatment of fluffing, fragmentation, dry, layering and/or reduction.

14. methods as claimed in claim 13, the Temperature Treatment wherein reducing comprises described paper pulp is cooled to below approximately-150 ℃.

15. methods as described in claim 13 or 14, the Temperature Treatment of wherein said reduction comprises makes described paper pulp soak into and/or be immersed in cryogenic liquid.

16. methods as claimed in claim 15, wherein said cryogenic liquid is selected from liquid nitrogen, liquid helium, liquid hydrogen, liquid oxygen, liquid neon or their mixture.

17. methods as described in any one in claim 1 to 16, the solution of wherein said cellulose is preferably prepared by one or more steps of carrying out in following steps:

The paper pulp of the cellulose that i. slurrying/dissolving step is processed in a),

Solution or the slurries of the paper pulp of ii dipping cellulose, and/or

Iii yellow,

Step b wherein) the described solution forming in obtains to form viscose solution by the molten fibre of Mierocrystalline cellulose.

18. methods as claimed in claim 17, wherein impregnated in the paper pulp of described cellulose and comprise that concentration is that approximately 16 % by weight are to the slurries or solution of the caustic solution of approximately 18 % by weight.

19. methods as described in claim 17 or 18, wherein impregnated in the paper pulp of described cellulose and comprise that concentration is that approximately 16.5 % by weight are to the slurries or solution of the caustic solution of approximately 17.5 % by weight.

20. methods as described in any one in claim 17 to 19, wherein at least a portion impregnation stage, it is in the slurries or solution of approximately 30 ℃ to approximately 50 ℃ that the paper pulp of described cellulose be impregnated in to temperature.

21. methods as described in any one in claim 17 to 20, wherein at least a portion impregnation stage, it is in the slurries or solution of approximately 40 ℃ to approximately 48 ℃ that the paper pulp of described cellulose be impregnated in to temperature.

22. methods as described in any one in claim 17 to 20, wherein at least a portion impregnation stage, it is in the slurries or solution of approximately 35 ℃ to approximately 45 ℃ that the paper pulp of described cellulose be impregnated in to temperature.

23. methods as described in any one in claim 17 to 22, wherein impregnated in the paper pulp of described cellulose substantially containing in the slurries or solution of manganese.

24. methods as described in any one in claim 17 to 23, wherein impregnated in the paper pulp of described cellulose in the slurries or solution that contain impregnated additive.

25. methods as claimed in claim 24, wherein said impregnated additive is ethoxylated alcohol.

26. methods as described in claim 24 or 25, wherein said impregnated additive is Berol 388.

27. methods as described in any one in claim 17 to 26, wherein before yellow, make the paper pulp of described cellulose or slurries prepared therefrom or solution carry out the one or more steps in drain step, broken step and/or aging step.

28. methods as described in any one in claim 17 to 27, wherein yellow is to carry out at the temperature of approximately 20 ℃ to approximately 30 ℃ at least in part.

29. methods as described in any one in claim 17 to 28, wherein yellow is by making paper pulp or solution prepared therefrom, slurries or the chip of cellulose contact and carry out with dithiocarbonic anhydride.

30. methods as claimed in claim 29, wherein, with the weighing scale of the total fiber element that exists, are used approximately 30% to approximately 40% dithiocarbonic anhydride.

31. methods as described in claim 29 or 30, wherein, with the weighing scale of the total fiber element that exists, are used approximately 32% to approximately 38% dithiocarbonic anhydride.

32. methods as described in any one in claim 17 to 31, wherein molten fibre is to carry out at the temperature of approximately 10 ℃ to approximately 25 ℃ at least in part.

33. methods as described in any one in claim 17 to 32, wherein step b) in the caustic alkali content of described viscose solution of preparation with described solution weight, count approximately 4% to approximately 8%.

34. methods as described in any one in claim 17 to 33, wherein step b) in the content of cellulose of described viscose solution of preparation with described solution weight, count approximately 5% to approximately 10%.

35. methods as described in any one in claim 17 to 34, wherein, when completing steps ii, reduce to prevent that by the temperature of described slurries or solution alkalization from occurring.

36. methods as described in any one in claim 1 to 16, the solution of wherein said cellulose is that the paper pulp of the cellulose by making to process in a) in step contacts and stirs the mixture with ionic liquid and prepares.

37. methods as claimed in claim 36, wherein said ionic liquid comprises EMIM acetate or BMIM acetate.

38. methods as described in any one in claims 1 to 37, wherein at step b) in the solution of the described cellulose that forms have take lower one or more: Rv as approximately more than 200, TVW as approximately more than 100 and/or fibre count as approximately 100 fibers/gram below.

39. methods as described in any one in claims 1 to 38, wherein at step b) in the solution of the described cellulose that forms have take lower one or more: Rv as approximately more than 500 and/or fibre count as approximately 20 fibers/gram below.

40. methods as described in any one in claims 1 to 39, wherein step b) in the solution of the described cellulose that forms there is the K value at least about 400.

41. methods as described in any one in claim 1 to 40, wherein step b) in the solution of the described cellulose that forms there is the K value at least about 600.

42. methods as described in any one in claim 1 to 41, wherein in step (ii), in described solution dipping and/or that form in step (b) in, in described solution that exist and/or cast described cellulose forming product in step (c) in, exist described cellulosic at least about 15%, be by treated non-dissolving pulp acquisition.

43. methods as described in any one in claim 1 to 42, wherein in step (ii), in described solution dipping and/or that form in step (b) in, in described solution that exist and/or cast described cellulose forming product in step (c) in, exist described cellulosic at least about 50%, be by treated non-dissolving pulp acquisition.

44. methods as described in any one in claim 1 to 43, wherein in step (ii), in described solution dipping and/or that form in step (b) in, in described solution that exist and/or cast described cellulose forming product in step (c) in, exist described cellulosic at least about 90%, be by treated non-dissolving pulp acquisition.

45. methods as described in any one in claim 1 to 44, wherein said molded article is fiber.

46. methods as described in any one in claim 1 to 44, wherein said molded article is rope, yarn, cloth or cigarette filter.

47. methods as claimed in claim 45, it also comprises makes step c) cellulosic fibre of casting forms the step of goods.

48. methods as claimed in claim 47, wherein said goods are rope, yarn, cloth or cigarette filter.

49. cellulose forming products that obtained by the method described in any one in claim 1 to 48.

50. systems for processing of cellulose, it comprises at least one electron beam source and for the paper pulp of untreated cellulose is exposed to from the device of described at least one electron beam source ejected electron bundle, described at least one electron beam source can be from a plurality of positions divergent bundle.

51. systems as claimed in claim 50, wherein said system comprises single electron beam source, it can move or be moved into a plurality of different positionss for the paper pulp divergent bundle radiation to described cellulose.

52. systems as claimed in claim 51, wherein said system comprises a plurality of electron beam sources, it can maybe cannot move or be moved independently.

53. systems as claimed in claim 52, wherein said system comprise be positioned at described for the paper pulp of untreated cellulose is exposed on the device of electron beam and under electron beam source.

54. systems as described in any one in claim 50 to 53, wherein saidly comprise e Foerderanlage for the device that makes untreated cellulose pulp be exposed to electron beam.

55. systems as claimed in claim 54, wherein said e Foerderanlage comprises conveying belt.