CN1352716A - Method for separating lignocellulose-containing biomass - Google Patents

Abstract

The invention relates to a method for separating lignocellulose-containing biomass, especially wood, into the essential components in the form of lignin, hemicellulose and cellulose, with the following steps: a) pre-hydrolyzing the lignocellulose-containing biomass by treating it with water or steam; b) extracting the hydrolyzed hemicellulose obtained by pre-hydrolyzation with an aqueous medium; c) extracting the process-modified lignin that remains in the residue with an alkanolamine, isolating the lignin, recovering the alkanolamine, whereby the alkanolamine is not substituted by alkyl groups at the nitrogen atom, and d) obtaining a cellulose raw material. The inventive method is characterized in that hemicelluloses and lignin can be specifically separated from the cellulose in two different process steps. For this purpose, simple and commercially available system components can be used that facilitate an economical operation also with small installations.

Description

The method of the living beings of separating lignocellulose-containing

The present invention relates to a kind ofly to be used for separating (particularly from timber or grain straw) living beings of lignocellulose-containing and become the method for the basis of lignin, hemicellulose and Cellulosed molded article.

The shortcoming of conventional paper paste-making method mainly is the water consumption height, the high and higher relatively production cost of organic matter content in the waste water.The latter particularly by cleaning alkali lye and waste liquid stream or residual solution stream supplementary costs caused.Do not use the sulfur-containing compound just can not separating lignin in the conventional method; And use sulphur compound can produce the smell problem.(sulfate, sulphite Milox) are the chemical cracking lignin to typical slurring method, and the method for mainly dissolving pyrolysis product (lignin sulfonic acid).

By the design of conventional method, consider that from economic angle yearly productive capacity is higher than 200000 tons and just can moves.Generally, the production of chemical pulp (Chemiezellstoff) only accounts for the small part of production capacity, about 4%.On the other hand, every chemical pulp processor wishes to obtain by the required paper pulp of their interests, and paper pulp becomes different credit ratings as far as possible.

In newer method, the Formacell method be a kind of mainly be dissolving and the method for only a small amount of cracking.ASAM and Organocell are complex methods.Wherein, particularly the ASAM method requires the chemicals recovery system of a complexity.

It is easy separating lignin and other byproduct that the method for dissolved lignin has an advantage.

With paper paper pulp (Papierzellstoff) (paper, cardboard, suede paper (Fluff)) situation difference, rising conclusive for chemical pulp is the chemical property of paper pulp fiber, but not its physical property, because the structure of fiber is destroyed in the chemical pulp process.What work here is following standard: the degree of polymerization and polymerization distribute, the dissolubility among whiteness and the NaOH.

The shortcoming of the paper pulp method of industrial employing is the reactivity loss that drying must cause.What is called not dry pulp (after pulp and the bleaching, humidity is not less than 30% dry pulp) is high reaction activity on the contrary.Be transportation paper pulp, need be in blocks and dry on paper machine.Need a large amount of technical fees for this reason, at least paper pulp is processed into derivative and is unfavorable for productivity ratio, therefore produced expensive here for the reactionization of chemical pulp is subsidiary.For chemically further processing will be more suitable many be the fibers form (dry) that exists after the pulp.

In steam-explosive method, in order to surpass the softening temperature of lignin and polysaccharide, the pressure in 20 Palestine and Israels is common by prior art.In conjunction with high pressure, the vapor (steam) temperature that is higher than 200 ℃ causes that on the one hand cellulosic strong chain decomposes, and also causes the condensation of lignin on the other hand, and this result has caused relatively poor extractibility.Steam unlikely enters the crystal region of lignocellulose structure; Just in this point, the there can not modification.

The prior art of steam-blast aspect has record in many patents, it relates generally to method design and basic process.Most of research is carried out as raw material with timber.In most cases, difficult point is the optimization to intensity factor (Severity-Faktor) (vapor (steam) temperature is to the integration of action time).

Using the shortcoming of water vapour is can not or to have only and used under the high-tech condition of cost and auxiliary agent could have been introduced in the steam.Or rather, living beings must contact with the material that adds before vapour explosion, and this generally is accompanied by relatively poor distribution or high dose.Similarly, this also is suitable for steam refining (Steam-Refining) method (being right after steam leaching (Dampfaufschluss) method that machinery is broken (Auffaserung)), it uses mechanical device to break with less high pressure steam (10-15 crust) processing.

It is the vapour explosion method that chip or other living beings are used the II of Stake system of StakeTech StakeTechnology company that the unique paper pulp that can realize on commercial scale that can turn round fully continuously leaches (Zellstoffaufschluss) method.

Removing lignin is challenge maximum in all slurring methods.Disclosed the work of the lignin that is used for alcohol extracting timber in 19 end of the centurys.The target that has the slurring method that is used for the development environment close friend that is different from present establishment at that time.Ever-increasing comment of traditional slurring method being given the influence of environment, to contaminated wastewater, the stricter law regulations that discharging and residue are handled in air are improved the effort of wood substance utilization in addition and can be regarded the main cause of constantly making great efforts to develop new eco-friendly slurring method in nearly 20 years intentinonally as.Because the status of chemical pulp is (only account for world's pulp production 4%) time,, research and development work is used to prepare the slurring method of paper with paper pulp so concentrating on.But to chemical pulp, comparison paper be the more important thing is with paper pulp and is quantitatively removed delignification.

Be enriched with high content of lignin in the timber middle sheet.Timber shows hard thus.Under commercial scale, after paper pulp leaches, to introduce before the bleaching, the numerical value of the content of lignin of maximum permission is 40.

Significant especially also have grain straw to make raw material, produces 12,500 ten thousand tons of straws because the U.S. is annual, and Europe is annual even produce 17,000 ten thousand tons of straws.Many countries at first are (for example China) and African country in the Asia, lack the raw material timber that is used to prepare paper pulp, so that regulation is used straw.Known processing method is the vapour explosion or the Su Da pulp (paper pulp leaching) of straw for example.Preceding a kind of method needs expensive mechanical realization, can not solve the problem of clean separation cellulose and lignin.Break never not cmpletely, this just needs post processing refining, especially must be with below the fibrous suspension high dilution to 2%.Separating lignin still must use sodium hydroxide solution.A kind of method in back has caused high environmental pressure by " straw slurries (straw pulp) " grinding and/or wastewater treatment need be expensive in alkali delignification process.In " non-wooden " process of lapping, often do not carry out the method input, as in the prior art to the paper pulp leaching method of timber.Aspect timber pulp (Holzaufschluss), carry out with the chemical reagent that reclaims boiling near the cyclic process of sealing effectively at present.But leaching " non-wooden " fiber, often very little as straw aspect device, to carry out same high method input.Even when unit scale can reclaim the chemical reagent of boiling economically, still have problems, because the silicon of high-load is difficult to tackle for traditional leaching method.Countermeasure promptly is that the leaching chemical reagent with major part consumption is discharged in the environment.Like this, for example pulp factories only reclaims the boiling chemical reagent based on straw 60%.

The prior art that two kinds of different use ammonia are arranged in conjunction with pulp (paper pulp leaching): use ammonia at high temperature to come in fragmentation ligno-cellulosic materials and the Asplund treater (Refiner) under ammonia pressure chip plastify by blast sample lax (J.J.O ' Connor Tappi 55 (3), (1972) 353-358) plasticizing: the energy that requires much less of breaking of this timber is imported (R.C.Peterson and R.W.Strauss are at polymer science magazine (J.Polymer Sci.) C36 (1971) 241-250).Under the both of these case, lignin all can not be removed basically.

The lignin that uses alkanolamine to remove in the lignocellulose is introduced by Elton Fisher and R.S.Bower (J.Am.Chem.Soc.63 (1941) 1881-1883) first.Use monoethanolamine to handle (cue: moisture alkohol and amine alkali pulp, the acceleration of soda delignification process, no sulphur delignification process) at the seventies as the additive that is used for the sodium hydroxide solution of pulp.Thus, may reduce or even alternative sulfur-bearing chemical reagent.

The problem that exists is to leach chemical reagent sodium hydroxide solution and the processing of monoethanolamine and separating of lignin.Usually lignin is by adding under the sour condition by separating out acquisition in the sodium hydroxide solution.From sodium hydroxide solution/alkanolamine solution, obtain lignin by this method and must not can simplify the processing and the recovery of leaching chemical reagent.Usually as the first step of NaOH recovery, the lignin after burning concentrates among the NaOH also can cause the loss of alkanolamine, and this may relate to huge cost.

May therefore abandon using the additive of monoethanolamine again as the NaOH of preparation high yield material.Not having under the situation target is the preparation chemical pulp.Under all situations, monoethanolamine is applied to fresh timber (most of is needle timber).Boiling is carried out in reinforced running (intermittently running) mode in pressure vessel.

Additive (the patent: CA1232109 Kauppi, " alkanolamine and the NH of Peter K. of the use introduced monoethanolamine seldom as ammonia spirit arranged equally ₄OH is used for the high yield pulp " and EP 149 753 Gordy, " unvulcanised is learned mechanical pulp " of John).120 ℃ or higher temperature are handled in the chip process down, and monoethanolamine is used as plasticiser in the ammonia spirit of these dilutions, and the machinery that is used for cardboard or the timber that is equipped with made of paper below this has simplified is broken.

Disclose according to US 2 192 202, introduced a kind of paper pulp that is used for the rugose wood cellulosic material and leached,, wherein use 70wt-% alkanolamine at least as finishing agent especially for the method for obtaining alpha-cellulose and other value product.Processing procedure by carrying out adding to depress between room temperature and 200 ℃ in boiling 4-20 hour.NaOH can select common use.Then, the separating treatment agent is also bleached with the paper pulp that the diluted mineral acid washing obtains.But thus the separation of the paper pulp each component of Shi Xianing not cmpletely, the quality that obtains is also unsatisfactory.

In view of the above, task of the present invention provides a kind of method of classification of the living beings that are used for lignocellulose-containing, has wherein eliminated the shortcoming that prior art is mentioned basically.Should obtain with the form of the least possible pollution wood components hemicellulose separated from one another, lignin and cellulose so that according to said method further the personnel of processing can use this raw material.Here should provide no sulphur free from chloride slurring method, it also without the sodium hydroxide solution operation, has saved expensive recovery, waste gas and purification method for effluent whereby.Particularly chemical pulp obtain should with save time, the mode of chemical reagent and the energy carries out in little dispersal unit.Cellulose should be not dry pulp form, and high workability is promptly arranged, and can directly further be processed as cellulose derivative.Thus, should be by the preparation of the paper pulp of each chemical pulp processor's standard tailoring favourable on the cost and still can realize to further being processed with under the active situation of highest response, in the integrated machining chain of timber until becoming cellulose derivative.

By the present invention, above-mentioned task becomes the method for the solvent of lignin, hemicellulose and Cellulosed molded article to be achieved by a kind of living beings that are used to separate especially from the lignocellulose-containing of timber, and it has the following step:

A) carry out the prehydrolysis of the living beings of lignocellulose-containing by water or steam treatment;

B) hemicellulose of the hydrolysis that prehydrolysis is generated extracts with water-bearing media;

C) lignin that will stay the process modification in the residue extracts with alkanolamine, separates wooden

Element reclaims alkanolamine, wherein on the alkanolamine nitrogen-atoms no alkyl replacement and

D) obtain the cellulose coarse fodder.

Realized the decomposition of lignocellulose and resolved into its component by method of the present invention, wherein at first water or steam treatment make its prehydrolysis, hemicellulose with the hydrolysis that generates extracts with water-bearing media then, extracts residue with alkanolamine again and obtains the cellulose coarse fodder.

For the inventive method (promptly being classified as solvent cellulose, polysaccharide and lignin), can use the lignocellulose of all kinds.As the living beings of lignocellulose-containing suitable different types of plant growth material arranged, as timber, the oat shell, corn and cereal bar, bagasse, various grain straws, as wheat stalk, rice straw and oat stalk.Common for timber, no matter round log or economic wood preferably with pulverised form, for example use with the chip form.For fibrous raw material, as annual plant, suitable is by cutting into the fiber of chopping.Preferred (geschredderte) timber that uses pulverizing or wood shavings, its kind is broad leaf tree, beech or coniferous tree.

The moisture of the living beings of lignocellulose-containing can particularly be bordering between 0% after the strong drying of 50 quality percentage compositions for the about 80 quality percentage compositions of the typical content of the lignocellulose of new harvesting.

The step that the present invention begins comprises that water or steam treatment come the living beings of prehydrolysis lignocellulose-containing.Preferably the mass ratio with water vapour and living beings (based on dry) is adjusted to about 1: 1 to 3: 1, about 3: 1 to 10: 1 of the mass ratio of water and living beings, particularly about 6: 1.Here, a kind of so-called vapour explosion method can be carried out, also the steam refining method may be used living beings.The prehydrolysis of preferred living beings is carried out under the condition of gentleness, and wherein the purpose of this method step is to decompose hemicellulose basically, extracts by water-bearing media so that it can have difficulty ground as the separation of compound sugar subsequently, as washes with water and carry out.Prehydrolysis is method step known in the pulp industry, needn't further inquire into here.Wherein cellulose and lignin should be destroyed as few as possible.

Is whole decomposition that the prehydrolysis process can be finished hemicellulose by the present invention in the first step of method because in extraction step alkanolamine attack cellulose neither, also not attack hemicellulose, and be on the contrary to its stabilisation.But prehydrolysis a) also can be carried out in very little scope set by step.Being prehydrolysis to such degree, so that the acid that is combined on the hemicellulose can dissociate, and b set by step) these acid of dissociating are washed off.This plays a role to preparation high yield paper pulp especially.Excessive acid and the alkanolamine that uses below reaction will cause loss.Therefore minimal prehydrolysis may be just enough.

For the efficient that improves prehydrolysis also can carry out two step prehydrolysis under the same conditions of cooking, but efficient can be higher, promptly at first uses steam, uses hot water then in same temperature.

If use for example stalk, then can cancel set by step a) and b as living beings) prehydrolysis, direct c set by step), preferably below 160 ℃, particularly under about 115-135 ℃ high temperature, extract, below 170 ℃ about to obtain paper paper pulp about.Also can select with stalk at about 150 ℃-190 ℃ particularly about 170 ℃ of prehydrolysis, after this c set by step to this), preferably, extract under particularly about 115 ℃ to 135 ℃ high temperature, below 170 ℃ about to obtain chemical pulp below 160 ℃.Obtaining here of sugar reaches by the concentrated of prehydrolysis thing, carries out suitable further processing subsequently.Pulp quality according to hope can be selected suitable scheme.

Simultaneously also may add stabilizing agent for the condensation that prevents lignin component.The living beings of lignocellulose-containing step a) be may carried out in addition, be i.e. acid or alkali preliminary treatment carried out before the prehydrolysis.The productive rate that this means desirable product can further improve.

After the vapour explosion method or steam refining method for example utilized, the raw material of having broken well can be used hot water treatment usually, so that the hemicellulose that dissolving and separating most decompose.Prehydrolysis and softening living beings are also by removing the hemicellulose of the hydrolysis of generation with the extraction of water-bearing media.This is preferably extruded remaining water and heat washes.The machinery that can carry out living beings is broken subsequently, for example is ground into the decentralization of hope in treater, and its quality according to hope has significance.

Can choose wantonly subsequently and use ammonia treatment.This can be in any proper time point, at b set by step) clean after, use ammonia spirit, carry out with ammonia or with liquefied ammonia.

The preferred mass ratio of regulating liquefied ammonia and treating material (based on dry) is about 0.1: 1 to 4: 1.

Then carry out extracting the living beings of removing hemicellulose of the lignin of the process modification that stays in the residue, obtain the cellulose coarse fodder with alkanolamine.Consider especially that as alkanolamine all remove its nitrogen-atoms and do not have the alkanolamine that alkyl replaces.For example get rid of like this: N-methyl monoethanolamine and N, N-dimethyl monoethanolamine is not because these are had an effect in the process of the lignin that extracts timber.

The preferred monoethanolamine of using is made extractant, and it can the preheating form, particularly uses down at least about 80 ℃.Here shown from unpretreated living beings, to the living beings of prehydrolysis, again to obviously strengthening with these a series of middle extraction effects of the pretreated living beings of ammonia.The content of lignin of extract living beings for ammonia treatment under same extraction conditions compare the only living beings high approximately 60% of prehydrolysis.

, promptly in suitable autoclave or successional extractor, carry out preferably under pressure by extraction of the present invention.Can for example realize same good result by the extraction under the atmospheric pressure to stalk.

In the intermittently operated, promptly in autoclave, remove hemicellulose washing, optional chopping and by suitable manner with the pretreated living beings of ammonia and water, one or more extractants of wherein containing, between about 80-220 ℃, heat at least about 1 hour.Here the solvent prepared of the lignin catabolite component of promising generation also.

The preferably continuous extraction of andnon-continuous operation manner relatively.This can carry out like this, promptly allows the living beings of loading in the extractant percolation excess pressure reactor of preheating or with material to be extracted, promptly living beings and extractant adverse current are carried.This dual mode is with respect to autoclave, and the advantage of promptly static running is owing to drawn catabolite and got rid of side reaction basically with extractant.In addition can be under same extraction effect,, carry out at a lower temperature with the bath raio of extractant with little chip.Here, the dissolubility of organic solvent lignin in monoethanolamine higher relatively (250 grams per liter).

In the preferred embodiment of the invention, leaching process is a multistep, promptly finishes by at least twice extraction of carrying out in succession with alkanolamine.Here, the preferred use with one goes on foot identical alkanolamine total amount in the extraction.Wherein, can finish with counter-flow extraction effectively, because realized the shortest extraction time like this.

If for example carry out two step prehydrolysis, this makes and can coordinate well with the method for preparing chemical-mechanical paper pulp (cmp) employing, at this moment preferably add the steam treatment of the chip that floods with spirit of vinegar in advance and in so-called " tiltedly screw reactor ", carry out (real prehydrolysis), carry out the extraction of sugar then by countercurrent action, follow and break.

Monoethanolamine (below be abbreviated as MEA) has different advantages as extractant.In slurring method, MEA has stoped the lignin condensation and has been grafted on the cellulose, and this has prevented cellulosic DP-degraded, has improved delignification, has reduced the requirement of bleached chemical reagent.

Alkanolamine extracts and can carry out under lower temperature (about 100-120 ℃), if carried out the pretreated words of ammonia earlier.Although obtain low kappa value at a lower temperature.Contained side reaction in addition strongly.

Obtained the cellulose coarse fodder behind the extraction step.For this reason, dye consumingly by dark-brown to the lignin extraction thing of black by suitable manner according to the solid/liquid separation method in common is separated from the crude pulp fiber.If the also lignin residue of remaining process modification is removed in crude pulp in expectation fully, so can be with suitable solvent by washing or countercurrent washing be extracted.Solvent used herein then separates with extractant with lignin by distillation, according to said method reclaims, and therefore re-uses.

Residue after the solvent distillation is removed can merge with the extract that separates from fiber.Thus with water and as the alkanolamine of extractant by distillation, preferred vacuum distillation separates.What be fit to also has other by other separation method of wishing to concentrate lignin extraction thing (under extreme case until siccative).The separation of realization lignin also can be added non-solvent in the alkanolamine solution of lignin.Like this, lignin is separated out with the solids form, can be by suitable solid/liquid separation method, and as filtering, centrifugal, thin film evaporation or membrane separating method separate from the extractant alkanolamine.The separation of lignin can randomly be introduced CO in the lignin of Nong Suoing/alkanolamine extract for example by to extracting the back water with alkanolamine or better diluting with slurry ₂Finish.By by the concentrating of thin film evaporation or suitable other distillating method, be recovered to most of pure alkanolamine.With the residue distillation of alkanolamine, then the water in the precipitated liquid after the lignin separation (equally under vacuum) distillation is removed.Whereby by introducing CO ₂Separate out with centrifugal realization lignin.With CO ₂The adduct alkanolamine * CO that generates ₂Can be decomposed into alkanolamine and CO once more fully by heat or by spraying into of steam ₂Residue comprises with regard to its molal weight is strong and decomposing, but chemically unaltered substantially lignin.Therefore, these can be used as chemical raw material once more, for example are used to prepare the chemical raw material of thermoplastic or polyurethane.

The hemicellulose that decomposes exists with the aqueous solution or form of suspension, equally can be for further using.

The Kappa value of crude pulp is the highest about 20, preferably is lower than about 10.This respectively corresponding to content of lignin＜3 quality percentage compositions or＜1.5 quality percentage compositions, degree of bleaching advantageously is enhanced.

In the reality, can use so-called " tiltedly screw reactor " to come prehydrolysis, be prepared breaking and washing of carrying out usually in " cmp " (abbreviation of top explanation) process then.Preference is used NH as using " tiltedly screw reactor " ₄The preliminary treatment of OH/ alkanolamine is carried out recited above breaking then and is carried out lignin extraction completely with the counter-flow extraction form.This two step, what produce under first kind of situation was the fraction that contains the many water that are repeatedly used of low concentration lignin, and at this concentrated lignin, what produce under second kind of situation is the fraction that contains high concentration lignin and many alkanolamines.Merge these two fractions with the ratio of many water/many alkanolamines about 2/1 and at high temperature pass through CO ₂Realized separating out of lignin.From the fraction of the few water of many alkanolamines, only need distill moisture seldom,, so simultaneously lignin concentration improved more than 20% so that can for example reclaim most of alkanolamine by thin film evaporation.

For pressing method of the present invention, the method that is used for the living beings of separating lignocellulose-containing not of the same race has been described once more in a flowchart in attached Fig. 1 and 2 with description of drawings.Be so-called prehydrolysis among Fig. 1, for example with the form of vapour explosion method or steam refining method, it sends to the separation hemicellulose after extracting with water-bearing media.Then, break in treater, it affects the carrying out of other procedure.Then choose wantonly and carry out ammonia treatment.Here, for example can relate to so-called ammonia blast.Can break again in treater subsequently, the extraction of using alkanolamine, particularly monoalkanolamine afterwards is to carry out to cause lignin to separate with cellulosic at intermittence or continuous function mode.Ammonia treatment is optional, and it can directly carry out after extracting with alkanolamine after prehydrolysis is finished or after vapour explosion or the steam refining method.

A kind of alkanolamine leaching process is introduced in Fig. 2 in detail.Shown the recovery cyclic process of removal process of the extractant of a kind of solvent that use is described and application here.This scheme makes and can operate especially economically.

The present invention is in conjunction with a large amount of advantages.An advantage is that at first the chemical reagent that shows no sign of any sulfur-bearing is used for pulp.Will not be used for bleaching by chloride chemical reagent in addition.

(steam refining in pure steam treatment process, vapour explosion), be different from the present invention, must select very high so-called intensity factor, promptly by the integration of vapor (steam) temperature to action time, so that can decompose hemicellulose and lignin fruitfully, but under exacting terms like this, cellulosic molal weight can reduce equally greatly, and the lignin sliver is easy to condensation.The advantage of this one-step method must exchange for the compromise of the quality aspect of classification component.

One of advantage of the inventive method is that also the hemicellulose in two distinct methods steps is correspondingly measured with lignin and separated with cellulose pointedly.This also produces following result, and cellulosic molal weight reduces widely, and the content of the lignin before the bleaching is lower than the numerical value in the said method significantly and is lower than numerical value in the method (sulfate and sulfite process) of industrial employing.

The steam of the prehydrolysis of hemicellulose use can be used for the preheating of extractor in addition.It has realized double utilization thus.Same for breaking the energy that consumes owing to extract softening seldom strongly of artifact matter.Break mostly and after prehydrolysis, finish, after extraction step, finish under the individual cases, and needn't tolerate significant mechanical power loss.

Another advantage is to prevent to do with sodium hydroxide solution the extractant of lignin, as usually by vapour explosion method or steam refining method.The use of sodium hydroxide solution has caused the construction and the running of so-called reclaimer in the cellulose factory just.By having only this auxiliary device to have the running of economic implications to limit its size with certain scale.

When using grain straw to make raw material, exempted multistep required for NaOH, expensive traditional recovery or wet oxidation.For alkanolamine, reclaim and be simple vacuum distillation process.With CO ₂The adduct alkanolamine * CO that generates ₂Can or spray into steam by heat and be decomposed into alkanolamine and CO more fully ₂This has eliminated the necessity that reclaims sodium salt.Very effective by making that with the simple prehydrolysis of carrying out alkanolamine extracts, so that crude pulp has had about 50%ISO brightness.Alkanolamine is extracted in can not had pressure under the stalk moisture situation seldom yet and carries out, and this allows to use simple equipment.

So-called " caustic lye of soda ", promptly the mixture of at least 20% sodium hydroxide solution and vulcanized sodium in sulfate (power) method uses with the higher relatively bath raio to living beings (for example with the chip form) at 10: 1.In addition, living beings must be the same sizes in narrow relatively boundary, because otherwise in leaching method, for example bigger chip inadequately allows caustic lye of soda pass during boiling.On the contrary, the present invention allows not carry out with the much smaller bath raio of being extracted in of alkanolamine (about 3: 1), particularly carries out under the continuous operations mode.This positive impact steam consumption and the recovery in the leaching process.

Aspect the method for the present invention also advantageously the living beings after the prehydrolysis in suitable treater or fiber disassembler, cut with very little mechanical energy consumption with steam so that subsequently with the leaching process of alkanolamine in effective time can not be affected because of diffusion process.

The little dispersal unit that is used to produce chemical pulp can not operate under preferred economic condition, because must carry out the recovery of sodium hydroxide solution.Use alkanolamine to make extractant: to carry out not consumed energy under the distinctive heat of evaporation by being recovered in of distillation for material favourable on the double meaning.The separation of lignin can not use acid to carry out, and this has been avoided expensive processing method equally, and favourable to environment.

Be used to prevent that the additive of lignin condensation from also being unnecessary, this provides cost savings.Because can exempt the preliminary treatment with chemical reagent, this is essential in only using vapour explosion and steam refining method, so there is not its distribution problem.Thus, has very low scrap rate (coarse wood components, it is not enough to be broken owing to relatively poor distribution) by method of the present invention.

In addition, has the decrystallization of other method raising relatively with the paper pulp after the alkanolamine extraction.This is really to very favourable as chemical pulp, because produced the uniform workability of the chemical reagent that is used to prepare cellulose derivative whereby.Use possibility to help operating cost equally than the ammonia of much less in pure ammonia blast timber process.Can exempt expensive liquefied ammonia reclaims.

Because must be that the cost that is used to bleach is few more, if the Kappa value (content of lignin) after extracting is low more, the favourable precondition of same existence in the inventive method.Because totally continuous running, so specific investment is low, space/time income height.Can use and simply be purchased apparatus assembly.This has made and just can operate economically with small-size equipment (littler 10 times than the equipment that uses at present).In addition, may finish circulation in the alkanolamine removal process connects.Thus, consumption is seldom arranged in concentration process, less water requirement and less cost of energy are arranged in the still-process.

By the present invention, can consider or be used for total the decomposition or the prehydrolysis among a small circle, there is the possibility of another variation thus.If select the alkanolamine of multistep to extract by replacing single step in the method for the present invention, this is chosen in efficient and the production capacity aspect that method carries out so other advantage.

By the sugar also having realized by method of the present invention improving because of breaking before or after the prehydrolysis from.May improve the efficient of prehydrolysis in addition with two step prehydrolysis.The time of staying of the sugar that decomposes, short and effective extraction caused less furfural to generate in addition.

The advantage that continuous method is carried out is: it has been eliminated liquid and has replaced displacement mutually, just as necessary in boiling vessel in traditional slurring method.In boiling vessel, exchange and washing methods efficient are low and experienced considerable time there.In addition, in the reality in the repulsion process selectivity like this so that produce undesirable mixing or unclear transition region, so just be necessary surcharge in removal process.May use in the continuation method equipment of exerting pressure needn't be set.

In traditional boiling vessel, do not exist by the necessity of water/steam flooding except that the air (otherwise existing prehydrolysis danger non-homogeneous and that stably carry out) in the smear metal; Because break in the process by of the present invention, for example use method in common in preparation " cmp " process, exist uniform condition.Prehydrolysis and washing (as in the conventional method inevitably) leave breaking in the process that the danger of sour residue carries out equally within the scope of the present invention in afterwards the smear metal and do not exist.

Dry run can be cancelled, if little dispersal unit is moved economically; This is possible with method of the present invention.Specific investment and operating cost have obviously been reduced whereby.In addition, method of the present invention provides the productive rate higher than other chemical pulp method; Needn't carry out cold alkaline extraction for reaching low hemicellulose residual volume equally.

The bleaching that obtains product is for example carried out with peracetic acid, and this just can directly carry out acetyl groupization subsequently without solvent exchange, highly provides cost savings.

Below, the present invention is described in detail by embodiment, but instruction of the present invention should not be limited to this.Concerning the professional, in the scope that the present invention discloses, other embodiment is clearly.

Embodiment

Use following analytical method among the embodiment: the definite/content of lignin of a.kappa numerical value

This carries out according to Zellcheming specification IV/37/80.Wherein, with 0.1n liquor potassic permanganate (3.16lg/l) titration.The milliliter number of the every gram cellulose correspondence that consumes in the titration process equals the kappa value.Content of lignin is estimated with 0.15 by kappa is on duty.The optical density of b.MEA extract is measured as lignin concentration

In 1mm quartz glass circle vessel, with 100 times of diluted extract of MEA, at wavelength X=281nm, the absorption maximum place of lignin is (referring to Fengel, the 159th page of " Wood " of Wegener, table 6-5, the extinction coefficient of lignin: that the organic solvent lignin is suitable for is ε=24-26[l/g*cm] measure.

Calculating the extinction coefficient that λ=281nm place obtains by optical density by the measurement (with the concentration series of organic solvent lignin in the monoethanolamine) of distinctive UV spectrum is ε=26[l/g*cm].This is used to calculate the concentration of the lignin that is extracted by MEA.C.DP determines

The known Cuoxam method of definite usefulness of DP is carried out.

Method is following carries out: 1. prehydrolysis:

Do not add acid:

Chip in boiling vessel with being steam heated to 160 ℃, remain on then 160 ℃ 1 hour.The pH value of condensate is 4.6.

Add acid

The chip of chopping is heated to the final temperature of prehydrolysis in 20-30 minute under the condition that adds sulfuric acid or hydrochloric acid in 10 liters of autoclaves in advance.Steam to the mass ratio of chip (humidity that 50 quality percentage compositions are arranged) in 1: 1 to 3: 1 scope.Final temperature is between 120 ℃-180 ℃.The time of staying is the longest to be 60 minutes.2. use the preliminary treatment of ammonia:

In advance the chip of chopping is ℃ to handle a few minutes down in 80＜T＜120 in 0.1: 1 to 4: 1 the voltage-resistant reactor of liquefied ammonia in that pressurization and mass ratio are housed, then by opening the material that ball valve moment draws off pressure reactor.Still the chip that contains ammonia then further extracts to be handled.

In optional processing, the chip of chopping at room temperature soaks with the ammonia of the commercial ammoniacal liquor that gets (25 quality percentage composition) form in advance, filters from ammoniacal liquor then and extracts.

Embodiment 1 (comparing embodiment)

The chip (40g) that chopping and prehydrolysis (160 ℃, 1 hour) are crossed is used Liquid Ammonia Treatment, by removing in the pressure reaction still, collides into single fiber by the moment unloading then in the boiling blender.The kappa value calculates 142.90 ℃ of following alkaline extraction 1 hour (NaOH of 8 quality percentage compositions is about the calculating of chip based on the stove oven dry) afterwards; Fully wash with about 50 times distilled water, centrifugation to solid content is 30-40% in cylindric washer, determines that the kappa value is 131.

Embodiment 2 (comparing embodiment)

The chopping and the chip (40g) of prehydrolysis (160 ℃, 1 hour) be by liquefied ammonia, and monoethanolamine and water (80g: 40g: 20g) in the mixture of Zu Chenging, boiling in 140 ℃ autoclave pressure, moment is by drawing off washing and drying in the reactor then.The kappa value is 143, presses after the alkaline extraction of embodiment 1, and the kappa value is 129.

Embodiment 3:

Influence with pressure in the monoethanolamine leaching process

10g chopping, the chip of prehydrolysis and ammonia blast is used 110ml MEA at every turn, in 2 hours under a kind of situation under atmospheric pressure (boiling under refluxing), under 3 bar pressures that in autoclave, obtain under the another kind of situation 180 ℃ of extractions.Optical density (measuring at λ=281nm) is respectively 0.25 and 0.55.This shows that pressure is the important parameter in the leaching process.

Embodiment 4:

The influence of the consumption of extractant monoethanolamine

The chip of 10g chopping and prehydrolysis uses the MEA that the following describes consumption in 3 hours, under the pressure that produces in autoclave, 155 ℃ of extractions.This result illustrates in Fig. 3.

This lignin amount that shows the extraction in wide region is irrelevant with the consumption based on the monoethanolamine of the chip of 10g natural humidity (50 quality percentage composition).

Embodiment 5:

Temperature Influence

The chip of 10g chopping and prehydrolysis is used 110ml MEA at every turn, under the pressure that produces in autoclave in 2 hours, extracts in different temperatures.

Table 1

Temperature [℃]	Pressure [crust]	Optical density
			??155	????3	?????0.48
??180	????6	?????0.83
			??198	????9	?????0.62

Obviously the extracted amount that does not have further to improve lignin far above the temperature of the boiling point (170 ℃) of MEA; This may with begin to be decomposed into acetaldehyde at the above MEA of boiling point and ammonia is relevant.

Embodiment 6:

The influence of extraction time

The chip of 10g chopping and prehydrolysis uses 110ml MEA in preset time at every turn, under the pressure that autoclave produces 155 ℃ of extractions.It seems that it is necessary being extracted in 155 ℃ in 2 hours the autoclave, to obtain stable ratio.

Table 2

Time [hour]	Optical density
		?????0.5	?????0.154
?????1	?????0.33
		?????2	?????0.48
?????3	?????0.47

Embodiment 7:

Extraction with the derivative of monoethanolamine

N-methyl monoethanolamine and N, N-dimethyl monoethanolamine demonstrates aspect extraction does not have effect, because nitrogen-atoms is replaced by alkyl.Embodiment 8:

The pretreated influence of chip

The chip of 10g chopping is after different preliminary treatment, under the pressure that produces in autoclave, 155 ℃ of extractions.Here show that preliminary treatment has very big influence to extracting the result.A) use 110ml MEA, experience 3 hours

Table 3

Preliminary treatment	Optical density
		No prehydrolysis	????0.43
Prehydrolysis is arranged	????0.47
		Prehydrolysis+NH 3Blast	????0.73

B) use 30ml MEA and experience 3 hours

Table 4

Preliminary treatment	Optical density
		Prehydrolysis	????1.50
Prehydrolysis+NH 3Blast	????2.07
		Prehydrolysis+NH 3Blast is also used MEA	????1.31

C) use 110ml MEA, experience 1 hour

Table 5

Preliminary treatment	Optical density
		Prehydrolysis	????0.33
Prehydrolysis+NH 3Blast	????0.55
		Prehydrolysis+NH 3Blast is also used MEA	????0.30

When the ammonia explosion time took place, the extraction of lignin improves greatly.On the other hand, before blast, MEA and ammonia are added clastic facies together for the NH that does not add MEA ₃No good effect explodes.

Embodiment 9:

Repeatedly extract the influence of handling same sample

Should prove whereby and extract the efficient of handling.The chip of 10g chopping and prehydrolysis under the pressure that autoclave produces 155 ℃ of extractions.

Table 6

Process	Time [h]	??MEA[ml]	Chip [g]	Optical density
					1. extract	????2	????110	????10	????0.48
2. extract	????2	????60	????5.5	????0.083

Chip has lost lignin basically in first process.

Table 7

Process	Time [h]	??MEA[ml]	Chip [g]	Optical density
					1. extract	????3	????30	????10	????0.419
2. extract	????2	????30	????10	????0.036

Even also in first process, content of lignin has been reduced to 10% (the relatively optical density) that is lower than initial value with a small amount of MEA.

Table 8

Process	Time [branch]	??MEA[ml]	Chip [g]	Optical density
					1. extract	????45	????30	????10	????0.266
2. extract	????45	????30	????10	????0.189
					3. extract	????45	????30	????10	????0.066

Only 45 minutes extraction time and a spot of monoethanolamine just make content of lignin Jiang Shi gradually.

Embodiment 10:

Continuous extraction

Be set forth in result in the continuous leaching process according to Fig. 4.

List the row 1 (100 ℃) that accumulation is extracted, the lignin amount of row 2 (140 ℃) and row 3 (170 ℃) is with the % explanation of absolute content of lignin.Extraction rate is about 45ml in 1 hour.Use the chip (40g) of chopping and prehydrolysis.

Used equipment is the withstand voltage chromatographic column with the chip filling.It is heated to fixed temperature by the conductive heater band; This temperature keeps constant by electrical adjustment.The monoethanolamine of preheating by high-pressure pump (HPLC) pumping pass through chip.Collect the fraction of each 25ml, thus measuring light density after being diluted to 100 times.

Ordinate has been listed the relative percentage by the lignin that extracts in the timber among Fig. 4.100% of the lignin of Ti Quing amount wherein corresponding to the lignin that originally in timber, contained.

When using 40g humidity to be the timber of 50 quality percentage compositions, timber content is 20g.For the typical content of lignin of beech is 22 quality percentage compositions, then contain the 4.4g lignin in view of the above.This 4.4g lignin is 100 corresponding to the ordinate value among Fig. 4, and the lignin total amount that is about to contain in the timber extracts.Correspondingly be applicable to less ordinate value:

Table 9

The lignin that extracts accounts for the % of contained lignin in the original timber	Still in timber, there is lignin amount (g) amount (% *)	The kappa value **
			????100	????0????????0	????0
????90	????0.44?????2.2	????14.7
			????80	????0.88?????4.4	????29.3
????70	????1.32?????6.6	????44
			????20	????3.52?????17.6	????117.3
????10	????3.96?????19.8	????132
			????0	????4.4??????22	????146.7

^*The absolute percentage of the lignin that contains in the timber

^*The kappa value is a parameter commonly used in pulp industry; It is removed by absolute content of lignin

Obtain with 0.15.

Here with the row among Fig. 42, promptly dark post is that example illustrates, dark post has reached nearly 80% in the 4th fraction.Because explanation accounts for the amount of lignin of extraction of the percentage meter of content of lignin original in the timber on the ordinate, reaching a conclusion thus is, after the 4th fraction, only also has 20% also to extract in the lignin that contains in the original timber.Because press 45 milliliters of/hour extractions of extraction rate, each level is divided into 25ml, thus approximately can draw, after 4 fractions=100ml extract, extraction time surpassed 2 hours some.

Embodiment 11:

Method of the present invention is carried out with eucalyptus (Eucalyptus Urograndis).Carry out following mensuration: a) cellulose productive rate of eucalyptus and wood sugar content:

Table 10

Paper pulp	The cellulose productive rate	Wood sugar content
			Highly purified Solucell *	????95.9	????1.9
The paper pulp (the present invention) of low wood sugar content	????97.55	????1.9

^*H.Sixta, A.Borgards, " Das Papier " the 4 (1999), the 220th page and with nextpage b) wood sugar content and the DP of eucalyptus:

Table 11

Paper pulp	Content of cellulose	Wood sugar content	??DP
				Highly purified Solucell	????95.9	????1.9	??620
The paper pulp (the present invention) of low wood sugar content	????98.7	????1.2	??750

C) reserve capability of acetic acid:

Table 12

Paper pulp	The reserve capability of acetic acid
			????％
Acetylation paper pulp is purchased	????38
		Acetylation paper pulp is purchased, and uses Liquid Ammonia Treatment, then water exchange NH 3, use the acetic acid exchanged water at last	????77
Paper pulp, not dry (the present invention)	????105
		Paper pulp is in 105 ℃ of dryings 1 hour (the present invention)	????54

D) the clearly visible X-ray diffractogram that obtains among Fig. 5.The peak of finding is as follows:

Table 13

The peak	° 2 Θ are old	β is old	INT is old	° 2 Θ are new	β is new	INT is new	INT (F) is new
								??1	??16.110	??4.803	??353.2	??15.540	??3.885	??303.6	??11793.8
??2	??21.000	??7.000	??250.0	??20.901	??7.808	??203.6	??15900.8
								??3	??22.610	??4.070	??859.7	??22.266	??2.418	??706.8	??17088.5
??4	??34.300	??1.000	??30.0	??34.372	??2.668	??72.1	??1923.7

Basis (Untergrund)=47.7+2.61*2 Θ

Table 14

Peak 1: peak 2: peak 3: peak 4:

2Θ＝15.540° 2Θ＝20.901° 2Θ＝22.266° 2Θ＝34.372°

β＝3.885° β＝7.808° β＝2.418° β＝2.668°

INT＝??304c/s?????＝69％ INT＝??204c/s?????＝93％ INT＝??707c/s?????＝100％ INT＝??72c/s??????＝11％

Embodiment 12:

The prehydrolysis of eucalyptus

Carry out the prehydrolysis of eucalyptus with method of the present invention.Provided the quality table of comparisons under the influence of considering to pulverize in the following table 15 by the disc type treater:

Table 15

Carbohydrate is based on the quality percentage composition of dry mass	Former smear metal (by tree)	Prehydrolysis with the smear metal of not pulverizing	The prehydrolysis of the smear metal of pulverizing with the disc type treater	The smear metal of not pulverizing after the purge step	The smear metal of pulverizing with the disc type treater after the purge step	Crude pulp from the smear metal of not pulverizing	The crude pulp of the smear metal of pulverizing from the disc type treater
								Galactolipin	????1.3	????0.47	????0.58	????+	????-	????-	????-
Glucose	????44.0	????54.5	????56.8	????61.5	????60.9	????93.9	????95.5
								Wood sugar	????11.1	????4.5	????5.1	????3.1	????2.4	????2.3	????2.3
Mannose	????1.0	????0.63	????0.64	????0.65	????+	????+	????+
								The monose total amount	????57.7	????60.1	????63.1	????65.2	????63.3	????96.2	????97.8

-=can not detect-+=(0.3mg/100mg) embodiment 13 below detectable limit

Influence a) for preliminary treatment under the room temperature more than 30 minutes with ammoniacal liquor pretreated, use 25% ammoniacal liquor, its consumption is right

The 30g water content is that the beech chip of 70 quality percentage compositions uses the pure NH of 7g ₃By

With extracting lignin in the impregnated chip of ammoniacal liquor is to carry out under 140 ℃ with 60g MEA

Finished in 2 hours.Here obtaining the kappa value is 10.B) comparative test (not dipping) obtains the kappa value under other same experimental condition be 18.

Draw temperature to using MEA and the influence of lignin extraction when carrying out preliminary treatment with useless ammoniacal liquor being arranged by Fig. 6.Here be clear that very much, under same extraction temperature, carry out to reduce the kappa value after the preliminary treatment with ammoniacal liquor.For reaching certain kappa value, can under lower about 15-20 ℃ extraction temperature, handle by corresponding preliminary treatment., be clear that to kappa=f (extraction temperature) by the extrapolated curve that goes down along low temperature,, extract temperature and can reduce to 100-110 ℃ by with the ammoniacal liquor dipping.Low extraction temperature has determined side reaction to carry out in small range.Have/useless/by straight line ln (kappa) slope of 1/T is got 0.87 without the ratio of the activation energy of the pretreated extraction of ammoniacal liquor.

Embodiment 14:

The influence that multistep is extracted

Using the same generally monoethanolamine of measuring to extract in the process of lignin, the kappa value is strong when the monoethanolamine amount of using is distributed in two leaching process in succession reduces.This shows in Fig. 7, has illustrated that wherein eucalyptus pulps went on foot with monoethanolamine extraction (30-1-boiling vessel in a step and two; T=160 ℃, t ₁Go on foot=90 minutes, t ₂Go on foot=120 minutes) afterwards kappa value.

Embodiment 15:

The influence of pressure in leaching process:

This illustrates in Fig. 8, has wherein described carrying out for two steps with monoethanolamine and has extracted (parameter: have and do not have pressure, autoclave is used in experiment, T=160 ℃, t=2 * 60 minute) afterwards, the kappa value of eucalyptus pulps.

Embodiment 16:

The influence of water content in the MEA leaching process of lignin:

Under be 50% in mass ratio MEA/ water=4.9/1 and the timber humidity condition of (in the leaching process in the system total 0 moisture～17%), for 160 ℃ of following extraction conditions of 2 hours, as broad as long with the extraction of the chip that carries out with pure MEA (the interior total moisture content of system～8% in the leaching process).In contrast, when mass ratio MEA/ water=2.6/1 (in the leaching process in the system total moisture content～26%), the extraction effect variation.

Embodiment 17:

Hemicellulose level is to the influence of the extractibility of lignin

Extract the material that uses for being used for MEA at present, prehydrolysis degree difference is very big.Correspondingly, Can Yu hemicellulose level changes between 1.5-16 quality percentage composition.Also do not record by the remarkable influence of monoethanolamine the extractibility of lignin.

Embodiment 18:

According to method step " prehydrolysis-washing-MEA extraction-washing " situation under productive rate, under the situation of using same timber type,, also be higher than newer slurring method apparently higher than traditional slurring method.Eucalyptus pulp with low wood sugar content (acetate degree) can realize the high a lot of productive rate of prehydrolysis-sulfate process than the modern times.Illustrate in this point form below.

Table 16

	Paper pulp test (applicant)			20L autoclave (applicant)	Invention	Modern prehydrolysis-sulfate process **
								Test	????X	????XI	????XII	????VII-E01	????59X	The Solucell viscose glue	High-purity Solucell
Gu liquid in the prehydrolysis/than	????3∶1	????3∶1	????3∶1	????3∶1	????4.5∶1
								Acid concentration	????0	??4.75％AcOH	??5％AcOH	????1.7％AcOH	????0.2％AcOH
Heat time heating time (branch)	????30	????30	????18	????120	????60
								The prehydrolysis temperature (℃)	????170	????170	????170	????170	????160
The prehydrolysis time (branch)	????120	????90	????90	????90	????60
								DP	????460	????750	????680	????970	????1215	????550	????620
Glucose *	????97.4	????97.9	????97.2	????98.7	????92.2	????93.8	????95.9
								Wood sugar *	????1.9	????1.7	????2.2	????1.2	????6.9	????3.6	????1.9
Mannose *	????0.75	????0.3	????0.7	????0.1	????0.9	????0.5	????0.2
								Productive rate (cellulose)	????44.6	????45.5	????45.3	????49.1	????48.6	????38.5	????34.5
Relative productive rate (%)	????86	????88	????87	????94	????93.5	????74	????66.3
								Timber requirement (m to 1ADMT paper pulp 3)	????3.55	????3.5	????3.5	????3.2	????3.3	????4.1	????4.6

*): the composition of eucalyptus (O.Kordsachia, R.Patt, II.Sixta Das Papier 2 (1999), 96:52% cellulose, 20% Portugal

Uronic acid oxylan (Glucuronoxylan), 2% glucomannan and 23% lignin * *): Bacell method (II.Sixta, the 4 (1999), the 220th page of A.Borgards " Das Papier " and with nextpage) embodiment 19 for example:

The change of prehydrolysis condition

According to wood species, prehydrolysis condition (go through the time, temperature, the kind and the concentration of acid heat time heating time) can adapt, to reach the hemicellulose residual content of hope.Following table has illustrated the situation (heating about 30 minutes) that reaches with the test in the autoclave in the laboratory:

Table 17

Test	Liquid	??FV	??T℃	Retention time	Cellulose (as glucose assays)	Wood sugar	Mannose
								The VH-27 European beech	????0.6％ ????H 2SO 4	??3∶1	??160	????60	????98.0	??1.7	????0.3
The VF-4 dragon spruce	????0.3％ ????H 2SO 4	??4∶1	??150	????60	????93.9	??2.7	????3.4
								The VH-P-M1 stalk	Water	??6.5∶1	??160	????180	????93.7	??6.1	????0.2
The VE-4 eucalyptus	????0.3％ ????H 2SO 4	??4.5∶1	??150	????60	????98.8	??1.0	????0.2

Acetic acid is not enough to be used for the hemicellulose of complete prehydrolysis beech.For the beech chip, not adding the content that acid may reach hemicellulose in the prehydrolysis is about 3 quality percentage compositions.Mannose content under this condition＜1%.Therefore alpha-cellulose content 〉=96%, this is enough to chemical pulp-except to acetylation paper pulp.But low wood sugar content≤2 quality percentage compositions that acetylation paper pulp requires may be realized in eucalyptus in beech and with little exacting terms with harsh leaching (Aufschlu β) condition.Do not find the deterioration of chip target size in full-sized transition.In bigger autoclave, result even better.

Embodiment 20:

Carry out prehydrolysis, wherein hydrolysis temperature as shown in Figure 9, is changed.Clearly show that by Fig. 9 under the situation that improves sulfuric acid concentration, the residual content of wood sugar obviously reduces.

Embodiment 21:

Stalk is as living beings

Stalk cuts roughly with scissors, with bath raio be 10: 1 water little laboratory with autoclave (volume is 300ml) in, under 170 ℃, prehydrolysis under about 7 bar pressures, this is with about 30 minutes of heating, temperature retention time is to finish in 120 minutes.After removing the prehydrolysis product, after the washing stalk after the wet prehydrolysis is mixed MEA with ratio at 1: 6.5 again.160 ℃ of heating 30 minutes, remained on this temperature and 3 bar pressures following 3 hours again.

The analysis result that the result obtains forming below:

Cellulose (glucose form) 93.7%

Wood sugar 6.1%

Mannose 0.2%

Productive rate is 40%, and whiteness is 50%.

Embodiment 22:

Repeat embodiment 21, but do not carry out prehydrolysis.The whiteness that obtains is 22%.

Embodiment 23:

Test with autoclave to atmosphere opening.Directly use MEA to extract the stalk of chopping to this.Condition is 160 ℃, and bath raio is 10: 1=MEA/ stalk, 180 minutes boiling.With expect opposite, do not producing insufferable smell during the stalk of prehydrolysis with the MEA boiling, less than by the steam of emerging in the autoclave yet.Whiteness is 29%.

Embodiment 24:

To check the accessory substance that wherein produces respectively by the product that obtains in the foregoing description by monoethanolamine.Find; the accessory substance of monoethanolamine; as N-methyl monoethanolamine; N; N-dimethyl monoethanolamine, N-acetyl group monoethanolamine and N-formoxyl single acetyl amine do not occur or have only 0.3% content (with respect to the MEA-lignin extraction thing of analyzing) to exist under the situation of using N-methyl monoethanolamine.To this, consider to use so-called headspace gas chromatography as analytical method.

Claims (27)

1. living beings that are used to separate the lignocellulose-containing that particularly derives from timber become the method for the basis of lignin, hemicellulose and Cellulosed molded article, and it has the following step:

A) pass through water or steam treatment pre-hydrolysis of biomass with lignocellulose-containing;

B) with the hemicellulose of water-bearing media extraction by the hydrolysis of prehydrolysis generation;

C) be extracted in the lignin of the process modification that stays in the residue with alkanolamine, separating lignin reclaims alkanolamine, wherein alkanolamine on nitrogen-atoms no alkyl replacement and

D) obtain the cellulose coarse fodder.

2. the method for claim 1 is characterized by, and prehydrolysis a) only proceeds to the degree that the acid of combination on the hemicellulose can be dissociated set by step, and b set by step) these pickling of dissociating are fallen.

3. claim 1 or 2 method is characterized by, and use as the living beings of lignocellulose-containing and pulverize or timber, particularly broad leaf tree, beech or the coniferous tree of wood shavings.

4. at least one method in the claim 1 to 3 is characterized by as living beings and uses grain straw.

5. the method for claim 4 is characterized by, not set by step a) and b) carry out prehydrolysis, and direct c set by step) be lower than about 170 ℃, preferably be lower than about 160 ℃, particularly extract, to obtain paper paper pulp at about 115-135 ℃ high temperature.

6. the method for claim 4 is characterized by, at about 150-190 ℃, and preferred about 170 ℃ of following prehydrolysis, c set by step then) be lower than about 170 ℃, preferably be lower than about 160 ℃, particularly under about 115 ℃-135 ℃ high temperature, extract, to obtain chemical pulp.

7. at least one method is characterized by during aforesaid right required, and the living beings of the lignocellulose-containing of prehydrolysis are carried out machinery and broken before carrying out step b).

8. at least one method is characterized by during aforesaid right required, and also added before the steam treatment of step a) and carried out acid or alkali preliminary treatment.

9. at least one method is characterized by during aforesaid right required, and prehydrolysis a) is carried out with vapour explosion method or steam refining method form set by step.

10. at least one method is characterized by during aforesaid right required, and added the solvent of one or more lignin after step b).

11. at least one method is characterized by during aforesaid right required, the mass ratio of water and living beings (based on dry) transferred to about 3: 1 to 10: 1, and particularly 6: 1, the mass ratio of water vapour and living beings was adjusted to about 1: 1 to 3: 1.

12. at least one method is characterized by during aforesaid right required, and extruded the water in the material that obtains before the step b), then its machinery was broken.

13. the method for claim 12 is characterized by, the material of breaking is also used hot wash.

14. at least one method is characterized by during aforesaid right required, and added after the step b) and used ammonia spirit, ammonia or liquefied ammonia are handled.

15. the method for claim 14 is characterized by, and handles with liquefied ammonia under the initial pressure that raises relative atmospheric pressure.

16. the method for claim 15, it is characterized by, the material that obtains is still warm through above-mentioned steam treatment with after washing, and uses under the condition of liquefied ammonia, the volume that the pending material of removing hemicellulose takies is by loose owing to reduce the pressure of at least 5 crust, increases as the blast.

17. the method for claim 16 is characterized by, the mass ratio of liquefied ammonia and treating material (based on dry) is adjusted to about 0.1: 1 to 4: 1.

18. at least one method is characterized by during aforesaid right required, and carried out at least twice in succession extraction with alkanolamine in the step c).

19. at least one method is characterized by during aforesaid right required, and was extracted under about 80 to 220 ℃ and carried out at least about 1 hour.

20. at least one method is characterized by during aforesaid right required, the extractant preheating with in the step c) particularly is heated at least about 80 ℃.

21. at least one method is characterized by during aforesaid right required, and used monoethanolamine as extractant.

22. at least one method is characterized by during aforesaid right required, after extraction, the residue of the lignin that is dissolved in the process modification in the alkanolamine that adheres on crude pulp is removed fully by solvent.

23. the method for claim 22, it is characterized by, the lignin and the alkanolamine of remaining process modification in the crude pulp are removed by washing or countercurrent washing with solvent, by distillation solvent is separated with the extractant alkanolamine with lignin then, and recyclable to reuse.

24. at least one method is characterized by during aforesaid right required, it is to finish by extrusion or centrifugation that alkanolamine and the lignin that is dissolved in process modification are wherein removed from crude pulp together.

25. at least one method is characterized by during aforesaid right required, the lignin of process modification is separated out from alkanolamine by adding non-solvent, separates by solid/liquid separation method.

26. the method for claim 25 is characterized by, the lignin of separating out separates from alkanolamine by filtration or centrifugation.

27. the method for claim 25 is characterized by, the lignin of process modification separates from alkanolamine in thin film evaporator or by film method.

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