EP0823948A1 - Verfahren zur herstellung einer pulpe aus zellulosehaltigem material, die pulpe selbst und deren verwendung - Google Patents
Verfahren zur herstellung einer pulpe aus zellulosehaltigem material, die pulpe selbst und deren verwendungInfo
- Publication number
- EP0823948A1 EP0823948A1 EP96914167A EP96914167A EP0823948A1 EP 0823948 A1 EP0823948 A1 EP 0823948A1 EP 96914167 A EP96914167 A EP 96914167A EP 96914167 A EP96914167 A EP 96914167A EP 0823948 A1 EP0823948 A1 EP 0823948A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- pulp
- solvent
- lignin
- cellulose
- formic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 73
- 239000000463 material Substances 0.000 title claims abstract description 50
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229920005610 lignin Polymers 0.000 claims abstract description 46
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 42
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 39
- 235000019253 formic acid Nutrition 0.000 claims abstract description 39
- 229920002678 cellulose Polymers 0.000 claims abstract description 30
- 239000001913 cellulose Substances 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010992 reflux Methods 0.000 claims abstract description 10
- 238000009835 boiling Methods 0.000 claims abstract description 7
- 239000007858 starting material Substances 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- 239000004566 building material Substances 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 31
- 238000010411 cooking Methods 0.000 claims description 26
- 239000010902 straw Substances 0.000 claims description 13
- 235000013339 cereals Nutrition 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 238000001577 simple distillation Methods 0.000 claims description 6
- 235000015696 Portulacaria afra Nutrition 0.000 claims description 5
- 244000177175 Typha elephantina Species 0.000 claims description 5
- 235000018747 Typha elephantina Nutrition 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 241000196324 Embryophyta Species 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- 239000011122 softwood Substances 0.000 claims description 4
- 240000008042 Zea mays Species 0.000 claims description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000011111 cardboard Substances 0.000 claims description 3
- 239000011121 hardwood Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000011094 fiberboard Substances 0.000 claims description 2
- 239000011087 paperboard Substances 0.000 claims description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 2
- 235000012141 vanillin Nutrition 0.000 claims description 2
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 235000009973 maize Nutrition 0.000 claims 1
- 238000004537 pulping Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 4
- 239000002023 wood Substances 0.000 abstract description 4
- 239000000945 filler Substances 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 230000029087 digestion Effects 0.000 description 33
- 239000000243 solution Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000000123 paper Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 235000000346 sugar Nutrition 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 150000008163 sugars Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000004061 bleaching Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 235000014633 carbohydrates Nutrition 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 240000003433 Miscanthus floridulus Species 0.000 description 1
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- LBAYFEDWGHXMSM-UHFFFAOYSA-N butaneperoxoic acid Chemical compound CCCC(=O)OO LBAYFEDWGHXMSM-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000009343 monoculture Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/006—Pulping cellulose-containing materials with compounds not otherwise provided for
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/003—Pulping cellulose-containing materials with organic compounds
Definitions
- the invention relates to a method for producing a pulp from cellulosic material, the pulp itself and its use.
- Pulp is understood to be a cellulose pulp that is required for the production of cellulose. Paper or cardboard, for example, is then produced from this pulp.
- the pulp-producing industry is finding it increasingly difficult to meet the requirements and requirements relating to environmental protection. In addition, it is e.g. no longer permitted in Germany after the environmental requirements of 1990 to use traditional methods for pulping, such as the sulfate method.
- sulfur-containing disintegrating agents to dissolve the lignin, which acts as a composite, from the cellulose-containing material, only the sulfite process is used in Germany.
- the so-called Acetosolv process emerged, in which the digestion liquid contains at least 50% by weight of acetic acid and additionally a small proportion of hydrochloric acid. After this digestion, the pulp thus obtained is washed with sodium hydroxide solution and optionally also with organic solvents in order to remove the lignin more or less completely.
- a disadvantage of this process is the relatively high acetic acid consumption and the use of sodium hydroxide solution and optionally organic solvents for washing the pulp.
- the pulp obtained in this way is regularly bleached in a subsequent step in order to achieve kappa numbers of at least below 25.
- downstream bleaching by means of a peroxide is provided, with a relatively high consumption of this bleaching agent being disadvantageous.
- EP 0 250 422 B1 has disclosed a process for producing bleached pulp from cellulose-containing material, which is also generally referred to as the Milox process.
- the digestion is carried out in a peroxyformyl, peroxyacetic, peroxypropion or peroxybutyric acid medium, the peroxo acid being obtained by mixing the respective acid with a relatively high proportion of hydrogen peroxide and then carrying out the digestion process.
- This pulping is followed by bleaching of the pulp, which is carried out in alkaline solution, the hydrogen peroxide has been added.
- the disadvantage of this process is again the use of an alkaline solution, such as sodium hydroxide solution, and the high proportion of hydrogen peroxide required.
- the present invention has for its object to provide a method for producing a pulp from cellulose-containing material that works as environmentally friendly as possible and at the same time extremely economical and efficient.
- a preferred embodiment of the method according to the invention is used when the cellulose-containing material used is not so easy to digest. This is the case, for example, with hardwood or coniferous wood, but also with grain straw, depending on the intended use of the pulp obtained from it.
- the cellulosic material is mixed with formic acid and water and heated slightly under reflux by an external energy source. Then a precisely predetermined amount of hydrogen peroxide is slowly added in constant dosage.
- Such a procedure has hitherto not been known by any prior art and enables a very economical procedure because the now exothermic reaction itself provides the heat necessary for cooking. This means that after the initial activation, no further external energy supply is required.
- Digestion solution is understood to mean the sum of the solvent, the cellulose-containing material and constituents, such as lignin and sugar, which may have been extracted therefrom. Furthermore, in the reaction according to the preferred embodiment it is advantageous that the equilibrium in the reaction of the formation of the peracid from formic acid and hydrogen peroxide is continuously shifted to the peracid side by the continuous addition of the hydrogen peroxide.
- aqueous formic acid can be used in a concentration range between approximately 60 to 99% by weight.
- 100% formic acid is not beneficial since at least a certain percentage of water is used in the manufacture of the pulp, i.e. should be present in the shooting process.
- a time period of about 30 to 120 minutes can be specified as the cooking time, depending on the cellulosic material used.
- the predetermined amount of hydrogen peroxide can be approximately 1 to 3% by weight, preferably 1 to 2% by weight, particularly preferably 1% by weight, based on the total weight of the cellulose-containing material and solvent. It is particularly advantageous that only a very small amount of added hydrogen peroxide is necessary, which is sufficient on the one hand to meet the requirements for the whiteness of the pulp thus produced for the production of paper and on the other hand is sufficient to approximately the temperature of the pulping solution to maintain the boiling point of the solvent without supplying additional energy in the form of heat. Good properties of the paper produced from the pulp according to the invention can thus be combined with a minimal expenditure of energy. It has proven advantageous to keep the liquid to material ratio in the range from 20: 1 to 25: 1.
- the method according to the invention can also be modified such that a gas such as air, oxygen, ozone or a comparable gas or a mixture of two or more of these gases is additionally introduced into the solvent.
- a gas such as air, oxygen, ozone or a comparable gas or a mixture of two or more of these gases is additionally introduced into the solvent.
- the oxidative power of these gases is used to increase lignin degradation and thus whiteness, and to lower the kappa number.
- the required digestion time is also reduced.
- the pulp can be separated from the solvent by simple sieving after the cooking time has ended.
- Sieving is understood in the broadest sense, i.e. separation by means of a suitable membrane, a filter or a frit is also possible, in which case the separation can take place continuously.
- the pulp so screened can then be washed with water and / or formic acid. Especially when washing with formic acid, the remaining lignin, which has already been removed from the cellulose-containing material, is washed out. By flushing the pulp with a stirrer, this flushing out can still be promoted.
- a method for producing a pulp from cellulose-containing material which is suitable, for example, for producing paper with a sufficient degree of whiteness (e.g. kappa number ⁇ 10) in a one-step process with minimal energy expenditure.
- the cooking temperature is reduced.
- Aqueous formic acid is then used as the solvent, to which hydrogen peroxide, as already described above, is added.
- the reduced cooking temperature can be around 70 to 80 ° C.
- the cooking temperature is preferably 70 ° C., since an optimum of performic acid is present at this temperature.
- the cooking time can be extended to up to 5 hours to achieve a higher degree of whiteness.
- the cooking time is then preferably about 3 hours, because it was found that after this time the pulp no longer brightened up appreciably. It has also proven advantageous to increase the liquid-to-material ratio to over 25: 1.
- elephant grass (Miscanthus) and / or corn leaves or stems can be used as the cellulose-containing material. Both materials, in particular elephant grass, can be digested very well. It can even the addition of hydrogen peroxide to the solvent can be dispensed with. For example, when using 99% formic acid and a cooking time of one hour, a kappa number of 4.7 was achieved.
- a particular advantage of the process according to the invention is that basically annual plants, in particular grain straw, can be used as the cellulose-containing material. This is particularly important for paper production, since until now wood has been used almost exclusively as the cellulosic material. Worldwide, over 200 million tons of paper are used each year. The demand continues to grow. The deforestation of large forest areas to cover the need for cellulose-containing material brings with it considerable environmental problems, such as climate changes and habitat destruction of flora and fauna. Wherever, if at all, reforestation is carried out, only rapidly growing monocultures are created, which in turn are very susceptible to pests and make no ecological sense. In addition, an increasing need for paper for various purposes can also be found in developing countries or countries of the so-called "third world".
- Wood as a cellulosic material, is usually missing for the usual production.
- the grain straw can serve as a sensible substitute in terms of costs and from an ecological point of view. Straw is often viewed as a nuisance and burned on the fields, which is harmful to the environment.
- Germany alone the total volume of each harvest is around 50 million tons of straw, so there is great potential for cellulosic material. This applies even more to countries such as the USA or Canada, which are known to have huge grain fields.
- the cultivation of simple annual plants can be an opportunity to use difficult soils and in bad climatic conditions. It is possible where the planting of more demanding cereals due to weather or Soil conditions are no longer possible to switch to management by means of simpler annual plants and thus to provide cellulose-containing material for the production of a pulp, which in turn is then used for paper production.
- the method according to the invention can also be applied to the hitherto customary cellulosic materials, such as hardwood or softwood. It is known that " it is generally more difficult with these materials to provide a sufficient degree of whiteness for the paper produced from the pulp, in which case it is advisable to proceed according to the particularly preferred embodiment and to reduce the cooking temperature and the inventive method optionally repeat the extension of the cooking time.
- Another aspect of the present invention relates to the lignin released from the pulp by the method according to the invention. After recycling the formic acid used as solvent, this is obtained by simple distillation from the distillation residue by precipitation in water. As a result of this precipitation of the water-insoluble lignin, it is simultaneously separated from the water-soluble sugars which are also present in the residue.
- the invention also relates to a pulp made of cellulose-containing material which can be obtained by the process according to the invention and optionally according to its preferred or particularly preferred embodiment.
- the invention also relates to the use of the pulp thus obtained for pulp production, for example for the paper industry or for the production of cardboard.
- the pulp produced by the process according to the invention can be used and used wherever pulp is required as a starting material for a product.
- chemical cellulose or another product made from regenerated or chemically modified cellulose can also be produced from the pulp according to the invention.
- the invention also relates to lignin which can be obtained by the process according to the invention.
- This lignin can be safely processed because it does not contain any sulfur or chlorine, as would usually be the case in the prior art processes for producing a pulp.
- the isolated lignin can be used, for example, as a building material, in particular as a starting material for particle board, medium-density fiberboard or as a filler material, if it is decomposed in excess with oxalic acid and either melted or boiled in a saturated formic acid solution and then steamed with cellulose fiber. This creates a waterproof black-brown mass.
- lignin is even more diverse. So it can serve as a starting material for the production of aroma substances such as vanillin or mulled wine aroma.
- the pulp obtained after washing was washed with aqueous formic acid in such a way that further fresh formic acid was added in a concentration range of 60 to 80% by weight, so as to flush out the remaining lignin.
- a paddle stirrer was then inserted into the reaction vessel and stirred for about 1 minute. This whipping by stirring creates a fiberization of the cellulose dressings and the washing out of the lignin is facilitated.
- the formic acid After the formic acid has been separated off, it is distilled off with the formic acid from the digestion reaction described above by simple distillation. A Liebig distillation apparatus with a 300 mm column is used on a laboratory scale. The formic acid used is largely recovered here.
- the lignin dissolved in the residue can easily be precipitated in water and processed further. Dissolved carbohydrates can be obtained by evaporation. The pulp is washed neutral with water and air-dried. A kappa number of 15 and a yield of 45% were achieved. 2. Making a pulp from corn leaves
- Cereal straw, formic acid and water are transferred into the reaction vessel in accordance with the percentages by weight given below and in accordance with the liquid-to-straw ratio also given there.
- this is again a round bottom flask, combined with a ground thermometer and a dimrotre reflux condenser.
- the reaction mixture is then heated slightly under reflux and then slowly hydrogen peroxide of the concentration given below is added continuously.
- the reaction is exothermic, so that the external energy supply, such as here via a heating pad or a heating plate, can at least initially be reduced and then completely eliminated.
- the digestion time is also given below.
- the pulp is separated from the pulping solution by simple sieving and mixed with further fresh formic acid in a concentration of 60 to 80% by weight, so as to flush out the remaining lignin.
- a paddle stirrer is then inserted into the reaction vessel and stirred for about one minute. This creates a defibrillation of the cellulose dressings and the lignin washout is facilitated.
- the formic acid After the formic acid has been separated off, it is recovered with the formic acid from the digestion by simple distillation. A Liebig distillation apparatus and a 300 mm column were again used for this on a laboratory scale. The formic acid used can largely be won. Usually in a percentage of over 95%.
- Digestion times of 30, 45, 60, 90 and 120 minutes were selected in the experiments. These were combined with formic acid concentrations of 50, 60, 75, 80, 85, 90, 95 and 100%.
- the amount of hydrogen peroxide added was varied between 1% and 2%. It was found that an addition of more than 1% does not bring any appreciable advantage, but only complicates the control of the digestion due to the even more violent exothermic reaction.
- the digestion temperature was always kept at the boiling point of the solvent.
- the liquid-to-straw ratio is referred to as the liquor ratio.
- the test parameters shown indicate optimized production processes, although the optimization in test 3.a) was carried out in such a way that not only was a maximum lignin removal achieved, but the lignin itself should still be obtained in as large a quantity as possible. It has been shown that optimal lignin removal is accompanied by an increased breakdown of the lignin to water solubility. The optimization was therefore carried out in such a way that lignin which had not been broken down or altered as far as possible should be obtained in addition to the lignin-free pulp.
- the straw is treated as stated under 3. After the cooking time has ended, a stirrer is used and the pulp obtained is broken down for about 1 minute. Then the pulping solution is separated from the pulp and further processed without drying.
- the parameters of an experiment for producing a pulp with a repetition step are given below.
- the repetition step is labeled 4.b.).
- Cooking temperature approx. 106 c > C 70-80 ° C
- Cooking temperature approx. 106 ° C 70-80 ° C
- the described production possibilities of a pulp can be further improved by using a gas such as air, oxygen, ozone or the like in addition to the digestion in order to utilize its oxidative power in the digestion.
- a gas such as air, oxygen, ozone or the like
- a mixture of two or more of the gases mentioned can also be used.
- the digestion process described above or one of its variants is then carried out in such a way that the corresponding type of gas or a gas mixture is additionally introduced into the reaction vessel from below by means of a wide nozzle. This can be done continuously or discontinuously.
- the escaping gas can then be used again or be disposed of in an environmentally friendly manner using the already known corresponding methods.
- the lignin is mixed with an excess of oxalic acid and melted or, in another process variant, boiled in saturated formic acid solution and then evaporated with cellulose fibers. This creates a waterproof black-brown mass that can be used as a filler or in the manner of a pressboard or fibreboard.
Landscapes
- Paper (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19516151 | 1995-05-03 | ||
DE19516151A DE19516151A1 (de) | 1995-05-03 | 1995-05-03 | Verfahren zur Herstellung einer Pulpe aus zellulosehaltigem Material, die Pulpe selbst und deren Verwendung |
PCT/EP1996/001823 WO1996035013A1 (de) | 1995-05-03 | 1996-05-02 | Verfahren zur herstellung einer pulpe aus zellulosehaltigem material, die pulpe selbst und deren verwendung |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0823948A1 true EP0823948A1 (de) | 1998-02-18 |
EP0823948B1 EP0823948B1 (de) | 2002-04-03 |
Family
ID=7760931
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96914167A Expired - Lifetime EP0823948B1 (de) | 1995-05-03 | 1996-05-02 | Verfahren zur herstellung einer pulpe aus zellulosehaltigem material |
Country Status (12)
Country | Link |
---|---|
US (1) | US6183597B1 (de) |
EP (1) | EP0823948B1 (de) |
JP (1) | JP3059998B2 (de) |
CN (1) | CN1098390C (de) |
AT (1) | ATE215632T1 (de) |
CA (1) | CA2217987A1 (de) |
DE (2) | DE19516151A1 (de) |
DK (1) | DK0823948T3 (de) |
ES (1) | ES2175091T3 (de) |
PT (1) | PT823948E (de) |
RU (1) | RU2139965C1 (de) |
WO (1) | WO1996035013A1 (de) |
Families Citing this family (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FI103588B (fi) * | 1996-01-19 | 1999-07-30 | Esa Rousu Consulting Oy | Menetelmä tekokuitujen ja muiden kuitujen raaka-aineen valmistamiseksi ruohovartisista kasveista |
FR2770543B1 (fr) * | 1997-10-30 | 2000-05-05 | Michel Delmas | Procede de production de pate a papier, lignignes sucres et acide acetique par fractionnement de matiere vegetale lignocellulosique em milieu acide formique/acide acetique |
RU2145986C1 (ru) * | 1998-08-25 | 2000-02-27 | Иоссель Юрий Яковлевич | Способ изготовления целлюлозы |
EP1180171B1 (de) * | 1999-05-06 | 2003-10-08 | Compagnie Industrielle De La Matiere Vegetale | Verfahren zur herstellung von zellstoff, lignin, zucker und essigsäure durch fraktionierung des lignocellulosematerials mittels ameisensäure und essigsäure |
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EP2694723A1 (de) | 2011-04-01 | 2014-02-12 | University of Limerick | Lignozelluloseverarbeitung |
FI123052B (fi) * | 2011-09-23 | 2012-10-15 | Chempolis Oy | Esikäsittelymenetelmä vesiliukoisten sokereiden tuottamiseksi lignoselluloosamateriaalista |
CN103898783B (zh) * | 2012-12-25 | 2016-02-10 | 济南圣泉集团股份有限公司 | 一种由生物质原料制备纸浆的工艺 |
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-
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- 1995-05-03 DE DE19516151A patent/DE19516151A1/de not_active Withdrawn
-
1996
- 1996-05-02 AT AT96914167T patent/ATE215632T1/de not_active IP Right Cessation
- 1996-05-02 DE DE59609018T patent/DE59609018D1/de not_active Expired - Fee Related
- 1996-05-02 CA CA002217987A patent/CA2217987A1/en not_active Abandoned
- 1996-05-02 WO PCT/EP1996/001823 patent/WO1996035013A1/de active IP Right Grant
- 1996-05-02 EP EP96914167A patent/EP0823948B1/de not_active Expired - Lifetime
- 1996-05-02 RU RU97120707A patent/RU2139965C1/ru active
- 1996-05-02 JP JP8533002A patent/JP3059998B2/ja not_active Expired - Lifetime
- 1996-05-02 US US08/945,345 patent/US6183597B1/en not_active Expired - Fee Related
- 1996-05-02 CN CN96193631A patent/CN1098390C/zh not_active Expired - Fee Related
- 1996-05-02 DK DK96914167T patent/DK0823948T3/da active
- 1996-05-02 ES ES96914167T patent/ES2175091T3/es not_active Expired - Lifetime
- 1996-05-02 PT PT96914167T patent/PT823948E/pt unknown
Non-Patent Citations (1)
Title |
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See references of WO9635013A1 * |
Also Published As
Publication number | Publication date |
---|---|
CA2217987A1 (en) | 1996-11-07 |
ES2175091T3 (es) | 2002-11-16 |
US6183597B1 (en) | 2001-02-06 |
ATE215632T1 (de) | 2002-04-15 |
EP0823948B1 (de) | 2002-04-03 |
JPH10511147A (ja) | 1998-10-27 |
DE19516151A1 (de) | 1996-11-07 |
DK0823948T3 (da) | 2002-07-29 |
DE59609018D1 (de) | 2002-05-08 |
CN1183126A (zh) | 1998-05-27 |
PT823948E (pt) | 2002-08-30 |
CN1098390C (zh) | 2003-01-08 |
WO1996035013A1 (de) | 1996-11-07 |
JP3059998B2 (ja) | 2000-07-04 |
RU2139965C1 (ru) | 1999-10-20 |
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