EP0021264A1 - Process for the delignification of lignocellulosic materials - Google Patents
Process for the delignification of lignocellulosic materials Download PDFInfo
- Publication number
- EP0021264A1 EP0021264A1 EP80103278A EP80103278A EP0021264A1 EP 0021264 A1 EP0021264 A1 EP 0021264A1 EP 80103278 A EP80103278 A EP 80103278A EP 80103278 A EP80103278 A EP 80103278A EP 0021264 A1 EP0021264 A1 EP 0021264A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- dinitroanthraquinone
- nitro
- anthraquinone
- weight
- nitroanthraquinone
- 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 description 45
- 239000012978 lignocellulosic material Substances 0.000 title description 8
- 238000010411 cooking Methods 0.000 claims abstract description 34
- YCANAXVBJKNANM-UHFFFAOYSA-N 1-nitroanthracene-9,10-dione Chemical class O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2[N+](=O)[O-] YCANAXVBJKNANM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 16
- 230000029087 digestion Effects 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims description 16
- XFLONXIGNOXKCG-UHFFFAOYSA-N 2,7-dinitroanthracene-9,10-dione Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)C3=CC([N+](=O)[O-])=CC=C3C(=O)C2=C1 XFLONXIGNOXKCG-UHFFFAOYSA-N 0.000 claims description 9
- NMNSBFYYVHREEE-UHFFFAOYSA-N 1,2-dinitroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=C([N+]([O-])=O)C([N+](=O)[O-])=CC=C3C(=O)C2=C1 NMNSBFYYVHREEE-UHFFFAOYSA-N 0.000 claims description 8
- XVMVHWDCRFNPQR-UHFFFAOYSA-N 1,5-dinitroanthracene-9,10-dione Chemical compound O=C1C=2C([N+](=O)[O-])=CC=CC=2C(=O)C2=C1C=CC=C2[N+]([O-])=O XVMVHWDCRFNPQR-UHFFFAOYSA-N 0.000 claims description 6
- UQKJUEALIQRECQ-UHFFFAOYSA-N 1,6-dinitroanthracene-9,10-dione Chemical compound O=C1C2=CC([N+](=O)[O-])=CC=C2C(=O)C2=C1C=CC=C2[N+]([O-])=O UQKJUEALIQRECQ-UHFFFAOYSA-N 0.000 claims description 6
- FAVDZWIRBSMLOV-UHFFFAOYSA-N 1,7-dinitroanthracene-9,10-dione Chemical compound C1=CC([N+]([O-])=O)=C2C(=O)C3=CC([N+](=O)[O-])=CC=C3C(=O)C2=C1 FAVDZWIRBSMLOV-UHFFFAOYSA-N 0.000 claims description 6
- MBIJFIUDKPXMAV-UHFFFAOYSA-N 1,8-dinitroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC([N+]([O-])=O)=C2C(=O)C2=C1C=CC=C2[N+](=O)[O-] MBIJFIUDKPXMAV-UHFFFAOYSA-N 0.000 claims description 6
- OPXXCGAYBFDPHY-UHFFFAOYSA-N 2,6-dinitroanthracene-9,10-dione Chemical compound [O-][N+](=O)C1=CC=C2C(=O)C3=CC([N+](=O)[O-])=CC=C3C(=O)C2=C1 OPXXCGAYBFDPHY-UHFFFAOYSA-N 0.000 claims description 4
- KXMLYSJUXIUOHI-UHFFFAOYSA-N 1-amino-4-nitroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C([N+]([O-])=O)=CC=C2N KXMLYSJUXIUOHI-UHFFFAOYSA-N 0.000 claims description 3
- HNKYUEBEJOEAJG-UHFFFAOYSA-N 1-ethoxy-5-nitroanthracene-9,10-dione Chemical compound O=C1C=2C(OCC)=CC=CC=2C(=O)C2=C1C=CC=C2[N+]([O-])=O HNKYUEBEJOEAJG-UHFFFAOYSA-N 0.000 claims description 3
- XXUOKOYLVBHBCG-UHFFFAOYSA-N 1-hydroxy-4-nitroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C([N+]([O-])=O)=CC=C2O XXUOKOYLVBHBCG-UHFFFAOYSA-N 0.000 claims description 3
- QCVMOSGPTRRUQZ-UHFFFAOYSA-N 2-nitroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC([N+](=O)[O-])=CC=C3C(=O)C2=C1 QCVMOSGPTRRUQZ-UHFFFAOYSA-N 0.000 claims description 3
- VGIVZECXTZAEHI-UHFFFAOYSA-N 8-nitro-9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC([N+]([O-])=O)=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O VGIVZECXTZAEHI-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- VOZLLWQPJJSWPR-UHFFFAOYSA-N 1-chloro-5-nitroanthracene-9,10-dione Chemical compound O=C1C2=C(Cl)C=CC=C2C(=O)C2=C1C=CC=C2[N+](=O)[O-] VOZLLWQPJJSWPR-UHFFFAOYSA-N 0.000 claims description 2
- PMOCDYOEOUEPAN-UHFFFAOYSA-N 1-nitro-9,10-dioxoanthracene-2-carboxylic acid Chemical compound C1=CC=C2C(=O)C3=C([N+]([O-])=O)C(C(=O)O)=CC=C3C(=O)C2=C1 PMOCDYOEOUEPAN-UHFFFAOYSA-N 0.000 claims description 2
- FYXKXZFTZBYYNP-UHFFFAOYSA-N 2-Methyl-1-nitroanthraquinone Chemical compound C1=CC=C2C(=O)C3=C([N+]([O-])=O)C(C)=CC=C3C(=O)C2=C1 FYXKXZFTZBYYNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002023 wood Substances 0.000 description 18
- 241000218657 Picea Species 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 3
- 150000004056 anthraquinones Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000006396 nitration reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000005077 polysulfide Substances 0.000 description 3
- 229920001021 polysulfide Polymers 0.000 description 3
- 150000008117 polysulfides Polymers 0.000 description 3
- 235000018185 Betula X alpestris Nutrition 0.000 description 2
- 235000018212 Betula X uliginosa Nutrition 0.000 description 2
- 240000000731 Fagus sylvatica Species 0.000 description 2
- 235000010099 Fagus sylvatica Nutrition 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- CKDYLXCYEQVJHE-UHFFFAOYSA-N 1,2,6-trihydroxy-3-nitroanthracene-9,10-dione Chemical compound OC1=C([N+]([O-])=O)C=C2C(=O)C3=CC(O)=CC=C3C(=O)C2=C1O CKDYLXCYEQVJHE-UHFFFAOYSA-N 0.000 description 1
- SDICTISQCKLMEB-UHFFFAOYSA-N 1,4-diamino-5-nitroanthracene-9,10-dione Chemical compound O=C1C=2C(N)=CC=C(N)C=2C(=O)C2=C1C=CC=C2[N+]([O-])=O SDICTISQCKLMEB-UHFFFAOYSA-N 0.000 description 1
- OPZUWDAYFQMSMY-UHFFFAOYSA-N 1,5-dihydroxy-4,8-dinitro-9,10-dioxoanthracene-2,6-disulfonic acid Chemical compound C1=C(S(O)(=O)=O)C(O)=C2C(=O)C3=C([N+]([O-])=O)C=C(S(O)(=O)=O)C(O)=C3C(=O)C2=C1[N+]([O-])=O OPZUWDAYFQMSMY-UHFFFAOYSA-N 0.000 description 1
- CUIHODIOWPLCMG-UHFFFAOYSA-N 1,5-dihydroxy-4,8-dinitroanthracene-9,10-dione Chemical compound O=C1C2=C(O)C=CC([N+]([O-])=O)=C2C(=O)C2=C1C([N+]([O-])=O)=CC=C2O CUIHODIOWPLCMG-UHFFFAOYSA-N 0.000 description 1
- JHVMTWUDBADLCI-UHFFFAOYSA-N 1,8-dichloro-3-nitroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC([N+](=O)[O-])=CC(Cl)=C3C(=O)C2=C1Cl JHVMTWUDBADLCI-UHFFFAOYSA-N 0.000 description 1
- GJCHQJDEYFYWER-UHFFFAOYSA-N 1,8-dihydroxy-4,5-dinitroanthracene-9,10-dione Chemical compound O=C1C2=C([N+]([O-])=O)C=CC(O)=C2C(=O)C2=C1C([N+]([O-])=O)=CC=C2O GJCHQJDEYFYWER-UHFFFAOYSA-N 0.000 description 1
- MKBOTTRSSNRPPF-UHFFFAOYSA-N 1-amino-2,4-dinitroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C([N+]([O-])=O)=CC([N+]([O-])=O)=C2N MKBOTTRSSNRPPF-UHFFFAOYSA-N 0.000 description 1
- SSLUBNFUCQBYTP-UHFFFAOYSA-N 1-amino-4-nitro-9,10-dioxoanthracene-2-carboxylic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C([N+]([O-])=O)=CC(C(O)=O)=C2N SSLUBNFUCQBYTP-UHFFFAOYSA-N 0.000 description 1
- QQBJRPSLIUWNTI-UHFFFAOYSA-N 1-bromo-4-nitro-9,10-dioxoanthracene-2-sulfonic acid Chemical compound C1=CC=C2C(=O)C3=C(Br)C(S(=O)(=O)O)=CC([N+]([O-])=O)=C3C(=O)C2=C1 QQBJRPSLIUWNTI-UHFFFAOYSA-N 0.000 description 1
- AOCQSZUIFJHWNF-UHFFFAOYSA-N 1-bromo-4-nitroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(Br)=CC=C2[N+](=O)[O-] AOCQSZUIFJHWNF-UHFFFAOYSA-N 0.000 description 1
- NGQRAAQPTFAOQG-UHFFFAOYSA-N 1-chloro-2-nitroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=C(Cl)C([N+](=O)[O-])=CC=C3C(=O)C2=C1 NGQRAAQPTFAOQG-UHFFFAOYSA-N 0.000 description 1
- FHJIMXQVBSTKAF-UHFFFAOYSA-N 1-ethoxy-4-nitroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C([N+]([O-])=O)=CC=C2OCC FHJIMXQVBSTKAF-UHFFFAOYSA-N 0.000 description 1
- CYXGLGFQKSCUSV-UHFFFAOYSA-N 1-methyl-2-nitroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC([N+]([O-])=O)=C2C CYXGLGFQKSCUSV-UHFFFAOYSA-N 0.000 description 1
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- QBBPBRYGFOXJOB-UHFFFAOYSA-N 3,7-dihydroxy-4,8-dinitro-9,10-dioxoanthracene-2,6-disulfonic acid Chemical compound O=C1C2=CC(S(O)(=O)=O)=C(O)C([N+]([O-])=O)=C2C(=O)C2=C1C([N+]([O-])=O)=C(O)C(S(O)(=O)=O)=C2 QBBPBRYGFOXJOB-UHFFFAOYSA-N 0.000 description 1
- JTJMVZPSIKNOLB-UHFFFAOYSA-N 3-nitro-9,10-dioxoanthracene-2-carboxylic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=C(C(=O)O)C([N+]([O-])=O)=C2 JTJMVZPSIKNOLB-UHFFFAOYSA-N 0.000 description 1
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 1
- CZZFIABCNJUYFY-UHFFFAOYSA-N 8-chloro-5-nitro-9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C(C(=CC=C2Cl)[N+]([O-])=O)=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O CZZFIABCNJUYFY-UHFFFAOYSA-N 0.000 description 1
- 241000208140 Acer Species 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 241000219495 Betulaceae Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000726768 Carpinus Species 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000166124 Eucalyptus globulus Species 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- 244000305267 Quercus macrolepis Species 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- -1 amino, hydroxyl Chemical group 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000005338 nitrobenzoic acids Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- D21C3/22—Other features of pulping processes
- D21C3/222—Use of compounds accelerating the pulping processes
Definitions
- the invention relates to a method for delignifying lignocellulose materials with the addition of nitroanthraquinone compounds.
- a process has now been found for delignifying lignocellulose materials by digesting lignocellulose materials with conventional cooking liquids under conventional cooking conditions, which is characterized in that one or more nitroanthraquinone compounds are added.
- lignocellulose materials can be delignified using the method according to the invention.
- conifers such as spruce, pine and fir, hardwoods such as beech, birch, eucalyptus, aspen, poplar, willow, hornbeam, alder, oak and maple and straw and bagasse from annual plants are suitable.
- Spruce, pine, fir, birch and beech are preferably delignified by the method according to the invention.
- one or more nitroanthraquinone compounds are added to the cooking liquid.
- One of the usual cooking liquids for alkaline cooking processes or sulfite processes or similar processes can be used as the cooking liquid.
- alkaline cooking process includes various processes such as the soda process, the sulfate process, the polysulfide process and the like
- sulfite process as used herein includes various processes such as the alkaline, neutral and acidic sulfite process which Bisulfite processes and the like (see P. Lengyel, S.
- the additives according to the invention are preferably made to alkaline cooking liquids, as are used, for example, in the processes known as the soda process, sulfate process and polysulfide process.
- the additives according to the invention are very particularly preferably added to alkaline cooking liquids, such as are used in the process known as the soda process.
- the delignified material can be worked up in a customary manner, for example by displacing the cooking liquid from the lignocellulosic material by adding water or an aqueous liquid which is inert to the lignocellulosic material.
- the lignocellulose material processed in this way and optionally mechanically shredded can be used without further treatment or subjected to customary bleaching processes.
- the delignified lignocellulosic material can be further treated in the following way:
- the material is in an aqueous suspension, the content of which is 2 to 40% by weight of lignocellulosic material, at 2 to 20 for 0.5 to 60 minutes at 20 to 90 ° C Wt .-% of an alkali metal base, and then optionally treated with oxygen or an oxygen-containing gas for 0.5 to 120 minutes at a temperature of 80 to 150 ° C and an oxygen partial pressure of 1.4 to 14 kg / cm 2 .
- the lignocellulosic material used is made of wood, it is advantageous to convert it into chips first.
- nitroanthraquinone compounds can also be added to the lignocellulose material during the impregnation.
- nitroanthraquinone compounds act on the lignocellulose material in a pretreatment phase together with the digestion chemicals in the temperature range of about 90-150 ° C. leave that the lignin content is not substantially, ie less than 20%, and that the proportion of nitroanthraquinone compounds which has not penetrated into the lignocellulose material can be recovered if necessary.
- one or more nitroanthraquinone compounds are added to the digestion process.
- mono- and / or dinitroanthraquinones are suitable, which may optionally have one or more further substituents in addition to the nitro groups.
- further substituents are alkyl, alkoxy, halogen, amino, hydroxyl, carboxy and / or sulfo groups and / or fused iso- or heterocyclic rings.
- Preferred further substituents are alkyl and alkoxy groups each having 1 to 4 carbon atoms, and chloro and / or sulfo groups.
- the number of further substituents can be, for example, 1 to 6, preferably 1 to 4.
- nitroanthraquinone compounds to be added are: 1- and 2-nitroanthraquinone; 1,5-, 1,6-, 1,7-, 1,8-, 2,6- and 2,7-dinitroanthraquinone; 1-nitro-5-, 1-nitro-7-, 1-nitro-8-sulfo-anthraquinone; 1-nitro-4-chloro-5-sulfo-anthraquinone; 1-nitro-5-, 1-nitro-6-, 1-nitro-8-, 2-nitro-1-chloro-anthraquinone; 2-nitro-4,5-dichloro-anthraquinone; 2-nitro-1,4-, 1-nitro-5,8-diamino-anthraquinone; 1-nitro-4-amino-anthraquinone; 1,3-dinitro-4-amino-anthraquinone; 1-nitro-4-hydroxy anthraquinone; 1-nitro-3,4-, 1-nitro-5,8-, 1,5-dinitro
- 1- and 2-nitroanthraquinone 1,5-, 1,6-, 1,7-, 1,8-, 2,6- and 2,7-dinitroanthraquinone, 1-nitro-5-chloro-anthraquinone are preferred, 1-nitro-8-sulfo-anthraquinone, 1-nitro-4-amino-anthraquinone, 1-nitro-4-hydroxy-anthraquinone, 1-nitro-2-carboxy-anthraquinone, 1-nitro-5-ethoxy-anthraquinone and / or 2-methyl-1-nitro-anthraquinone, especially the aforementioned dinitro compounds.
- the aforementioned compounds can be added individually or in any mixtures with one another.
- mixtures which contain unsubstituted mono- and / or dinitroanthraquinones is particularly preferred.
- Such mixtures can be obtained, for example, in the industrial nitration of anthraquinone and / or mononitroanthraquinone.
- mixtures of mono- and / or dinitroanthraquinones can be used in the process according to the invention, which are obtained when anthraquinone is mono- or dinitrogenized on an industrial scale and / or mononitroanthraquinone mixtures are nitrated and, for example, the isomers important as dye intermediates from the products obtained, for example 1 Nitro, 1,5 and / or 1,8 dinitro anthraquinone.
- Particularly preferred mixtures for example contain from 0 to 3 wt .-% 1-Nitroanthrac h inon 5 to 12 wt .-% of 1,5-dinitroanthraquinone, 15 to 35 wt .-% of 1,6-dinitroanthraquinone , 15 to 35% by weight of 1,7-dinitroanthraquinone, 15 to 50% by weight of 1,8-dinitroanthraquinone, 0.5 to 3% by weight of 2,6-dinitroanthraquinone and 0.5 to 3% by weight .-% 2,7-dinitroanthraquinone.
- nitroanthraquinone compounds according to the invention can take place, for example, in amounts of 0.001 to 10% by weight, based on the lignocellulose material used. 0.01 to 1.0% by weight of the additives, based on lignocellulose material, are preferably used.
- the method according to the invention has the advantage that it leads to a substantial acceleration of delignification in the soda process. A significant acceleration is also observed in the sulfate process and polysulfide process.
- the process according to the invention has the further advantage that substances and mixtures of substances which have hitherto been undesirable by-products in the nitration of anthraquinone can be recycled in a technically advantageous manner.
- the increase in the delignification speed can be used in different ways depending on the circumstances.
- a predetermined kappa number can be reached in a shorter time, ie the capacity of an already installed pulp cooker can be expanded. However, it can also be digested at a lower maximum cooking temperature. Energy is saved in both cases.
- a reduced use of chemicals which in a known manner (see TAPPI, 50 (8), p. 400 (1967)) has a favorable effect on the reduced formation smelling by-products.
- TAPPI, 50 (8), p. 400 (1967) has a favorable effect on the reduced formation smelling by-products.
- the way in which these advantages can be optimally used depends on the circumstances of the pulp manufacturing process used.
- the process according to the invention also has a stabilizing effect on the cellulose, so that the cellulose can be obtained in a higher yield for a given kappa number.
Landscapes
- Paper (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Aufschliessen von Lignocellulose-Materialien unter üblichen Kochbedingungen mit üblichen Kochflüssigkeiten unter Zusatz von Nitroanthrachinon-Verbindungen.Digestion of lignocellulose materials under normal cooking conditions with conventional cooking liquids with the addition of nitroanthraquinone compounds.
Description
Die Erfindung betrifft ein Verfahren zur Delignifizierung von Lignocellulose-Materialien unter Zusatz von Nitro- anthrachinon-Verbindungen.The invention relates to a method for delignifying lignocellulose materials with the addition of nitroanthraquinone compounds.
In Svensk Papperstidning 71, S. 857-863 (1968) ist beschrieben, daß Nitrobenzol und Nitrobenzoesäuren eine inhibierende Wirkung auf die alkalische Kettenkürzungsreaktion bei der Delignifizierung haben. In der gleichen Literaturstelle ist angegeben, daß diese Erkenntnisse sich nicht in einer technischen Anwendung durchgesetzt haben.Svensk Papperstidning 71, pp. 857-863 (1968) describes that nitrobenzene and nitrobenzoic acids have an inhibitory effect on the alkaline chain shortening reaction in the delignification. In the same literature reference it is stated that these findings have not become established in a technical application.
Es wurde nun ein Verfahren zur Delignifizierung von Lignocellulose-Materialien durch Aufschließen von Lignocellulose-Materialien mit üblichen Kochflüssigkeiten bei üblichen Kochbedingungen gefunden, das dadurch gekennzeichnet ist, daß man eine oder mehrere Nitroanthrachinon-Verbindungen zusetzt.A process has now been found for delignifying lignocellulose materials by digesting lignocellulose materials with conventional cooking liquids under conventional cooking conditions, which is characterized in that one or more nitroanthraquinone compounds are added.
Nach dem erfindungsgemäßen Verfahren können die verschiedensten Lignocellulose-Materialien delignifiziert werden. Beispielsweise sind Nadelhölzer, wie Fichte, Kiefer und Tanne, Laubhölzer, wie Buche, Birke, Eucalyptus, Espe, Pappel, Weide, Hainbuche, Erle, Eiche und Ahorn und Stroh und Bagasse von Einjahrespflanzen geeignet. Vorzugsweise werden nach dem erfindungsgemäßen Verfahren Fichte, Kiefer, Tanne, Birke und Buche delignifiziert.A wide variety of lignocellulose materials can be delignified using the method according to the invention. For example, conifers such as spruce, pine and fir, hardwoods such as beech, birch, eucalyptus, aspen, poplar, willow, hornbeam, alder, oak and maple and straw and bagasse from annual plants are suitable. Spruce, pine, fir, birch and beech are preferably delignified by the method according to the invention.
Beim erfindungsgemäßen Verfahren zur Delignifizierung von Lignocellulosematerialien wird der Kochflüssigkeit eine odere mehrere Nitroanthrachinon-Verbindungen zugesetzt. Als Kochflüssigkeit kann eine der üblichen KochFlüssigkeiten für alkalische Kochverfahren oder Sulfit- Verfahren oder ähnliche Verfahren verwendet werden. Der Begriff "alkalische Kochverfahren" umfaßt verschiedene Verfahren, beispielsweise das Soda-Verfahren, das SulfatVerfahren, das Polysulfid-Verfahren und ähnliche, und der hier verwendete Begriff "Sulfit-Verfahren" umfaßt verschiedene Verfahren, beispielsweise das alkalische, neutrale und saure Sulfitverfahren, das Bisulfitverfahren und ähnliche (s. P. Lengyel, S. Morvay, Chemie und Technologie der Zellstoffherstellung, Güntter-Staib Verlag, Biberach/Riss, 1973, Seiten 62 ff). Bevorzugt erfolgen die erfindungsgemäßen Zusätze zu alkalischen Kochflüssigkeiten, wie sie beispielsweise in den als Sodaprozeß, Sulfatprozeß und Polysulfidprozeß bekannten Verfahren verwendet werden. Ganz besonders bevorzugt erfolgen die erfindungsgemäßen Zusätze zu alkalischen Kochflüssigkeiten, wie sie in dem als Sodaprozeß bekannten Verfahren verwendet werden.In the process according to the invention for delignifying lignocellulosic materials, one or more nitroanthraquinone compounds are added to the cooking liquid. One of the usual cooking liquids for alkaline cooking processes or sulfite processes or similar processes can be used as the cooking liquid. The term "alkaline cooking process" includes various processes such as the soda process, the sulfate process, the polysulfide process and the like, and the term "sulfite process" as used herein includes various processes such as the alkaline, neutral and acidic sulfite process which Bisulfite processes and the like (see P. Lengyel, S. M orvay, Chemistry and Technology of Pulp Production, Güntter-Staib Verlag, Biberach / Riss, 1973, pages 62 ff). The additives according to the invention are preferably made to alkaline cooking liquids, as are used, for example, in the processes known as the soda process, sulfate process and polysulfide process. The additives according to the invention are very particularly preferably added to alkaline cooking liquids, such as are used in the process known as the soda process.
Beispielsweise kann man das erfindungsgemäße Verfahren in einem geschlossenen Reaktionsgefäß durchführen, in dem das Lignocellulose-Material mit der Kochflüssigkeit bei Maximaltemperaturen im Bereich von 150 bis 200°C, vorzugsweise von 160 bis 180°C, über einen Zeitraum von 0,5 bis 480 Minuten, vorzugsweise von 15 bis 200 Minuten. behandelt wird.For example, one can perform the inventive method in a closed reaction vessel in which the lignocellulosic material with the cooking liquor at maximum temperatures in the range of 150 to 200 ° C, preferably from 160 to 180 ° C, over a period of 0, 5 to 48 0 Minutes, preferably from 15 to 200 minutes. is treated.
Nach dieser Aufschlußbehandlung kann das delignifizierte Material auf übliche Weise aufgearbeitet werden, beispielsweise indem man die Kochflüssigkeit vom Lignocellulosematerial verdrängt durch Zugabe von Wasser oder einer wäßrigen, gegenüber dem Lignocellulosematerial inerten Flüssigkeit. Das so bearbeitete und gegebenenfalls zusätzlich mechanisch zerfaserte Lignocellulose- material kann ohne weitere Behandlung verwendet oder üblichen Bleichverfahren unterworfen werden.After this digestion treatment, the delignified material can be worked up in a customary manner, for example by displacing the cooking liquid from the lignocellulosic material by adding water or an aqueous liquid which is inert to the lignocellulosic material. The lignocellulose material processed in this way and optionally mechanically shredded can be used without further treatment or subjected to customary bleaching processes.
Alternativ kann das delignifizierte Lignocellulosematerial auf folgende Weise weiter behandelt werden: Das Material wird in einer wäßrigen Suspension, deren Gehalt an Lignocellulosematerial 2 bis 40 Gew.-% beträgt, während 0,5 bis 60 Minuten bei 20 bis 90°C mit 2 bis 20 Gew.-% einer Alkalimetallbase, und gegebenenfalls anschließend mit Sauerstoff oder einem sauerstoffhaltigen Gas während 0,5 bis 120 Minuten bei einer Temperatur von 80 bis 150°C und einem Sauerstoffpartialdruck von 1,4 bis 14 kg/cm2 behandelt.Alternatively, the delignified lignocellulosic material can be further treated in the following way: The material is in an aqueous suspension, the content of which is 2 to 40% by weight of lignocellulosic material, at 2 to 20 for 0.5 to 60 minutes at 20 to 90 ° C Wt .-% of an alkali metal base, and then optionally treated with oxygen or an oxygen-containing gas for 0.5 to 120 minutes at a temperature of 80 to 150 ° C and an oxygen partial pressure of 1.4 to 14 kg / cm 2 .
Wenn das eingesetzte Lignocellulosematerial aus Holz besteht ist es vorteilhaft, dieses zunächst in Schnitzel überzuführen.If the lignocellulosic material used is made of wood, it is advantageous to convert it into chips first.
Die Nitroanthrachinonverbindungen können dem Lignocellulosematerial auch schon während der Imprägnierung zugesetzt werden.The nitroanthraquinone compounds can also be added to the lignocellulose material during the impregnation.
Es kann auch vorteilhaft sein, Nitroanthrachinonverbindungen auf das Lignocellulosematerial in einer Vorbehandlungsphase zusammen mit den Aufschlußchemikalien in dem Temperaturbereich von etwa 90 - 150°C derart einwirken zu lassen, daß der Ligningehalt nicht wesentlich, d.h. zu weniger als 20 % in Lösung gebracht wird und daß gegebenenfalls der nicht in das Lignocellulosematerial eingedrungene Anteil an Nitroanthrachinonverbindungen zurückgewonnen werden kann.It can also be advantageous to have nitroanthraquinone compounds act on the lignocellulose material in a pretreatment phase together with the digestion chemicals in the temperature range of about 90-150 ° C. leave that the lignin content is not substantially, ie less than 20%, and that the proportion of nitroanthraquinone compounds which has not penetrated into the lignocellulose material can be recovered if necessary.
Erfindungsgemäß werden in das Aufschlußverfahren eine oder mehrere Nitroanthrachinonverbindungen zugesetzt. Hierfür kommen beispielsweise Mono- und/oder Dinitroanthrachinone in Frage, die gegebenenfalls zusätzlich zu den Nitrogruppen einen oder mehrere weitere Substituenten aufweisen können. Als weitere Substituenten kommen beispielsweise Alkyl-, Alkoxy-, Halogen-, Amino-, Hydroxy-, Carboxy- und/oder Sulfogruppen und/oder annelierte iso- oder heterocyclische Ringe in Frage. Bevorzugt als weitere Substituenten sind Alkyl- und Alkoxygruppen mit je 1 bis 4 C-Atomen, sowie Chloro- und/oder Sulfogruppen. Die Anzahl der weiteren Substituenten kann beispielsweise 1 bis 6, vorzugsweise 1 bis 4, sein. Beispiele für zuzusetzende Nitroanthrachinon-Verbindungen sind: 1- und 2-Nitroanthrachinon; 1,5-, 1,6-, 1,7-, 1,8-, 2,6- und 2,7-Dinitroanthrachinon; 1-Nitro-5-, 1-Nitro-7-, 1-Nitro-8-sulfo-anthrachinon; 1-Nitro-4-chlor-5-sulfo- anthrachinon; 1-Nitro-5-, 1-Nitro-6-, 1-Nitro-8-, 2-Nitro-1-chlor-anthrachinon; 2-Nitro-4,5-dichlor-anthrachinon; 2-Nitro-1,4-, 1-Nitro-5,8-diamino-anthrachinon; 1-Nitro-4-amino-anthrachinon; 1,3-Dinitro-4-amino-anthrachinon; 1-Nitro-4-hyroxy-anthrachinon; 1-Nitro-3,4-, 1-Nitro-5,8-, 1,5-Dinitro-4,8-dihydroxy-anthrachinon; 1,5-Dinitro-4,8-dihydroxy-3,7-disulfo-anthrachinon; 1,8-Dinitro-4,5-dihydroxy-anthrachinon; 1,5-Dinitro-2,6-dihydroxy-3,7-disulfo-anthrachinon; 2-Nitro-3,4,7-tri- hydroxy-anthrachinon; 1-Nitro-4-ethoxy-anthrachinon; 1-Nitro-2-, 2-Nitro-3-carboxy-anthrachinon; 1-Nitro-3-carboxy-4-amino-anthrachinon, 4,4'-Dinitro-1,1'-dian- thrimid; 1-Nitro-4-, 2-Nitro-1-methyl-anthrachinon; 1-Nitro-4-brom-anthrachinon; 1-Nitro-3-sulfo-4-brom-anthrachinon und 1-Nitro-5-ethoxy-anthrachinon.According to the invention, one or more nitroanthraquinone compounds are added to the digestion process. For this purpose, for example, mono- and / or dinitroanthraquinones are suitable, which may optionally have one or more further substituents in addition to the nitro groups. Examples of further substituents are alkyl, alkoxy, halogen, amino, hydroxyl, carboxy and / or sulfo groups and / or fused iso- or heterocyclic rings. Preferred further substituents are alkyl and alkoxy groups each having 1 to 4 carbon atoms, and chloro and / or sulfo groups. The number of further substituents can be, for example, 1 to 6, preferably 1 to 4. Examples of nitroanthraquinone compounds to be added are: 1- and 2-nitroanthraquinone; 1,5-, 1,6-, 1,7-, 1,8-, 2,6- and 2,7-dinitroanthraquinone; 1-nitro-5-, 1-nitro-7-, 1-nitro-8-sulfo-anthraquinone; 1-nitro-4-chloro-5-sulfo-anthraquinone; 1-nitro-5-, 1-nitro-6-, 1-nitro-8-, 2-nitro-1-chloro-anthraquinone; 2-nitro-4,5-dichloro-anthraquinone; 2-nitro-1,4-, 1-nitro-5,8-diamino-anthraquinone; 1-nitro-4-amino-anthraquinone; 1,3-dinitro-4-amino-anthraquinone; 1-nitro-4-hydroxy anthraquinone; 1-nitro-3,4-, 1-nitro-5,8-, 1,5-dinitro-4,8-dihydroxyanthraquinone; 1,5-dinitro-4,8-dihydroxy-3,7-disulfo-anthraquinone; 1,8-dinitro-4,5-dihydroxyanthraquinone; 1,5-dinitro-2,6-dihydroxy-3,7-disulfo-anthraquinone; 2-nitro-3,4,7-tri-hydroxyanthraquinone; 1-nitro-4-ethoxy-anthraquinone; 1-nitro-2-, 2-nitro-3-carboxy-anthraquinone; 1-nitro-3-carboxy-4-amino-anthraquinone, 4,4'-dinitro-1,1'-dianhrimide; 1-nitro-4-, 2-nitro-1-methylanthraquinone; 1-nitro-4-bromo-anthraquinone; 1-nitro-3-sulfo-4-bromo-anthraquinone and 1-nitro-5-ethoxy-anthraquinone.
Es ist auch möglich, anstelle der Nitroanthrachinonverbindungen oder zusätzlich die partiell kernhydrierten Derivate von Nitroanthrachinonverbindungen und/oder deren tautomere Formen einzusetzen.It is also possible to use the partially nuclear hydrogenated derivatives of nitroanthraquinone compounds and / or their tautomeric forms instead of the nitroanthraquinone compounds or in addition.
Bevorzugt werden 1- und 2-Nitroanthrachinon, 1,5-, 1,6-, 1,7-, 1,8-, 2,6- und 2,7-Dinitroanthrachinon, 1-Nitro-5-chlor-anthrachinon, 1-Nitro-8-sulfo-anthrachinon, 1-Nitro-4-amino-anthrachinon, 1-Nitro-4-hydroxy-anthrachinon, 1-Nitro-2-carboxy-anthrachinon, 1-Nitro-5-ethoxy-anthrachinon und/oder 2-Methyl-l-nitro-anthrachinon, insbesondere die vorgenannten Dinitroverbindungen, zugesetzt.1- and 2-nitroanthraquinone, 1,5-, 1,6-, 1,7-, 1,8-, 2,6- and 2,7-dinitroanthraquinone, 1-nitro-5-chloro-anthraquinone are preferred, 1-nitro-8-sulfo-anthraquinone, 1-nitro-4-amino-anthraquinone, 1-nitro-4-hydroxy-anthraquinone, 1-nitro-2-carboxy-anthraquinone, 1-nitro-5-ethoxy-anthraquinone and / or 2-methyl-1-nitro-anthraquinone, especially the aforementioned dinitro compounds.
Die vorgenannten Verbindungen können jeweils für sich alleine oder in beliebigen Mischungen untereinander zugesetzt werden.The aforementioned compounds can be added individually or in any mixtures with one another.
Besonders bevorzugt ist der Zusatz von Mischungen, die nicht weiter substituierte Mono- und/oder Dinitroanthrachinone enthalten. Solche Mischungen können beispielsweise bei der technischen Nitrierung von Anthrachinon und/oder Mononitroanthrachinon erhalten werden. Insbesondere können in das erfindungsgemäße Verfahren Mischungen von Mono- und/oder Dinitroanthrachinonen eingesetzt werden, die anfallen, wenn man Anthrachinon in technischem Maßstab mono- oder dinitriert und/oder Mononitroanthrachinongemische nitriert und aus den dabei anfallenden Produkten beispielsweise die als Farbstoffzwischenprodukte wichtigen Isomeren, z.B. 1-Nitro-, 1,5-und/oder 1,8-Dinitro-anthrachinon, abtrennt. Die letztgenannten Mischungen, die als wesentliche Bestandteile z.B. 1,5-, 1,6-, 1,7-, 1,8-, 2,6- und/oder 2,7-Dinitro-anthrachinon enthalten können, stellten bisher unerwünschte Nebenprodukte bei der Anthrachinon-Nitrierung dar. Insbesondere bevorzugte Mischungen enthalten beispielsweise 0 bis 3 Gew.-% 1-Nitroanthrachinon, 5 bis 12 Gew.-% 1,5-Dinitroanthrachinon, 15 bis 35 Gew.-% 1,6-Dinitroanthrachinon, 15 bis 35 Gew.-% 1,7-Dinitroanthrachinon, 15 bis 50 Gew.-% 1,8-Dinitro- anthrachinon, 0,5 bis 3 Gew.-% 2,6-Dinitroanthrachinon und 0,5 bis 3 Gew.-% 2,7-Dinitroanthrachinon.The addition of mixtures which contain unsubstituted mono- and / or dinitroanthraquinones is particularly preferred. Such mixtures can be obtained, for example, in the industrial nitration of anthraquinone and / or mononitroanthraquinone. In particular, mixtures of mono- and / or dinitroanthraquinones can be used in the process according to the invention, which are obtained when anthraquinone is mono- or dinitrogenized on an industrial scale and / or mononitroanthraquinone mixtures are nitrated and, for example, the isomers important as dye intermediates from the products obtained, for example 1 Nitro, 1,5 and / or 1,8 dinitro anthraquinone. The last-mentioned mixtures, which may contain, for example, 1,5-, 1,6-, 1,7-, 1,8-, 2,6- and / or 2,7-dinitroanthraquinone as essential constituents, have so far been undesirable by-products in the anthraquinone-nitration. Particularly preferred mixtures for example contain from 0 to 3 wt .-% 1-Nitroanthrac h inon 5 to 12 wt .-% of 1,5-dinitroanthraquinone, 15 to 35 wt .-% of 1,6-dinitroanthraquinone , 15 to 35% by weight of 1,7-dinitroanthraquinone, 15 to 50% by weight of 1,8-dinitroanthraquinone, 0.5 to 3% by weight of 2,6-dinitroanthraquinone and 0.5 to 3% by weight .-% 2,7-dinitroanthraquinone.
Die erfindungsgemäßen Zusätze von Nitroanthrachinon- Verbindungen können beispielsweise in Mengen von 0,001 bis 10 Gew.-% erfolgen, bezogen auf eingesetztes Lignocellulose-Material. Vorzugsweise werden 0,01 bis 1,0 Gew.-% der Zusätze, bezogen auf Lignocellulose-Material, eingesetzt.The additions of nitroanthraquinone compounds according to the invention can take place, for example, in amounts of 0.001 to 10% by weight, based on the lignocellulose material used. 0.01 to 1.0% by weight of the additives, based on lignocellulose material, are preferably used.
Das erfindungsgemäße Verfahren hat den Vorteil, daß es zu einer wesentlichen Beschleunigung der Delignifizierung im Sodaprozeß führt. Auch beim Sulfatprozeß und Polysulfidprozeß wird eine deutliche Beschleunigung beobachtet. Das erfindungsgemäße Verfahren hat weiterhin den Vorteil, daß bisher als unerwünschte Nebenprodukte bei der Nitrierung von Anthrachinon anfallende Stoffe und Stoffgemische einer technisch vorteilhaften Verwertung zugeführt werden können.The method according to the invention has the advantage that it leads to a substantial acceleration of delignification in the soda process. A significant acceleration is also observed in the sulfate process and polysulfide process. The process according to the invention has the further advantage that substances and mixtures of substances which have hitherto been undesirable by-products in the nitration of anthraquinone can be recycled in a technically advantageous manner.
Die Vergrößerung der Delignifiziergeschwindigkeit kann je nach den Gegebenheiten in unterschiedlicher Weise genutzt werden. Eine vorgegebene Kappa-Zahl kann z.B. in kürzerer Zeit erreicht, d.h. die Kapazität eines bereits installierten Zellstoff-Kochers erweitert werden. Es kann aber auch bei erniedrigter maximaler Kochtemperatur aufgeschlossen werden. In beiden Fällen wird Energie eingespart. Anstelle einer Verkürzung der Kochzeit und/oder einer Erniedrigung der maximalen Kochtemperatur kann auch mit einem verminderten Chemikalieneinsatz gearbeitet werden, was sich in bekannter Weise (s. TAPPI, 50(8), S. 400 (1967)) günstig auf die verringerte Bildung stark riechender Nebenprodukte auswirkt. In welcher Weise diese Vorteile im Einzelfall optimal genutzt werden können hängt von den Gegebenheiten des angewendeten Zellstoffherstellungsverfahrens ab.The increase in the delignification speed can be used in different ways depending on the circumstances. A predetermined kappa number can be reached in a shorter time, ie the capacity of an already installed pulp cooker can be expanded. However, it can also be digested at a lower maximum cooking temperature. Energy is saved in both cases. Instead of shortening the cooking time and / or lowering the maximum cooking temperature, it is also possible to work with a reduced use of chemicals, which in a known manner (see TAPPI, 50 (8), p. 400 (1967)) has a favorable effect on the reduced formation smelling by-products. The way in which these advantages can be optimally used depends on the circumstances of the pulp manufacturing process used.
Außer der Beschleunigung der Delignifizierung wird mit dem erfindungsgemäßen Verfahren eine stabilisierende Wirkung auf die Cellulose erzielt, so daß bei gegebener Kappa-Zahl der Zellstoff in höherer Ausbeute erhalten werden kann.In addition to accelerating delignification, the process according to the invention also has a stabilizing effect on the cellulose, so that the cellulose can be obtained in a higher yield for a given kappa number.
Schnitzel von Fichtenholz wurden in einem Laborkocher mit einer Sodakochlauge aufgeschlossen, die 22 % aktives Alkali enthielt (bezogen auf das Gewicht des Holzes). Das Verhältnis von Flüssigkeit zu Holz betrug 4:1, die Ankochzeit 60 Minuten, die Fertigkochzeit bei 175°C 80 Minuten (Aufschluß A). In gleicher Weise wurde ein weiterer Aufschluß durchgeführt (Aufschluß B), bei dem jedoch dem Gemisch aus Holz und Kochlauge 0,1 Gew.-% (bezogen auf ofentrockenes Holz) einer Dinitroanthrachinonmischung folgender Zusammensetzung zugesetzt wurde:
- 30,7 Gew.-% 1,8-Dinitroanthrachinon
- 27,1 Gew.-% 1,6-Dinitroanthrachinon
- 23,0 Gew.-% 1,7-Dinitroanthrachinon
- 10,0 Gew.-% 1,5-Dinitroanthrachinon
- 1,1 Gew.-% 2,7-Dinitroanthrachinon
- 1,0 Gew.-% 2,6-Dinitroanthrachinon
- 0,7 Gew.-% 1-Nitroanthrachinon
- 6,4 Gew.-% sonstige Nitroanthrachinonderivate.
- 30.7% by weight 1,8-dinitroanthraquinone
- 27.1% by weight 1,6-dinitroanthraquinone
- 23.0% by weight of 1,7-dinitroanthraquinone
- 10.0% by weight 1,5-dinitroanthraquinone
- 1.1 wt% 2,7-dinitroanthraquinone
- 1.0 wt% 2,6-dinitroanthraquinone
- 0.7% by weight 1-nitroanthraquinone
- 6.4% by weight of other nitroanthraquinone derivatives.
Bei diesen Aufschlüssen wurden folgende Ergebnisse erhalten:
- a) Schnitzel von Fichtenholz wurden in einer Sodakochlauge aufgeschlossen,.die 22 % aktives Alkali enthielt (bezogen auf das Gewicht des Holzes). Das Verhältnis von Flüssigkeit zu Holz betrug 4:1, die Ankochzeit 60 Minuten, die Fertigkochzeit bei 175°C 116 Minuten. Bei diesem Aufschluß betrug die Zellstoffausbeute 51,5 % bei einer Kappa-Zahl von 67.a) Chips of spruce wood were digested in a soda liquor containing 22% active alkali (based on the weight of the wood). The ratio of liquid to wood was 4: 1, the boil-up time was 60 minutes, the finished boil-off time at 175 ° C was 116 minutes. With this digestion, the pulp yield was 51.5% with a kappa number of 67.
- b) Es wurde verfahren wie bei a), jedoch wurde der Kochlauge 0,1 Gew.-% (bezogen auf ofentrockenes Holz) der in Beispiel 1 beschriebenen Dinitroanthrachinonmischung zugefügt. Bei diesem Aufschluß wurde eine Kappa-Zahl von 67 bereits nach einer Fertigkochzeit von 56 Minuten bei 175°C erzielt. Die Zellstoffausbeute betrug 53,6 %.b) The procedure was as in a), but 0.1% by weight (based on oven-dry wood) of the dinitroanthraquinone mixture described in Example 1 was added to the cooking liquor. In this digestion, a kappa number of 67 was achieved after a final cooking time of 56 minutes at 175 ° C. The pulp yield was 53.6%.
- a) Es wurde verfahren wie in Beispiel 2 a).a) The procedure was as in Example 2 a).
- b) Es wurde verfahren wie in Beispiel 2 b). Die Ausbeute von 51,5 % Zellstoff wurde bereits nach 86 Minuten Fertigkochzeit bei 175°C erzielt. Die Kappa-Zahl lag bei 53.b) The procedure was as in Example 2 b). The yield of 51.5% pulp was achieved after 86 minutes of cooking at 175 ° C. The kappa number was 53.
- a) Schnitzel von Fichtenholz wurden in einem Laborzellstoffkocher einem Sulfataufschluß unterworfen. Das Verhältnis von Kochlauge zu Holz betrug 4:1. Die Kochlauge enthielt 17,5 % effektives Alkali bei einer Sulfidität von 47 %. Die Ankochzeit betrug 60 Minuten, die Fertigkochzeit bei 175°C 40 Minuten. Die Zellstoffausbeute betrug 53,7 %, die Kappa-Zahl 54.a) Chips of spruce wood were subjected to sulfate digestion in a laboratory pulp cooker. The ratio of cooking liquor to wood was 4: 1. The cooking liquor contained 17.5% effective alkali with a sulfidity of 47%. The cooking time was 60 minutes, the finished cooking time at 175 ° C 40 minutes. The pulp yield was 53.7% and the kappa number 54.
-
b) In einem weiteren Aufschluß entsprechend a) wurde unter den selben Bedingungen gearbeitet, der Kochlauge wurden jedoch 0,1 Gew.-% (bezogen auf ofentrockenes Holz) eines Dinitroanthrachinongemisches folgender Zusammensetzung zugefügt:
- 33,0 Gew.-% 1,6-Dinitroanthrachinon
- 21,7 Gew.-% 1,8-Dinitroanthrachinon
- 21,6 Gew.-% 1,7-Dinitroanthrachinon
- 6,5 Gew.-% 1,5-Dinitroanthrachinon
- 1,9 Gew.-% 2,6-Dinitroanthrachinon
- 1,8 Gew.-% 2,7-Dinitroanthrachinon
- 1,4 Gew.-% 1-Nitroanthrachinon.
Nach einer Fertigkochzeit von 40 Minuten bei 175°C wurde eine Zellstoffausbeute von 52,4 % erhalten bei einer Kappa-Zahl von 46.b) In a further digestion in accordance with a), the same conditions were used, but 0.1% by weight (based on oven-dry wood) of a dinitroanthraquinone mixture of the following composition was added to the cooking liquor:- 33.0% by weight 1,6-dinitroanthraquinone
- 21.7% by weight 1,8-dinitroanthraquinone
- 21.6% by weight 1,7-dinitroanthraquinone
- 6.5% by weight 1,5-dinitroanthraquinone
- 1.9 wt% 2,6-dinitroanthraquinone
- 1.8 wt% 2,7-dinitroanthraquinone
- 1.4% by weight 1-nitroanthraquinone.
After a final cooking time of 40 minutes at 175 ° C, a pulp yield of 52.4% was obtained with a kappa number of 46.
- a) Schnitzel von Fichtenholz wurden bei einem Verhältnis von Kochlauge zu Holz von 4:1 einem Aufschluß nach dem Sulfatverfahren unterworfen. Das effektive Alkali, bezogen auf das Gewicht des Holzes, betrug 17,5 %, die Sulfidität 47 %. Nach einer-Ankochzeit von 60 Minuten und einer Fertigkochzeit von 45 Minuten bei 175°C wurde eine Zellstoffausbeute von 52,7 % bei einer Kappa-Zahl von 48 erzielt.a) Wood chips from spruce wood were subjected to a digestion according to the sulfate process at a ratio of cooking liquor to wood of 4: 1. The effective alkali, based on the weight of the wood, was 17.5%, the sulfidity 47%. After a cooking time of 60 minutes and a final cooking time of 45 minutes at 175 ° C., a pulp yield of 52.7% achieved with a kappa number of 48.
- b) Bei einem weiteren Aufschluß wurde entsprechend a) verfahren, jedoch wurden, bezogen auf ofentrockenes Holz, 0,1 Gew.-% des in Beispiel 4 angegebenen Gemisches von Dinitroanthrachinonen zugesetzt. Eine Kappa-Zahl von 48 wurde bereits nach 39 Minuten Fertigkochzeit bei 175°C erzielt. Die Zellstoffausbeute betrug 52,7 %.b) In a further digestion, the procedure was as in a), but, based on oven-dry wood, 0.1% by weight of the mixture of dinitroanthraquinones given in Example 4 was added. A kappa number of 48 was achieved after just 39 minutes of cooking at 175 ° C. The pulp yield was 52.7%.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT80103278T ATE2279T1 (en) | 1979-06-25 | 1980-06-12 | PROCESSES FOR DELIGNIFICATION OF LIGNOCELLULOSIC MATERIALS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2925544 | 1979-06-25 | ||
| DE19792925544 DE2925544A1 (en) | 1979-06-25 | 1979-06-25 | METHOD FOR DELIGNIFYING LIGNOCELLULOSE MATERIALS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0021264A1 true EP0021264A1 (en) | 1981-01-07 |
| EP0021264B1 EP0021264B1 (en) | 1983-01-19 |
Family
ID=6074073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP80103278A Expired EP0021264B1 (en) | 1979-06-25 | 1980-06-12 | Process for the delignification of lignocellulosic materials |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US4350566A (en) |
| EP (1) | EP0021264B1 (en) |
| JP (1) | JPS568403A (en) |
| AT (1) | ATE2279T1 (en) |
| AU (1) | AU5932980A (en) |
| BR (1) | BR8003938A (en) |
| CA (1) | CA1154208A (en) |
| DE (2) | DE2925544A1 (en) |
| ES (1) | ES8103227A1 (en) |
| FI (1) | FI72541C (en) |
| NO (1) | NO155585C (en) |
| NZ (1) | NZ194113A (en) |
| ZA (1) | ZA803766B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5728265A (en) * | 1995-06-12 | 1998-03-17 | Henkel Corporation | Process for enhancing white liquor penetration into wood chips by contacting the chips with a mixture of the white liquor and a polymethylalkyl siloxane |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1449828A (en) * | 1973-04-26 | 1976-09-15 | Canadian Ind | Oxygen pulping process |
| JPS5143403A (en) * | 1974-10-09 | 1976-04-14 | Honshu Paper Co Ltd | Arukariparupuno seizohoho |
| US4036080A (en) * | 1974-11-29 | 1977-07-19 | The Garrett Corporation | Multi-rim flywheel |
| CA1073161A (en) * | 1975-09-05 | 1980-03-11 | Canadian Industries Limited | Delignification process |
| JPS5845562B2 (en) * | 1976-07-21 | 1983-10-11 | 株式会社日立製作所 | Vibration status display control method for turbines, etc. |
| CA1097463A (en) * | 1976-12-13 | 1981-03-17 | Naphtali N. Vanderhoek | Pulping processes |
| US4036680A (en) * | 1976-12-14 | 1977-07-19 | Canadian Industries, Ltd. | Delignification of lignocellulosic material with a soda pulping liquor containing a Diels Alder adduct of benzoquinone or naphthoquinone in admixture with a nitro aromatic compound |
| CA1094264A (en) * | 1976-12-14 | 1981-01-27 | Canadian Industries Limited | Delignification of lignocellulosic material with a soda liquor containing a cyclic keto compound and a nitro aromatic compound |
| JPS54100332A (en) * | 1978-01-20 | 1979-08-08 | Nippon Steel Chem Co Ltd | Quinone compound composition and its preparation |
-
1979
- 1979-06-25 DE DE19792925544 patent/DE2925544A1/en not_active Withdrawn
-
1980
- 1980-06-11 NO NO801742A patent/NO155585C/en unknown
- 1980-06-12 DE DE8080103278T patent/DE3061673D1/en not_active Expired
- 1980-06-12 AT AT80103278T patent/ATE2279T1/en active
- 1980-06-12 EP EP80103278A patent/EP0021264B1/en not_active Expired
- 1980-06-17 AU AU59329/80A patent/AU5932980A/en not_active Abandoned
- 1980-06-23 NZ NZ194113A patent/NZ194113A/en unknown
- 1980-06-23 JP JP8413180A patent/JPS568403A/en active Granted
- 1980-06-23 CA CA000354580A patent/CA1154208A/en not_active Expired
- 1980-06-23 FI FI802001A patent/FI72541C/en not_active IP Right Cessation
- 1980-06-24 ZA ZA00803766A patent/ZA803766B/en unknown
- 1980-06-24 BR BR8003938A patent/BR8003938A/en unknown
- 1980-06-25 ES ES492781A patent/ES8103227A1/en not_active Expired
-
1981
- 1981-04-27 US US06/257,842 patent/US4350566A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6258362B2 (en) | 1987-12-05 |
| JPS568403A (en) | 1981-01-28 |
| ES492781A0 (en) | 1981-02-16 |
| FI72541B (en) | 1987-02-27 |
| BR8003938A (en) | 1981-01-27 |
| NZ194113A (en) | 1982-06-29 |
| ES8103227A1 (en) | 1981-02-16 |
| FI72541C (en) | 1987-06-08 |
| DE3061673D1 (en) | 1983-02-24 |
| ZA803766B (en) | 1981-07-29 |
| US4350566A (en) | 1982-09-21 |
| FI802001A7 (en) | 1980-12-26 |
| EP0021264B1 (en) | 1983-01-19 |
| NO801742L (en) | 1980-12-29 |
| DE2925544A1 (en) | 1981-01-22 |
| NO155585B (en) | 1987-01-12 |
| CA1154208A (en) | 1983-09-27 |
| ATE2279T1 (en) | 1983-02-15 |
| AU5932980A (en) | 1981-01-08 |
| NO155585C (en) | 1987-04-22 |
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