CN109653012A - A method of dissolving pulp is prepared using stalk or energy-source plant - Google Patents
A method of dissolving pulp is prepared using stalk or energy-source plant Download PDFInfo
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- CN109653012A CN109653012A CN201710947155.XA CN201710947155A CN109653012A CN 109653012 A CN109653012 A CN 109653012A CN 201710947155 A CN201710947155 A CN 201710947155A CN 109653012 A CN109653012 A CN 109653012A
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- China
- Prior art keywords
- raw material
- solid
- dissolving pulp
- preg
- acid
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- 229920000875 Dissolving pulp Polymers 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 64
- 238000012545 processing Methods 0.000 claims abstract description 40
- 229920002678 cellulose Polymers 0.000 claims abstract description 38
- 239000001913 cellulose Substances 0.000 claims abstract description 38
- 239000003513 alkali Substances 0.000 claims abstract description 35
- 238000002360 preparation method Methods 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000010902 straw Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims description 55
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 48
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 44
- 239000000047 product Substances 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 26
- 239000002002 slurry Substances 0.000 claims description 26
- 238000004061 bleaching Methods 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 23
- 239000004094 surface-active agent Substances 0.000 claims description 23
- 235000019253 formic acid Nutrition 0.000 claims description 22
- 239000012752 auxiliary agent Substances 0.000 claims description 21
- 239000000835 fiber Substances 0.000 claims description 20
- 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 description 19
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 16
- 241000196324 Embryophyta Species 0.000 claims description 16
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 16
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 16
- 239000001630 malic acid Substances 0.000 claims description 16
- 235000011090 malic acid Nutrition 0.000 claims description 16
- 239000004155 Chlorine dioxide Substances 0.000 claims description 13
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 13
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 12
- -1 diethyl pentetic acid Chemical compound 0.000 claims description 12
- 229960001484 edetic acid Drugs 0.000 claims description 12
- 239000002738 chelating agent Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000003223 protective agent Substances 0.000 claims description 10
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 9
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 9
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 8
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 8
- 240000008042 Zea mays Species 0.000 claims description 8
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 8
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 8
- 238000013329 compounding Methods 0.000 claims description 8
- 235000005822 corn Nutrition 0.000 claims description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 8
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 8
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 8
- 239000010907 stover Substances 0.000 claims description 8
- 241001520808 Panicum virgatum Species 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- LWZFANDGMFTDAV-WYDSMHRWSA-N [2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCC(O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-WYDSMHRWSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000009897 hydrogen peroxide bleaching Methods 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 7
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 7
- 229920000053 polysorbate 80 Polymers 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 7
- 235000011067 sorbitan monolaureate Nutrition 0.000 claims description 7
- 239000002699 waste material Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims description 6
- 240000007594 Oryza sativa Species 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- 241000878006 Miscanthus sinensis Species 0.000 claims 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 claims description 3
- 150000004056 anthraquinones Chemical class 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000000969 xylosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)CO1)* 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 229960003330 pentetic acid Drugs 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229960003237 betaine Drugs 0.000 claims 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000010808 liquid waste Substances 0.000 abstract 1
- 229920002488 Hemicellulose Polymers 0.000 description 18
- 229920005610 lignin Polymers 0.000 description 13
- 229920000297 Rayon Polymers 0.000 description 12
- 230000006872 improvement Effects 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 238000001914 filtration Methods 0.000 description 9
- 229920000433 Lyocell Polymers 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 238000002803 maceration Methods 0.000 description 6
- 239000011343 solid material Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- 230000008676 import Effects 0.000 description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 3
- 235000017491 Bambusa tulda Nutrition 0.000 description 3
- 241001330002 Bambuseae Species 0.000 description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 239000011425 bamboo Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000002154 agricultural waste Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011814 protection agent Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical group CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241001349804 Juncus alpinoarticulatus Species 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009941 weaving 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
- D21C3/003—Pulping cellulose-containing materials with organic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C1/00—Pretreatment of the finely-divided materials before digesting
-
- 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
- D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
-
- 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
- D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
- D21C3/022—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes in presence of S-containing compounds
-
- 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
- D21C3/26—Multistage processes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/12—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds
- D21C9/14—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds with ClO2 or chlorites
- D21C9/142—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds with ClO2 or chlorites with ClO2/Cl2 in a multistage process involving ClO2/Cl2 exclusively
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
Abstract
The invention discloses a kind of methods for preparing dissolving pulp using stalk and energy-source plant, comprising the following steps: 1) pretreatment of raw material；2) pre-preg is handled；3) hydro-thermal process；4) mild alkali process；5) refinement treatment etc..Preparation method according to the present invention is directed to the property of raw material of agricultural crop straw class raw material and energy-source plant, devises a whole set of new dissolving pulp preparation process, provides more choices for its higher value application；Present invention process step is simple, and equipment and factory overheads cost are low；Treatment conditions are relatively mild, and chemical levels are few, and production energy consumption, chemical reagent cost and liquid waste processing difficulty are low；Simple treatment process and mild reaction condition, reduce the excessive degradation of cellulose, to improve or stabilize alpha-cellulose content, cellulosic degree of polymerization, purity and product yield.
Description
Technical field
The present invention relates to biomass to recycle field, in particular to one kind for producing viscose rayon, tencel
The preparation method of the dissolving pulp (high pure cellulose) of (Lyocell fiber) and other cellulose derivative products.
Background technique
Dissolving pulp is a kind of high pure cellulose, is that production viscose rayon, acetate fiber, nitrocellulose and cellulose ether etc. produce
The important intermediate products of product are widely used market in fields such as weaving, military project, food, coating, chemical industry.Domestic production is viscous
The raw material of glue fiber is mainly the dissolving pulp from cotton pulp and wood pulp, further includes a small amount of bamboo pulp dissolving pulp.In recent years, due to cotton
Cultivated area reduce, the usage amount of wood pulp increases year by year, while China is also increasing year by year the demand of dissolving pulp.2015
The dissolving pulp of year China's import is more than 2,000,000 tons, and in recent years import volume with the speed increase of annual 14-17%.Import dissolution
The quality of slurry is higher, and price is low, and the monthly price difference of nearly 4 years domestic dissolving pulps and import dissolving pulp is about 850 yuan/ton.Institute
With, domestic correlation leading enterprise while making great efforts to promote domestic dissolving pulp quality, also seek to produce dissolving pulp other are honest and clean
Valence raw material improves enterprise competitiveness to reduce production cost.
About the production technology of dissolving pulp, it is broadly divided into two kinds, i.e. acid sulfite process and prehydrolytic sulfate process
(Sixta, Handbook of Pulp, 2006).In the past, the production of dissolving pulp is based on acid sulfite process
(US5139617), but due to environment and other reasons, the production line newly reconstructed in recent years is substantially all using prehydrolysis sulfate
Method causes acid sulfite process technique proportion to be gradually reduced.In addition, also having on a small quantity using pulping process such as organic solvents
Carry out the preparation of dissolving pulp.Raw materials used mainly cotton linter, wood chip and bamboo chip.Since cotton in recent years is in poor harvest and cultivated area
Reduction, the usage amount of wood chip gradually increase, and directly remove hemicellulose by alkali steeping for raw material using commodity bleached wood pulp
Usually produce dissolving pulp new process also by Duo Jia viscose glue factory using (Zhang et al., CarbohydratePolymers,
2016,141,238-243).Non-wood material in addition to bamboo chip utilization, bagasse, Chinese alpine rush can also be used to production dissolving pulp,
But the factors such as the limitation due to region are not largely used to production (Yuan et al., Biotechnology for also
Biofuels,2017,10(1),38).So relevant enterprise and scientific research institution also carry out generation seeking other raw materials cheap and easy to get
For expensive wood pulp, to produce viscose rayon with high-purity cellulose products.
The present invention is big for agricultural crop straws (such as corn stover, straw, rice straw etc.) largely cheap and easy to get and
The property of raw material of the energy-source plant (Chinese silvergrass, switchgrass etc.) of plantation is measured, adaptability develops a kind of new dissolving pulp preparation side
Method.
Summary of the invention
In comprehensive utilization and existing dissolving pulp preparation process for agricultural waste material stalk and energy-source plant
Technology problem proposes a kind of new side that dissolving pulp is prepared using stalk and energy-source plant according to an aspect of the present invention
Method.
To achieve the above object, preparation method of the invention the following steps are included:
1) pretreatment of raw material: be tentatively crushed to raw material, feed particles length is made to be not more than 3 centimetres,
Wherein the raw material is stalk or energy-source plant, and the stalk is selected from corn stover, straw or rice straw etc., the energy
Source plant is selected from Chinese silvergrass or switchgrass etc..
2) pre-preg is handled: being added water to solid-to-liquid ratio 1:5-1:15 into feed particles obtained in step 1), is then added
Hydrochloric acid or sulfuric acid adjust pH=1-7, add auxiliary agent A and directly handle 20- in 40-95 DEG C of progress pre-preg after mixing evenly
90min after the completion of pre-preg, squeezes out pre-preg liquid, with the water of pre-preg xylose residue 5-20 times of weight of product by pre-preg raw material
It cleans；
Wherein, relative to the absolute dry mass of raw material, auxiliary agent A additional amount is 0.1%-2wt%, is living by chelating agent and surface
Property agent composition, the chelating agent be selected from EDTA (ethylenediamine tetra-acetic acid) and/or DTPA (diethyl pentetic acid), the surface
Activating agent be selected from neopelex, sodium lignin sulfonate, lauryl sodium sulfate, polyethylene glycol, Tween80,
The mixture of one or more of the surfactants such as Span20, empgen BB, nonylphenol polyoxyethylene ether, it is described
The mass values of chelating agent and the surfactant are 1:10 to 1:0.5；
3) it hydro-thermal process: is added into the pre-preg raw material cleaned obtained in step 2) according to solid-to-liquid ratio to 1:9-1:12
The auxiliary agent B of 8%-15wt% is added relative to the absolute dry mass of raw material in water, and it is anti-that hydro-thermal is then carried out under the conditions of 90-140 DEG C
Time 30-90 minute should be handled, after reaction, hydrolyzate is squeezed out, hydrolyzate can be used to prepare xylose product, then use solid
The water of 5-20 times of weight of product cleans remaining solid；
Wherein, relative to the absolute dry mass of raw material, the auxiliary agent B be citric acid with formic acid compound or malic acid and first
The compounding of acid, the citric acid (or malic acid) are 1:10-1:0.2 with the mass values of formic acid compounded.
4) mild alkali process: being added water according to solid-to-liquid ratio to 1:4-1:8 to the solid product after hydro-thermal process in step 3),
Relative to the absolute dry mass of solid product, the alkali of 3-12wt% and the auxiliary agent C of 0.1%-4wt% is added, mechanical stirring 2-15 divides
Clock premixing, then carries out reaction 30-150 minutes under the conditions of 90-140 DEG C；After reaction, waste liquid is squeezed out, then with admittedly
The water of 5-20 times of weight of body product cleans remaining solid, and the product after cleaning is crude fibre, after mild alkali process, washing material
It is spare and recycle black liquor；
The wherein mixture that the auxiliary agent C is made of cellulose protective agent and surfactant, the cellulose protection
Agent is selected from one or more of green oxygen, anthraquinone, magnesium sulfate, magnesia, and the surfactant is selected from dodecyl benzene sulfonic acid
The surfaces such as sodium, sodium lignin sulfonate, lauryl sodium sulfate, polyethylene glycol, Tween80, Span20, nonylphenol polyoxyethylene ether
One or more of in activating agent, the mass values of cellulose protective agent and surfactant used are 1:20 to 1:2.
5) refinement treatment: multistage bleaching refinement treatment is carried out to the washing material that step 4) obtains, the multistage bleaching can
Using multistage hydrogen peroxide bleaching, relative to coarse-fibred absolute dry mass, hydrogen peroxide single hop dosage is 3-8wt%, pH=8-
11,70-90 DEG C of temperature, it is preferable that 2-3 sections of hydrogen peroxide bleachings, fibre stuff is washed to pH neutrality after every section of bleaching, Gu
For liquor ratio to 1:6-1:12, after treatment is washed to obtain final dissolving pulp product (high pure cellulose).
Preferably, hydrochloric acid or sulphur acid for adjusting pH are added in the step 2) of preparation method according to the present invention to 2-4；
After the completion of pre-preg, pre-preg liquid is squeezed out, is washed pre-preg raw material with the water of 8-15 times of pre-preg raw material, most preferably 10 times weight
Only.
It is further preferred that in the step 3) of preparation method according to the present invention after reaction, waste liquid is squeezed out,
With 8-15 times of obtained solid, the water of most preferably 10 times weight cleans remaining solid.
It is further preferred that auxiliary agent B described in the step 3) of preparation method according to the present invention is citric acid and first
Sour compounding or malic acid is compounded with formic acid, and the citric acid (or malic acid) is 1 with the mass values of formic acid compounded:
2-1:0.5。
It is further preferred that in the step 4) of preparation method according to the present invention after reaction, waste liquid is squeezed out,
With 8-15 times of obtained solid, the water of most preferably 10 times weight cleans remaining solid.
Preferably, the multistage drift of chlorine dioxide and alkali density alternately can also be used in multistage bleaching described in step 5)
It is white, wherein relative to the absolute dry mass of fiber, chlorine dioxide single hop dosage is 0.1-1wt%, pH value=1-4, temperature 60-
100℃；Relative to the absolute dry mass of fiber, NaOH dosage is 0.5-4wt%, alternative addition 0- in alkali density in alkali density
The hydrogen peroxide of 4wt% adjusts pH value to 9-12, and single hop handles the time as 30-180min, it is preferable that using 3-4 sections of alternating
Processing.
Selectively, preparation method according to the present invention may further include following steps:
6) it removes the processing of metal ion: relative to the absolute dry mass of fiber, water and the EDTA of 0.1%-2wt% is added
Or DTPA, control pH are 3-7,70-90 DEG C of temperature, solid-to-liquid ratio 1:8-1:12, are handled time 30-90 minutes, it will slurry after processing
Material washing is neutrality to pH, obtains final dissolving pulp (high pure cellulose) product.
Beneficial effect
Preparation method according to the present invention is directed to the property of raw material of agricultural crop straw class raw material and energy-source plant, devises one
A whole set of new dissolving pulp preparation process, provides more choices for its higher value application；Present invention process step is simple, equipment
It is low with factory overheads cost；Treatment conditions are relatively mild, and chemical levels are few, production energy consumption, chemical reagent cost and useless
Liquid processing difficulty is low；Simple treatment process and mild reaction condition, reduce the excessive degradation of cellulose, thus improve or
Stabilize alpha-cellulose content, cellulosic degree of polymerization, purity and product yield.
Specific embodiment
Hereinafter, will be described in detail the present invention.Before doing so, it should be appreciated that in this specification and appended
Claims used in term should not be construed as being limited to general sense and dictionary meanings, and inventor should allowed
On the basis of the appropriate principle for defining term to carry out best interpretations, according to meaning corresponding with technical aspect of the invention and generally
Thought explains.Therefore, description presented herein is not intended to limitation originally merely for the sake of the preferred embodiment for illustrating purpose
The range of invention, it will thus be appreciated that without departing from the spirit and scope of the present invention, it can be obtained by it
His equivalents or improved procedure.
The raw material used due to preparation method according to the present invention is agricultural waste material stalk and energy-source plant, in order to just
In application, raw material can be carried out pre-processing preliminary broken, so that feed particles length is not more than 3 centimetres, or according to the present invention
The preparation method need feed pretreatment step to increase raw material uniformity coefficient, wherein can be by selectively carrying out machine
Tool processing is chemically treated to increase the mechanical lapping of raw material uniformity coefficient, such as disc mill, planetary ball mill etc. and handle, or
Addition soda acid discongests the modes such as agent under the premise of not influencing subsequent processes.
Pass through in the pre-preg processing of the step 2) of preparation method according to the present invention and is added by chelating agent and surface-active
Agent constitute auxiliary agent A can it is as much as possible removing raw material in extract and ash content, reduce subsequent purification cellulose pressure.
Wherein relative to the absolute dry mass of raw material, the additional amount of the auxiliary agent A is 0.1%-2wt%.The chelating agent be selected from EDTA and/
Or DTPA, chelating agent can remove the middle ash content of raw material, especially remove metal ion, if existed excessively in final product
Metal ion, then to it is subsequent application it is unfavorable, the surfactant be selected from neopelex, sodium lignin sulfonate,
The surfaces such as lauryl sodium sulfate, polyethylene glycol, Tween80, Span20, empgen BB, nonylphenol polyoxyethylene ether
The mixture of one or more of activating agent, surfactant can promote the removing of extract, be conducive to improve cellulose
Purity.The mass values of the chelating agent and the surfactant are 1:10 to 1:0.5, and the dosage of the chelating agent should not mistake
Greatly, but if ratio is less than 1:10, ash content removal effect is unobvious (removing of especially iron ion is unobvious), if ratio is big
In 1:0.5, then extract removal efficiency is too low (less than 50%).
To the preimpregnation cleaned obtained in step 2) in the hydro-thermal process of the step 3) of preparation method according to the present invention
Water is added according to solid-to-liquid ratio to 1:9-1:12 in stain raw material, the auxiliary agent of 8%-15wt% is added relative to the absolute dry mass of raw material
Then B carries out hydro-thermal reaction under the conditions of 90-140 DEG C and handles time 30-90 minutes, after reaction, hydrolyzate is squeezed out,
Hydrolyzate can be used to prepare xylose product, then with 5-20 times of solid product, preferably 8-15 times, and the water of most preferably 10 times weight will remain
Remaining solid is cleaned；
Wherein, relative to the absolute dry mass of raw material, the auxiliary agent B be citric acid with formic acid compound or malic acid and first
The compounding of acid keeps the temperature of hydro-thermal process more mild wherein formic acid, which is added, can accelerate the degradation and dissolution of hemicellulose, but
It is that can cause to corrode to equipment, increase equipment cost when formic acid dosage is greater than 8wt%；And the then peace of citric acid and malic acid
Complete is more, if but only with citric acid or malic acid, under identical hydrolysis efficiency, cost can be more much higher than with formic acid, institute
It is used in compounding with selection.In addition, citric acid and malic acid can be separated with calcium salt sedimentation.The citric acid (or malic acid)
It is 1:10-1:0.2, preferably 1:2-1:0.5 with the mass values of formic acid compounded.If ratio is less than 1:10, formic acid accounting
Equipment can be caused to corrode in the case where excessive；If ratio is greater than 1:0.2, in the case that formic acid accounting is too small, hydrolysis efficiency
It can reduce, hemicellulose removal efficiency is lower in raw material, influences the purity of subsequent fiber element product, and acid-hydrolyzed cost can increase
Add.The molal quantity of the acid of phase homogenous quantities, effective acid group of formic acid is greater than the biggish citric acid of molecular weight and malic acid.
By the way that the over dry relative to raw material is added in the mild alkali process of the step 4) of preparation method according to the present invention
Quality is added the alkali of 3-12wt% and the auxiliary agent C of 0.1%-4wt%, and is realized under relatively mild conditions to raw material
Boiling, thus the lignin in removing raw material as much as possible, but reservation cellulose as much as possible simultaneously, guarantee that fiber is known as
Higher yield.It is pre-mixed within mechanical stirring 2-15 minutes, reaction 30-150 minutes is then carried out under the conditions of 70-120 DEG C；Reaction
After, waste liquid is squeezed out, then with 5-20 times of solid product, preferably 8-15 times, the water of most preferably 10 times weight is by remaining solid
It cleans, the product after cleaning is crude fibre, and after boiling, washing material is spare and recycles black liquor.
Wherein, relative to the absolute dry mass of raw material, the alkali of 3-12wt% and the auxiliary agent C of 0.1%-4wt% is added, it is described to help
Agent C is the mixture of cellulose protective agent and surfactant.The fiber protection agent mainly protects cellulose, avoids alkali pair
The transition of cellulose is degraded；And the effect of the surfactant is first is that promote the protectant fine dispersion of cellulose and infiltration,
Second is that being conducive to the dissolution of lignin.The wherein mixture that the auxiliary agent C is made of cellulose protective agent and surfactant,
The cellulose protective agent is selected from one or more of green oxygen, anthraquinone, magnesium sulfate, magnesia, and the surfactant is selected from
Neopelex, sodium lignin sulfonate, lauryl sodium sulfate, polyethylene glycol, Tween80, Span20, nonyl phenol are poly-
One or more of in the surfactants such as ethylene oxide ether, the mass values of cellulose protective agent and surfactant used are 1:20
To 1:2.If the dosage of the cellulose protective agent and surfactant is less than above range, cellulose yield can be reduced,
Lose excessive, delignification is insufficient, influences further purification effect.
The washing material that step 4) obtains is carried out in the step 5) refinement treatment of preparation method according to the present invention more
The bleached refined processing of section, multistage hydrogen peroxide bleaching can be used in the multistage bleaching, relative to coarse-fibred absolute dry mass, peroxide
Change hydrogen single hop dosage be 3-8wt%, pH=8-11,70-90 DEG C of temperature, it is preferable that 2-3 sections of hydrogen peroxide bleachings, every section
Fibre stuff is washed to pH neutrality, solid-to-liquid ratio to 1:6-1:12 after bleaching, and after treatment is washed to obtain final dissolving pulp
Product (high pure cellulose).
Preferably, chlorine dioxide can also be used in multistage bleaching described in the step 5) of preparation method according to the present invention
With the multistage bleaching of alkali density alternately, wherein relative to the absolute dry mass of fiber, chlorine dioxide single hop dosage is 0.1-
1wt%, pH value=1-4, temperature are 60-100 DEG C；Relative to the absolute dry mass of fiber, NaOH dosage is 0.5- in alkali density
4wt%, the hydrogen peroxide of alternative addition 0-4wt% in alkali density adjust pH value to 9-12, and it is 30- that single hop, which handles the time,
180min, it is preferable that using 3-4 sections of alternate treatment.
Selectively, preparation method according to the present invention may further include following steps:
6) it removes the processing of metal ion: relative to the absolute dry mass of fiber, water and the EDTA of 0.1%-2wt% is added
Or DTPA, control pH are 3-7,70-90 DEG C of temperature, solid-to-liquid ratio 1:8-1:12, are handled time 30-90 minutes, it will slurry after processing
Material washing is neutrality to pH, obtains final xylose residue dissolving pulp (high pure cellulose) product.
Which kind of specifically used bleaching process can be selected according to material lignin residual volume and character.Multistage is pure in principle
Hydrogen peroxide bleaching is few for residual lignin, the sample that ash content is less and particle is tiny；And chlorine dioxide and alkali density combine
Technique be suitble to metal ion and lignin residue amount high, the biggish sample of particle.If necessary to further preparation higher purity
Cellulose products, can suitably increase ClO 2 bleaching and alkali density number of processing.
The crude fibre refinement treatment process can be handled only comprising multistage bleaching, also may include multistage bleaching processing
With the treatment process of demetalization ion, it is therefore an objective to which further removing lignin and metal ion (especially iron ion) mention
High microsteping purity.
Following embodiment is enumerated only as the example of embodiment of the present invention, does not constitute any limit to the present invention
System, it will be appreciated by those skilled in the art that modification in the range of without departing from essence and design of the invention each falls within the present invention
Protection scope.Unless stated otherwise, reagent and instrument used in the following embodiment are commercially available product.
Embodiment 1
A kind of preparation method of viscose rayon dissolving pulp, the specific steps are as follows:
A. air-dried corn stover be tentatively crushed, keep broken stalk partial size length spare less than 3 centimetres.
B. pre-preg processing, treatment conditions are as follows: solid-to-liquid ratio 1:9, temperature 70 C are based on are carried out to broken corn stover
The dry weight of corn stover, EDTA dosage are 0.3wt%, and lauryl sodium sulfate dosage is 0.9wt%, and dip time is 70 points
Clock.After treatment squeezes out and recycles maceration extract, is cleaned raw material with the water of 10 times of weight.After handling with this condition, extraction
Object removal efficiency is 86%, and ash content removal efficiency is 69%.
C. the material after cleaning to pre-preg carries out improvement hydro-thermal process, treatment conditions are as follows: solid-to-liquid ratio 1:9, temperature 115
DEG C, the dry weight based on material, Citric Acid Dosage 8wt%, formic acid dosage 4wt%, the processing time is 60 minutes.After the completion of processing,
Hydrolyzate is squeezed out and recycled, is then cleaned raw material with the water of 10 times of weight.After handling with this condition, hemicellulose removal efficiency
It is 87%.Hydrolyzate can be used for preparing xylose.
D. to improvement hydro-thermal process and clean material carries out mild alkali process, treatment conditions are as follows: solid-to-liquid ratio 1:5 is based on
The dry weight of material, NaOH dosage 10wt%, magnesium sulfate dosage 0.7wt%, the dosage of nonylphenol polyoxyethylene ether are 1.2wt%,
It 120 DEG C of temperature, handles 50 minutes.After treatment squeezes out and recycles black liquor, is then cleaned raw material with the water of 10 times of weight.?
After handling under this condition, the removal efficiency of lignin is 84%, and cellulose yield is 96%.
E. the hydrogen peroxide (relative to solid material oven dry weight) of 8wt% is added in the slurry of solids obtained to step D,
Solid-to-liquid ratio 1:9 is added water to, and adjusts pH value to 10.5 with NaOH；Heat up 18min, and temperature reaches 95 DEG C, keeps the temperature 120min；Bleaching
After, filtering stock to neutrality then proceedes to repeat this bleaching process twice, and finally washing obtains dissolving pulp product.
The total slurry yield of gained dissolving pulp product is 53%, the degree of polymerization 531, Fe ion concentration 35ppm, relative to original original
Expect that oven dry weight, hemi-cellulose content 0.1wt%, extract content 0.11wt%, alpha-cellulose content 92.7wt% are fully met
Viscose rayon production requirement.
Embodiment 2
A kind of preparation method of viscose rayon dissolving pulp, the specific steps are as follows:
A. air-dried straw be tentatively crushed, keep broken stalk partial size length spare less than 3 centimetres.
B. pre-preg processing, treatment conditions are carried out to broken straw are as follows: solid-to-liquid ratio 1:10, is based on object by 85 DEG C of temperature
The dry weight of material, EDTA dosage are 0.35wt%, and Span20 dosage is 1.2wt%, and dip time is 80 minutes.After treatment,
Maceration extract is squeezed out and recycled, is cleaned raw material with the water of 10 times of weight.After handling with this condition, extract removal efficiency is
87%, ash content removal efficiency is 67%.
C. the material after cleaning to pre-preg carries out improvement hydro-thermal process, treatment conditions are as follows: solid-to-liquid ratio 1:10, temperature 125
DEG C, the dry weight based on material, malic acid dosage 5wt%, formic acid dosage 5wt%, the processing time is 70 minutes.After the completion of processing,
Hydrolyzate is squeezed out and recycled, is then cleaned raw material with the water of 10 times of weight.After handling with this condition, hemicellulose removal efficiency
It is 85%.Hydrolyzate can be used for preparing xylose.
D. to improvement hydro-thermal process and clean slurry carries out mild alkali process, treatment conditions are as follows: solid-to-liquid ratio 1:7 is based on
The dry weight of material, the dosage of NaOH dosage 11wt%, green oxygen dosage 0.2wt%, Tween80 are 1wt%, 110 DEG C of temperature, are handled
70 minutes.After treatment squeezes out and recycles black liquor, is then cleaned raw material with the water of 10 times of weight.It handles with this condition
Afterwards, the removal efficiency of lignin is 87%, and cellulose yield is 98%.
E. the hydrogen peroxide (relative to solid material oven dry weight) of 7wt% is added in the solid material obtained to step D,
Solid-to-liquid ratio 1:10 is added water to, and adjusts pH value to 10.5 with NaOH；Heat up 18min, and temperature reaches 90 DEG C, keeps the temperature 120min；Drift
After white, filtering stock to neutrality then proceedes to repeat this bleaching process twice, and finally washing obtains dissolving pulp product.
The total slurry yield of gained dissolving pulp product is 55%, the degree of polymerization 563, Fe ion concentration 21ppm, relative to original original
Expect that oven dry weight, hemi-cellulose content 0.3wt%, extract content 0.2wt%, alpha-cellulose content 93.2wt% are fully met
Viscose rayon production requirement.
Embodiment 3
A kind of preparation method of viscose rayon dissolving pulp, the specific steps are as follows:
A. air-dried rice straw be tentatively crushed, keep broken stalk partial size length spare less than 3 centimetres.
B. pre-preg processing, treatment conditions are carried out to broken straw are as follows: solid-to-liquid ratio 1:10, is based on object by 90 DEG C of temperature
The dry weight of material, DTPA dosage are 0.6wt%, and neopelex dosage is 1wt%, and dip time is 66 minutes.Processing
After, maceration extract is squeezed out and recycled, is cleaned raw material with the water of 10 times of weight.After handling with this condition, extract removing
Rate is 91%, and ash content removal efficiency is 73%.
C. the slurry after cleaning to pre-preg carries out improvement hydro-thermal process, treatment conditions are as follows: solid-to-liquid ratio 1:12, temperature 130
DEG C, the dry weight based on material, malic acid dosage 3wt%, formic acid dosage 5wt%, the processing time is 75 minutes.After the completion of processing,
Hydrolyzate is squeezed out and recycled, is then cleaned raw material with the water of 10 times of weight.After handling with this condition, hemicellulose removal efficiency
It is 87%.Hydrolyzate can be used for preparing xylose.
D. to improvement hydro-thermal process and clean slurry carries out mild alkali process, treatment conditions are as follows: solid-to-liquid ratio 1:8 is based on
The dry weight of material, NaOH dosage 12wt%, magnesium sulfate dosage 0.4wt%, the dosage of sodium lignin sulfonate are 2wt%, temperature 140
DEG C, it handles 40 minutes.After treatment squeezes out and recycles black liquor, is then cleaned raw material with the water of 10 times of weight.In this condition
After lower processing, the removal efficiency of lignin is 88%, and cellulose yield is 97%.
E. the chlorine dioxide of 0.6wt% is added in the solid material obtained to step D (relative to solid material over dry weight
Amount), solid-to-liquid ratio 1:9 is added water to, and adjust pH value to 2.5；It is rapidly heated to 75 DEG C, keeps the temperature 60min；After bleaching, filtering stock
The hydrogen peroxide of the NaOH and 2wt% of 2wt% is then added, adds water to solid-liquid relative to solid material oven dry weight to neutrality
It than 1:9, is rapidly heated to 80 DEG C, keeps the temperature 60min；After alkali density, the chlorine dioxide of 0.2wt% is added in filtering stock to neutrality,
Solid-to-liquid ratio 1:9 is added water to, and adjusts pH value to 2.0；It is rapidly heated to 70 DEG C, after keeping the temperature 120min, washing to neutrality；Then again
The hydrogen peroxide repetition alkali density above-mentioned that the NaOH and 2wt% of 2wt% is added is primary, obtains dissolving pulp after the washing that is disposed
Product.
The total slurry yield of gained dissolving pulp product is 51%, the degree of polymerization 519, Fe ion concentration 39ppm, relative to original original
Expect that oven dry weight, hemi-cellulose content 0.5wt%, extract content 0.4wt%, alpha-cellulose content 92wt% are fully met viscous
Glue fiber production requirement.
Embodiment 4
A kind of tencel (Lyocell fiber) uses the preparation method of dissolving pulp, the specific steps are as follows:
A. air-dried switchgrass be tentatively crushed, keep broken stalk partial size length spare less than 3 centimetres.
B. pre-preg processing, treatment conditions are as follows: solid-to-liquid ratio 1:11, is based on by 95 DEG C of temperature are carried out to broken switchgrass
The dry weight of material, DTPA dosage are 0.7wt%, and polyethylene glycol dosage is 1.2wt%, and dip time is 55 minutes.Processing terminate
Afterwards, maceration extract is squeezed out and recycled, is cleaned raw material with the water of 10 times of weight.After handling with this condition, extract removal efficiency is
89%, ash content removal efficiency is 71%.
C. the slurry after cleaning to pre-preg carries out improvement hydro-thermal process, treatment conditions are as follows: solid-to-liquid ratio 1:11, temperature 135
DEG C, the dry weight based on material, Citric Acid Dosage 5wt%, formic acid dosage 7wt%, the processing time is 60 minutes.After the completion of processing,
Hydrolyzate is squeezed out and recycled, is then cleaned raw material with the water of 10 times of weight.After handling with this condition, hemicellulose removal efficiency
It is 90%.Hydrolyzate can be used for preparing xylose.
D. to improvement hydro-thermal process and clean slurry carries out mild alkali process, treatment conditions are as follows: solid-to-liquid ratio 1:7 is based on
The dry weight of material, NaOH dosage 10wt%, magnesium sulfate dosage 0.5wt%, the dosage of lauryl sodium sulfate are 2wt%, temperature
It 140 DEG C, handles 45 minutes.After treatment squeezes out and recycles black liquor, is then cleaned raw material with the water of 10 times of weight.At this
After handling under part, the removal efficiency of lignin is 84%, and cellulose yield is 95%.
E. the chlorine dioxide of 0.7wt% is added in the slurry of solids obtained to step D (relative to slurry of solids over dry weight
Amount), solid-to-liquid ratio 1:10 is added water to, and adjust pH value to 2.5；It is rapidly heated to 75 DEG C, keeps the temperature 60min；After bleaching, filtering stock
To neutrality, the hydrogen peroxide of the NaOH and 1wt% of 2wt% is then added, adds water to solid-to-liquid ratio 1:10, is rapidly heated to 80 DEG C,
Keep the temperature 60min；After alkali density, the chlorine dioxide of 0.2wt% is added in filtering stock to neutrality, adds water to solid-to-liquid ratio 1:10, and adjust
PH value is saved to 2.0；It is rapidly heated to 70 DEG C, after keeping the temperature 120min, washing to neutrality；Then add 2wt% NaOH and
It is primary that the hydrogen peroxide of 1wt% repeats alkali density above-mentioned；Finally carry out removing iron ion processing, EDTA dosage 1wt%, temperature
It 85 DEG C, handles the time 1 hour, solid-to-liquid ratio 1:10, obtains dissolving pulp product after the washing that is disposed.
The total slurry yield of gained dissolving pulp product is 49%, the degree of polymerization 609, Fe ion concentration 3ppm, relative to original original
Expect oven dry weight, hemi-cellulose content 0.2wt%, extract content 0.1wt%, alpha-cellulose content 94wt% fully meet day
Silk production requirement.
Comparative example 1
A kind of preparation method of viscose rayon dissolving pulp, the specific steps are as follows:
A. air-dried corn stover be tentatively crushed, keep broken stalk partial size length spare less than 3 centimetres.
B. pre-preg processing, treatment conditions are as follows: solid-to-liquid ratio 1:9, temperature 70 C are based on are carried out to broken corn stover
The dry weight of material, EDTA dosage are 0.3wt%, and dip time is 70 minutes.After treatment squeezes out and recycles maceration extract, uses
The water of 10 times of weight cleans raw material.After handling with this condition, extract removal efficiency is 71%, and ash content removal efficiency is 60%,
Extract removal efficiency significantly lower than in embodiment 1 86% and 69% ash content removal efficiency.
C. the slurry after cleaning to pre-preg carries out improvement hydro-thermal process, treatment conditions are as follows: solid-to-liquid ratio 1:9, temperature 115
DEG C, the processing time is 60 minutes.After the completion of processing, hydrolyzate is squeezed out and recycled, is then cleaned raw material with the water of 10 times of weight.
After handling with this condition, hemicellulose removal efficiency is 69%, hence it is evident that the hemicellulose removal efficiency lower than in embodiment 1 87%.
Hydrolyzate can be used for preparing xylose.
D. to improvement hydro-thermal process and clean slurry carries out mild alkali process, treatment conditions are as follows: solid-to-liquid ratio 1:5 is based on
The dry weight of material, NaOH dosage 10wt%, magnesium sulfate dosage 0.7wt%, the dosage of nonylphenol polyoxyethylene ether are 1.2wt%,
It 120 DEG C of temperature, handles 50 minutes.After treatment squeezes out and recycles black liquor, is then cleaned raw material with the water of 10 times of weight.?
After handling under this condition, the removal efficiency of lignin is 82%, and cellulose yield is 94%.
E. the hydrogen peroxide (relative to slurry of solids oven dry weight) of 8wt% is added in the slurry of solids obtained to step D,
Solid-to-liquid ratio 1:9 is added water to, and adjusts pH value to 10.5 with NaOH；Heat up 18min, and temperature reaches 95 DEG C, keeps the temperature 120min；Bleaching
After, filtering stock to neutrality then proceedes to repeat this bleaching process twice, and finally washing obtains dissolving pulp product.
The total slurry yield of gained dissolving pulp product is 56%, the degree of polymerization 564, Fe ion concentration 65ppm, relative to original original
Expect oven dry weight, hemi-cellulose content 5.1wt%, extract content 2.1wt%, content of lignin 1wt%, alpha-cellulose content
86.7wt% is not able to satisfy viscose rayon production requirement.The reason is that since pre-preg and hydro-thermal process are to extract, ash content, half
Cellulose removing is insufficient, then is handled with the subsequent processing condition of embodiment 1, causes final products impurity content higher, cannot
Meet viscose rayon production requirement.
Comparative example 2
A kind of tencel (Lyocell fiber) uses the preparation method of dissolving pulp, the specific steps are as follows:
A. air-dried switchgrass be tentatively crushed, keep broken stalk partial size length spare less than 3 centimetres.
B. pre-preg processing, treatment conditions are carried out to broken switchgrass are as follows: solid-to-liquid ratio 1:11,95 DEG C of temperature, dipping
Time is 55 minutes.After treatment squeezes out and recycles maceration extract, is cleaned raw material with the water of 10 times of weight.With this condition
After processing, extract removal efficiency is 66%, and ash content removal efficiency is 58%, hence it is evident that the extract removing lower than in embodiment 4 89%
Rate and 71% ash content removal efficiency.
C. the slurry after cleaning to pre-preg carries out improvement hydro-thermal process, treatment conditions are as follows: solid-to-liquid ratio 1:11, temperature 135
DEG C, the processing time is 60 minutes.After the completion of processing, hydrolyzate is squeezed out and recycled, is then cleaned raw material with the water of 10 times of weight.
After handling with this condition, hemicellulose removal efficiency is 69%, hence it is evident that the hemicellulose removal efficiency lower than in embodiment 4 90%.
Hydrolyzate can be used for preparing xylose.
D. to improvement hydro-thermal process and clean slurry carries out mild alkali process, treatment conditions are as follows: solid-to-liquid ratio 1:7 is based on
The dry weight of material, NaOH dosage 10wt%, magnesium sulfate dosage 0.5wt%, the dosage of lauryl sodium sulfate are 2wt%, temperature
It 140 DEG C, handles 45 minutes.After treatment squeezes out and recycles black liquor, is then cleaned raw material with the water of 10 times of weight.At this
After handling under part, the removal efficiency of lignin is 81%, and cellulose yield is 96%.
E. the chlorine dioxide of 0.7wt% is added in the slurry of solids obtained to step D (relative to slurry of solids over dry weight
Amount), solid-to-liquid ratio 1:10 is added water to, and adjust pH value to 2.5；It is rapidly heated to 75 DEG C, keeps the temperature 60min；After bleaching, filtering stock
To neutrality, the hydrogen peroxide of the NaOH and 1wt% of 2wt% is then added, adds water to solid-to-liquid ratio 1:10, is rapidly heated to 80 DEG C,
Keep the temperature 60min；After alkali density, the chlorine dioxide of 0.2wt% is added in filtering stock to neutrality, adds water to solid-to-liquid ratio 1:10, and adjust
PH value is saved to 2.0；It is rapidly heated to 70 DEG C, after keeping the temperature 120min, washing to neutrality；Then add 2wt% NaOH and
The hydrogen peroxide repetition alkali density above-mentioned of 1wt% is primary, obtains dissolving pulp product after the washing that is disposed.
The total slurry yield of gained dissolving pulp product is 56%, the degree of polymerization 634, Fe ion concentration 37ppm, relative to original original
Expect oven dry weight, hemi-cellulose content 2.3wt%, extract content 1.8wt%, alpha-cellulose content 89wt% are not able to satisfy day
Silk production requirement.The reason is that since pre-preg and hydro-thermal process are insufficient to extract, ash content, hemicellulose removing, then in fact
The subsequent processing condition processing for applying example 1, causes final products impurity content higher, is not able to satisfy tencel production requirement.Moreover, drift
It is handled after white without the removing of further progress iron ion, causes iron ion content excessively high (being greater than 5ppm), can not carry out subsequent
Tencel production.
Claims (7)
1. a kind of method for preparing dissolving pulp using stalk and energy-source plant, comprising the following steps:
1) pretreatment of raw material: be tentatively crushed to raw material, feed particles length is made to be not more than 3 centimetres,
Wherein the raw material is stalk or energy-source plant, and the stalk is selected from corn stover, straw or rice straw etc., and the energy is planted
Object is selected from Chinese silvergrass or switchgrass etc.；
2) pre-preg is handled: adding water to solid-to-liquid ratio 1:5-1:15 into feed particles obtained in step 1), hydrochloric acid is then added
Or sulfuric acid adjusts pH=1-7, adds auxiliary agent A and directly handles 20-90min in 40-95 DEG C of progress pre-preg after mixing evenly, in advance
After the completion of dipping, pre-preg liquid is squeezed out, is cleaned pre-preg raw material with the water of pre-preg xylose residue 5-20 times of weight of product；
Wherein, relative to the absolute dry mass of raw material, it is by chelating agent and surfactant that auxiliary agent A additional amount, which is 0.1%-2wt%,
Composition, the chelating agent are selected from EDTA (ethylenediamine tetra-acetic acid) and/or DTPA (diethyl pentetic acid), the surface-active
Agent is selected from neopelex, sodium lignin sulfonate, lauryl sodium sulfate, polyethylene glycol, Tween80, Span20, ten
The mixture of one or more of the surfactants such as dialkyl group glycine betaine, nonylphenol polyoxyethylene ether, the chelating agent with
The mass values of the surfactant are 1:10 to 1:0.5；
3) hydro-thermal process: being added water according to solid-to-liquid ratio to 1:9-1:12 into the pre-preg raw material cleaned obtained in step 2),
Relative to the absolute dry mass of raw material, the auxiliary agent B of 8%-15wt% is added, is then carried out at hydro-thermal reaction under the conditions of 90-140 DEG C
Reason time 30-90 minutes, after reaction, hydrolyzate is squeezed out, hydrolyzate can be used to prepare xylose product, then use solid product
The water of 5-20 times of weight cleans remaining solid；
Wherein, relative to the absolute dry mass of raw material, the auxiliary agent B be citric acid with formic acid compound or malic acid and formic acid
Compounding, the citric acid (or malic acid) are 1:10-1:0.2 with the mass values of formic acid compounded；
4) mild alkali process: water is added according to solid-to-liquid ratio to 1:4-1:8 to the solid product after hydro-thermal process in step 3), relatively
In the absolute dry mass of solid product, the alkali of 3-12wt% and the auxiliary agent C of 0.1%-4wt% is added, mechanical stirring 2-15 minutes pre-
Then mixing carries out reaction 30-150 minutes under the conditions of 90-140 DEG C；After reaction, waste liquid is squeezed out, then is produced with solid
The water of 5-20 times of weight of object cleans remaining solid, and the product after cleaning is crude fibre, and after mild alkali process, washing material is spare
And recycle black liquor；
The wherein mixture that the auxiliary agent C is made of cellulose protective agent and surfactant, the cellulose protective agent choosing
From one or more of green oxygen, anthraquinone, magnesium sulfate, magnesia, the surfactant is selected from neopelex, wood
The surface-actives such as quality sodium sulfonate, lauryl sodium sulfate, polyethylene glycol, Tween80, Span20, nonylphenol polyoxyethylene ether
One or more of in agent, the mass values of cellulose protective agent and surfactant used are 1:20 to 1:2；
5) refinement treatment: multistage bleaching refinement treatment is carried out to the washing material that step 4) obtains, the multistage bleaching can be used
Multistage hydrogen peroxide bleaching, relative to coarse-fibred absolute dry mass, hydrogen peroxide single hop dosage is 3-8wt%, pH=8-11, temperature
70-90 DEG C of degree, it is preferable that 2-3 sections of hydrogen peroxide bleachings, fibre stuff is washed to pH neutrality, solid-to-liquid ratio after every section of bleaching
To 1:6-1:12, after treatment is washed to obtain final dissolving pulp product (high pure cellulose).
2. the method according to claim 1 for preparing dissolving pulp using stalk and energy-source plant, which is characterized in that step 2)
Middle addition hydrochloric acid or sulphur acid for adjusting pH are to 2-4；After the completion of pre-preg, pre-preg liquid is squeezed out, with 8-15 times of pre-preg raw material, most
It is preferred that the water of 10 times of weight cleans pre-preg raw material.
3. the method according to claim 1 for preparing dissolving pulp using stalk and energy-source plant, which is characterized in that step 3)
In after reaction, waste liquid is squeezed out, with 8-15 times of obtained solid, the water of most preferably 10 times weight cleans remaining solid.
4. the method according to claim 1 for preparing dissolving pulp using stalk and energy-source plant, which is characterized in that step 3)
Described in auxiliary agent B be compounding for citric acid and formic acid or compounding for malic acid and formic acid, the citric acid (or malic acid) with
The mass values of the compounding of formic acid are 1:2-1:0.5.
5. the method according to claim 1 for preparing dissolving pulp using stalk and energy-source plant, which is characterized in that step 4)
In after reaction, waste liquid is squeezed out, with 8-15 times of obtained solid, the water of most preferably 10 times weight cleans remaining solid.
6. the method according to claim 1 for preparing dissolving pulp using stalk and energy-source plant, which is characterized in that step 5)
Described in multistage bleaching the multistage bleaching of chlorine dioxide and alkali density alternately can also be used, wherein relative to the exhausted of fiber
Dry mass, chlorine dioxide single hop dosage are 0.1-1wt%, and pH value=1-4, temperature is 60-100 DEG C；Over dry relative to fiber
Quality, NaOH dosage is 0.5-4wt% in alkali density, and the hydrogen peroxide of alternative addition 0-4wt%, adjusts pH in alkali density
Value is to 9-12, and single hop handles the time as 30-180min, it is preferable that using 3-4 sections of alternate treatment.
7. the method according to claim 1 for preparing dissolving pulp using stalk and energy-source plant, which is characterized in that the system
Preparation Method may further include following steps:
6) remove the processing of metal ion: relative to the absolute dry mass of fiber, be added water and 0.1%-2wt% EDTA or
DTPA, control pH are 3-7,70-90 DEG C of temperature, solid-to-liquid ratio 1:8-1:12, are handled time 30-90 minutes, by slurry after processing
Washing is neutrality to pH, obtains final dissolving pulp (high pure cellulose) product.
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| CN112522985A (en) * | 2020-12-10 | 2021-03-19 | 齐鲁工业大学 | Micro-chemical pulping of agricultural straw and full-component refining method of biomass |
| CN112726249A (en) * | 2020-12-29 | 2021-04-30 | 陕西科技大学 | Dissolving pulp prepared from corn straw skins and method |
| CN113957736A (en) * | 2021-10-26 | 2022-01-21 | 福建农林大学 | High-drainability wheat straw chemi-mechanical pulp and preparation method and application thereof based on acid catalysis |
| WO2022098963A1 (en) * | 2020-11-06 | 2022-05-12 | Kimberly-Clark Worldwide, Inc. | Non-wood pulp having high brightness and low debris |
| WO2022098958A1 (en) * | 2020-11-06 | 2022-05-12 | Kimberly-Clark Worldwide, Inc. | Dispersible non-wood pulp |
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| CN101058953A (en) * | 2007-05-17 | 2007-10-24 | 山东海龙股份有限公司 | Method of preparing bleaching dissolved pulp from corn stem |
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| WO2022098958A1 (en) * | 2020-11-06 | 2022-05-12 | Kimberly-Clark Worldwide, Inc. | Dispersible non-wood pulp |
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| CN113957736A (en) * | 2021-10-26 | 2022-01-21 | 福建农林大学 | High-drainability wheat straw chemi-mechanical pulp and preparation method and application thereof based on acid catalysis |
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