CN109653009A - A kind of preparation method by xylose residue production dissolving pulp - Google Patents
A kind of preparation method by xylose residue production dissolving pulp Download PDFInfo
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- CN109653009A CN109653009A CN201710946817.1A CN201710946817A CN109653009A CN 109653009 A CN109653009 A CN 109653009A CN 201710946817 A CN201710946817 A CN 201710946817A CN 109653009 A CN109653009 A CN 109653009A
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- Prior art keywords
- xylose residue
- preparation
- preg
- dissolving pulp
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- 125000000969 xylosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)CO1)* 0.000 title claims abstract description 91
- 229920000875 Dissolving pulp Polymers 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 229920002678 cellulose Polymers 0.000 claims abstract description 42
- 239000001913 cellulose Substances 0.000 claims abstract description 42
- 238000012545 processing Methods 0.000 claims abstract description 32
- 238000009835 boiling Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000002699 waste material Substances 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 239000007788 liquid Substances 0.000 claims description 52
- 239000004094 surface-active agent Substances 0.000 claims description 32
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- 239000000835 fiber Substances 0.000 claims description 28
- 239000002994 raw material Substances 0.000 claims description 28
- 239000003513 alkali Substances 0.000 claims description 27
- 238000004061 bleaching Methods 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 27
- 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 24
- 239000007787 solid Substances 0.000 claims description 24
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 21
- 239000012752 auxiliary agent Substances 0.000 claims description 18
- 239000002738 chelating agent Substances 0.000 claims description 15
- 239000003223 protective agent Substances 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
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 12
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 12
- 229960001484 edetic acid Drugs 0.000 claims description 12
- 239000004155 Chlorine dioxide Substances 0.000 claims description 11
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000005864 Sulphur Substances 0.000 claims description 8
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 8
- 229920000053 polysorbate 80 Polymers 0.000 claims description 8
- 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
- -1 empgen BB Chemical compound 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
- 235000011067 sorbitan monolaureate Nutrition 0.000 claims description 7
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims description 5
- 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 4
- 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 4
- 150000004056 anthraquinones Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- NHYCGSASNAIGLD-UHFFFAOYSA-N Chlorine monoxide Chemical compound Cl[O] NHYCGSASNAIGLD-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- 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
- 239000010808 liquid waste Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 32
- 235000011121 sodium hydroxide Nutrition 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- 229920000433 Lyocell Polymers 0.000 description 8
- 229920000297 Rayon Polymers 0.000 description 8
- 229920005610 lignin Polymers 0.000 description 8
- 229920002488 Hemicellulose Polymers 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 5
- 235000017491 Bambusa tulda Nutrition 0.000 description 5
- 241001330002 Bambuseae Species 0.000 description 5
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 239000011425 bamboo Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011814 protection agent Substances 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical group CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 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
- 230000008676 import Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241001343274 Dichrostachys spicata Species 0.000 description 1
- WTBIAPVQQBCLFP-UHFFFAOYSA-N N.N.N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O Chemical compound N.N.N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O WTBIAPVQQBCLFP-UHFFFAOYSA-N 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
- 229920002522 Wood fibre Polymers 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
- D21B1/00—Fibrous raw materials or their mechanical treatment
- D21B1/02—Pretreatment of the raw materials by chemical or physical means
- D21B1/021—Pretreatment of the raw materials by chemical or physical means by chemical means
-
- 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
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
Landscapes
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Paper (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a kind of preparation method by xylose residue production dissolving pulp, including 1) feed pretreatment steps, 2) pre-preg processing step；3) alkaline boiling processing step；4) refinement treatment step etc..Preparation method according to the present invention devises a whole set of dissolving pulp preparation process for this trade waste of xylose residue, 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 a kind of wood generated using xylose extraction process
Sugar residue produces the preparation method of xylose residue dissolving pulp (high pure cellulose).
Background technique
Dissolving pulp is a kind of special chemical pulp, is made of high-purity good fiber quality element, can be used to produce high added value
Product, mainly for the production of products such as viscose rayon, nitrocellulose, acetate fiber, glassine papers.Dissolving pulp major producing country, the world
For the U.S., South Africa, Canada, Brazil etc., China is the maximum country of consumption of world's dissolving pulp, accounts for the 40% of world's total amount.At present
China's dissolving pulp import volume is very big, and interdependency is about 60%, and the demand of Science in Future in China dissolving pulp and yield are still expected to
Keep higher growth rate.
Currently, the primary raw material of dissolving pulp is timber and cotton linter etc., in recent years, bamboo also becomes the important of dissolving pulp
Raw material.But different raw material need different technique to produce dissolving pulp, and preparing dissolving pulp both at home and abroad, there are mainly two types of techniques
Acid sulfite process can be used in method, in general, the low raw material of hemicellulose level；The high raw material of resin content, then must
Prehydrolytic sulfate process must be used.Wood type raw material mainly uses sulphite process and prehydrolytic sulfate process, and cotton linter master
It to use alkaline process (Sixta, Handbook of Pulp, 2006).Sulphite process is a kind of containing free SO2Bisulfite
The method of salt boiling at high temperature, past major part needlebush dissolving pulp and some leaf wood dissolving pulps are all in this way.
But this method is relatively stringent to ingredient requirement, liquid waste processing is complicated, is gradually substituted now by prehydrolytic sulfate process.China
The production of dissolving pulp is transformed into leaf wood and bamboo is the sulfuric acid of raw material also gradually from timber mixture sulphite digesting technoloy
Bisulfite cooking technique, kraft cooking device therefor uses import equipment mostly at present.
Cotton linter is a kind of preferable dissolving pulp raw material, and alkaline process treatment conditions are generally 150-175 DEG C, alkali charge 14-
18%.The pre-hydrolysis technique of prehydrolytic sulfate process generally uses 100-125 DEG C of inorganic acid to hydrolyze or 140-180 DEG C
The treatment conditions class of the techniques such as boiling, the bleaching of anacidity hydrolysis, subsequent sulfuric acid salt treatment process and traditional paper-making pulping industry
Seemingly.The method for preparing bamboo dissolving pulp is similar with timber dissolving pulp is prepared, and prehydrolytic sulfate process and prehydrolysis caustic soda can be used
Method.
Dissolving pulp production have developed rapidly in China, but existing above-mentioned production technology still has many problems and lacks
Point.Firstly, process conditions are similar with traditional pulp industry, generally all relatively acutely, reaction temperature is higher than treatment conditions
150 DEG C, alkali charge is greater than 20% etc.；Secondly, in order to obtain the dissolving pulp of high-quality, it will usually complicated treatment process is introduced,
Increase process costs, such as: enzymatic treatment, low temperature extraction technique etc.；Again, China's timber and bamboo timber resource are deficient, raw material
Price is higher, and it is even more impossible to meet existing industrial requirement for cotton linter source scarcity.
Xylose residue is the waste residue obtained after industrial xylose extraction process using lignocellulosics such as corncobs as raw material,
The annual xylose residue waste in China is about 1.3 × 108Ton.The research of resource utilization about xylose residue is more, but real
The part being utilized in production is seldom.Xylose residue cellulose and traditional paper pulp fiber, bamboo pulp fiber are significantly different, main
The shape of cellulose is micron particles (about 100 microns).There are no good higher value applications for this granular wood fibre
Mode can not also be applied in traditional paper industry.The microcosmic character of xylose residue fiber different from conventional wooden fibrous raw material,
Existing dissolving pulp preparation process is not appropriate for this special fibrous raw material.
The present invention is directed to this special and cheap fibrous raw material of xylose residue, while being intended to improve in existing industrial flow
The disadvantages for the treatment of conditions are violent, processing step is complicated, provides that a kind of raw material sources are cheap, treatment conditions are mild, simple process
Xylose residue dissolving pulp preparation method.The dissolving pulp can be used for producing viscose rayon, tencel (Lyocell fiber) and other fibres
Tie up plain derivative product.
Summary of the invention
The technology problem in resource utilization and existing dissolving pulp preparation process for above-mentioned xylose residue, according to
One aspect of the present invention proposes a set of mild preparation method by xylose residue production dissolving pulp.
To achieve the above object, preparation method of the invention the following steps are included:
1) pretreatment of raw material:, can be by selectively carrying out since raw material xylose slag often has a large amount of lump particles
Mechanical lapping etc. handles (such as disc mill, planetary ball mill etc.), Lai Zengjia raw material uniformity coefficient.
2) pre-preg is handled: solid-to-liquid ratio 1:5-1:15 is added water into the xylose residue of homogenizing obtained in step 1), then
Hydrochloric acid or sulphur acid for adjusting pH is added to 1-7, adds auxiliary agent A and is directly heated after mixing evenly to 40-95 DEG C of progress pre-preg
20-90min is handled, after the completion of pre-preg, squeezes out pre-preg liquid, will be presoaked with the water of pre-preg xylose residue 5-20 times of weight of product
Stain xylose residue is cleaned；
Wherein, relative to the absolute dry mass of xylose residue, the additional amount of the auxiliary agent A is 0.1%-2wt%.The auxiliary agent A
It is made of chelating agent and surfactant, the chelating agent is selected from EDTA (ethylenediamine tetra-acetic acid) and/or DTPA (diethyl three
Triamine pentaacetic acid), the surfactant is selected from neopelex, sodium lignin sulfonate, lauryl sodium sulfate, poly- second
One or more of surfactants such as glycol, Tween80, Span20, empgen BB, nonylphenol polyoxyethylene ether
Mixture, the mass values of the chelating agent and the surfactant are 1:10 to 1:0.5；
3) alkaline boiling is handled: into the pre-preg xylose residue cleaned obtained in step 2) according to solid-to-liquid ratio to 1:4-1:8
Water is added, the alkali of 3-12wt% and the auxiliary agent B of 0.1%-4wt%, mechanical stirring 2- is added relative to the absolute dry mass of xylose residue
It is pre-mixed within 15 minutes, reaction 30-150 minutes is then carried out under the conditions of 70-120 DEG C；After reaction, waste liquid is squeezed out, then
Remaining solid to be cleaned with the water of 5-20 times of weight of solid product, the product after cleaning is crude fibre, after boiling, washings
Expect spare and recycles black liquor；
The wherein mixture that the auxiliary agent B 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；
4) refinement treatment: multistage bleaching refinement treatment is carried out to the crude fibre that step 3) obtains, the multistage bleaching can be adopted
With 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, solid-liquid after every section of bleaching
Than to 1:6-1:12, after treatment is washed to obtain final dissolving pulp product (high pure cellulose).
Preferably, the multistage drift of chlorine dioxide and alkali density alternately can also be used in multistage bleaching described in step 4)
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:
5) 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.
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 cleaned pre-preg xylose residue with the water of pre-preg xylose residue 8-15 times of weight of product.
It is further preferred that squeezing out preimpregnation in the step 2) of preparation method according to the present invention after the completion of pre-preg
Stain liquid is cleaned pre-preg xylose residue with the water of pre-preg xylose residue 10 times of weight of product.
It is further preferred that chelating agent described in the step 2) of preparation method according to the present invention and the surface are living
Property agent mass values be 1:5 to 1:0.8；
Preferably, 5-12wt%, more preferably 10- is added in the step 3) of preparation method according to the present invention
The alkali of 12wt%；
Preferably, the cellulose protective agent of auxiliary agent B is constituted described in the step 3) of preparation method according to the present invention
Mass values with surfactant are 1:10 to 1:5.
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 product of pre-preg xylose residue, the water of most preferably 10 times weight cleans remaining solid.
Beneficial effect
Preparation method according to the present invention devises a whole set of dissolving pulp preparation process for this trade waste of xylose residue,
It provides more choices for its higher value application；Present invention process step is simple, and equipment and factory overheads cost are low；Handle item
Part is relatively mild, and chemical levels are few, and production energy consumption, chemical reagent cost and liquid waste processing difficulty are low；Simple processing
Process and mild reaction condition, reduce the excessive degradation of cellulose, to improve or stabilize alpha-cellulose content, fiber
The plain 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.
Due to xylose extraction process and the instable influence of raw material sources, there may be a large amount of lump particles for xylose residue.
Preparation method according to the present invention needs feed pretreatment step to increase raw material uniformity coefficient, wherein can be by there is selection
Property carry out mechanical treatment or chemical treatment increase the mechanical grinding of raw material uniformity coefficient, such as disc mill, planetary ball mill etc.
Mill processing, or soda acid is added under the premise of not influencing subsequent processes and discongests the modes such as agent.
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 xylose residue in residual sugar, extract and ash content, reduce subsequent purification cellulose
Pressure.Wherein relative to the absolute dry mass of xylose residue, the additional amount of the auxiliary agent A is 0.1%-2wt%.The chelating agent choosing
From EDTA and/or DTPA, chelating agent can remove the middle ash content of raw material, especially removing metal ion, if in final product
There are excessive metal ions, then unfavorable to subsequent application, the surfactant is selected from neopelex, wooden
Plain sodium sulfonate, lauryl sodium sulfate, polyethylene glycol, Tween80, Span20, empgen BB, Nonyl pheno
The mixture of one or more of the surfactants such as ether, surfactant can promote the removing of extract, be conducive to improve
The purity of cellulose.The mass values of the chelating agent and the surfactant are 1:10 to 1:0.5, the use of the chelating agent
Amount should not be too large, but if ratio is less than 1:10, ash content removal effect is unobvious (removing of especially iron ion is unobvious), such as
Fruit ratio is greater than 1:0.5, then extract removal efficiency is too low (less than 50%).
By being added relative to the exhausted of xylose residue in the alkaline boiling processing of the step 3) of preparation method according to the present invention
The alkali of 3-12wt% and the auxiliary agent B of 0.1%-4wt% is added in dry mass, and is realized under relatively mild conditions to xylose
The boiling of slag, thus the lignin in removing xylose residue as much as possible, but reservation cellulose as much as possible simultaneously, guarantee fine
Dimension is known as higher yield.
Wherein, relative to the absolute dry mass of xylose residue, the alkali of 3-12wt% and the auxiliary agent B of 0.1%-4wt% is added, it is described
Auxiliary agent B is the mixture of cellulose protective agent and surfactant.The fiber protection agent mainly protects cellulose, avoids alkali
Transition degradation to cellulose；And the effect of the surfactant is first is that promote the protectant fine dispersion of cellulose and infiltration
Thoroughly, second is that being conducive to the dissolution of lignin.
If the dosage of the cellulose protective agent and surfactant is less than above range, cellulose yield can drop
Low, loss is excessive, and delignification is insufficient, influences further purification effect.It is pre-mixed within mechanical stirring 2-15 minutes, then
Reaction 30-150 minutes is carried out under the conditions of 70-120 DEG C；After reaction, waste liquid is squeezed out, then with 5-20 times of solid product,
It is preferred that 8-15 times, the water of most preferably 10 times weight cleans remaining solid, and the product after cleaning is crude fibre, after boiling,
Washing material is spare and recycles black liquor；
The wherein mixture that the auxiliary agent B 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.
4) refinement treatment: multistage bleaching refinement treatment is carried out to the crude fibre that step 3) obtains, the multistage bleaching can be adopted
With 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, solid-liquid after every section of bleaching
Than to 1:6-1:12, 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 4) 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:
5) 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.
Xylose residue used in embodiment is the Feitian pharmaceutcal corporation, Ltd that raw material produces xylose from corncob is utilized, and is
A kind of trade waste after extraction xylose.
Embodiment 1:
A kind of preparation method of viscose rayon xylose residue dissolving pulp, the specific steps of which are as follows:
1) xylose residue is added water to solid-to-liquid ratio is 1:9, and PFI fiberizer is then added and is ground, fiberizer revolving speed
1460rpm, grinding clearance 0.24mm, defibrination revolution are 1000 turns.
2) xylose residue is added water to solid-to-liquid ratio is 1:10, and pH value is about 2.7 at this time；Heating-up time 15min, temperature reach 75
DEG C, relative to the weight of raw material xylose slag, the sodium dodecyl benzenylsulfonate of 0.5wt% and the EDTA of 0.2wt% are added, when heat preservation
Between be 60min；Pre-preg after treatment passes through washing (water consumption is 10 times of solid material quality, is washed in two times).It removes
Fall sugar remaining in xylose residue, part of ash and extract.After handling with this condition, extract removal efficiency is grey up to 86%
Dividing removal efficiency is 67%.
3) relative to xylose residue oven dry weight, the NaOH, 0.2wt% of 10wt% are added into the xylose residue that step 2) obtains
Anthraquinone and 2wt% sodium lignosulfonate, and water is added to adjust solid-to-liquid ratio to 1:5；Heat up 18min, and temperature reaches 90 DEG C, heat preservation
100min；After boiling, washs and recycle black liquor and slurry of solids.With this condition, delignification rate 87%, fiber
Plain yield is 95%.
4) relative to slurry of solids oven dry weight, the hydrogen peroxide of 8wt% is added into the slurry of solids that step 3) obtains,
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 51% (relative to original xylose residue oven dry weight), the degree of polymerization 551, Fe
Ion concentration 38.5ppm, hemi-cellulose content 0.2%, extract content 0.15%, alpha-cellulose content 93.2% are fully met
Viscose rayon production requirement.
Embodiment 2:
A kind of tencel (Lyocell fiber) uses the preparation process of dissolving pulp, the specific steps of which are as follows:
1) xylose residue is added water to solid-to-liquid ratio is 1:9, and single-plate paste mill is then added and is ground, fiberizer revolving speed
1500rpm, grinding clearance 0.2mm.
2) xylose residue adds water to solid-to-liquid ratio 1:10 after the processing of single hop mill, and with sulphur acid for adjusting pH value to 2.0；Heating
Time 15min, temperature reach 80 DEG C, and soaking time 60min is added 0.1wt%'s relative to the weight of raw material xylose slag
The Tween80 of DTPA and 0.5wt%.Pre-preg after treatment, by washing (water consumption is 10 times of solid material quality,
Wash in two times) remove sugar remaining in xylose residue, part of ash and extract.For extract removal efficiency up to 88%, ash content is de-
Except rate is 70%.
3) relative to xylose residue oven dry weight, the NaOH, 0.2wt% of 11wt% are added into the xylose residue that step 2) obtains
Green oxygen and 1wt% lauryl sodium sulfate, and water is added to adjust solid-to-liquid ratio to 1:6, heat up 18min, and temperature reaches 95 DEG C, protects
Warm 100min；After boiling, washs and recycle black liquor and slurry of solids.After the completion of processing, delignification rate up to 90%,
Cellulose yield is 97%.
4) relative to slurry of solids oven dry weight, the titanium dioxide of 0.6wt% is added into the slurry of solids that step 3) obtains
Chlorine adds water to solid-to-liquid ratio 1:9, and adjusts pH value to 2.5；It is rapidly heated to 75 DEG C, keeps the temperature 60min；After bleaching, filtering stock is extremely
Then neutrality is added the hydrogen peroxide of the NaOH and 2wt% of 2wt%, adds water to solid-to-liquid ratio 1:9, be 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 1:9, and adjust pH
It is worth to 2.0；It is rapidly heated to 70 DEG C, after keeping the temperature 120min, washing to neutrality；Then add the NaOH's and 2wt% of 2wt%
It is primary that hydrogen peroxide repeats alkali density above-mentioned；Removing iron ion processing is finally carried out, EDTA dosage 1wt%, locates by 85 DEG C of temperature
The reason time 1 hour obtains xylose residue dissolving pulp product after the washing that is disposed.
The total slurry yield of the dissolving pulp product be 45% (relative to original xylose residue oven dry weight), the degree of polymerization 538, Fe from
Sub- content 4.5ppm, hemi-cellulose content 0wt%, extract content 0.05wt%, alpha-cellulose content 96.4wt% are fully achieved
The quality requirement of tencel dissolving pulp.
Embodiment 3:
A kind of preparation process of viscose rayon dissolving pulp, the specific steps of which are as follows:
1) xylose residue is added water to solid-to-liquid ratio is 1:9, and PFI fiberizer is then added and is ground, fiberizer revolving speed
1460rpm, grinding clearance 0.21mm, reporting is 800 turns.
2) polished xylose residue is added water into solid-to-liquid ratio 1:10, and with sulphur acid for adjusting pH value to 1.5；Heating-up time
15min, temperature reach 70 DEG C, soaking time 90min, and relative to the weight of raw material xylose slag, EDTA dosage is 0.7wt%,
Polyethylene glycol dosage is 0.6wt%, and pre-preg after treatment, by washing, (water consumption is 10 times of solid material quality, is divided
Wash twice) remove sugar remaining in xylose residue, part of ash and extract.With this condition, extract removal efficiency is 84%,
Ash content removal efficiency is 67%.
3) relative to xylose residue oven dry weight, NaOH, 0.6wt% of 12wt% are added into the xylose residue that step 2) obtains
Magnesium sulfate and 2wt% Span20, and water is added to adjust solid-to-liquid ratio to 1:6, heat up 18min, and temperature reaches 90 DEG C, heat preservation
100min；After boiling, washs and recycle black liquor and slurry of solids.After handling with this condition, delignification rate is
86%, cellulose yield is 98%.
4) relative to slurry of solids oven dry weight, the titanium dioxide of 0.3wt% is added into the slurry of solids that step 3) obtains
Chlorine adds water to solid-to-liquid ratio 1:8, and adjusts pH value to 2；It is rapidly heated to 75 DEG C, keeps the temperature 60min；After bleaching, filtering stock is into
Property, the hydrogen peroxide of the NaOH and 1wt% of 3wt% is then added, adds water to solid-to-liquid ratio 1:8, is rapidly heated to 80 DEG C, keeps the temperature
60min；After alkali density, the chlorine dioxide of 0.3wt% is added in filtering stock to neutrality, adds water to solid-to-liquid ratio 1:8, and adjust pH
It is worth to 2.0；It is rapidly heated to 70 DEG C, after keeping the temperature 120min, washing to neutrality obtains dissolving pulp product.
The total slurry yield of dissolving pulp product is 48% (relative to original xylose residue oven dry weight), the degree of polymerization 543, Fe ion
Content 41.7ppm, hemi-cellulose content 0.1wt%, extract content 0.1wt%, alpha-cellulose content 94.4wt%, fiber product
Quality reaches the quality requirement of production viscose rayon.
Embodiment 4:
A kind of preparation process preparing cellulose acetate dissolving pulp, the specific steps of which are as follows:
1) xylose residue is added water to solid-to-liquid ratio is 1:8, and single-plate paste mill is then added and is ground, fiberizer revolving speed
1500rpm, grinding clearance 0.2mm.
2) xylose residue adds water to solid-to-liquid ratio 1:10 after the processing of single hop mill, and with sulphur acid for adjusting pH value to 1.5；Heating
Time 15min, temperature reaches 90 DEG C, soaking time 60min, and relative to the weight of raw material xylose slag, the dosage of DTPA is
The dosage of 0.5wt%, lauryl sodium sulfate are 1wt%, and pre-preg after treatment, by washing, (water consumption is solids
10 times for expecting quality wash in two times) remove sugar remaining in xylose residue, part of ash and extract.It handles with this condition
Afterwards, the removal efficiency of extract is 89%, and the removal efficiency of ash content is 71%.
3) relative to xylose residue oven dry weight, the NaOH, 0.2wt% of 12wt% are added into the xylose residue that step 2) obtains
Magnesia and 1wt% Tween80, and water is added to adjust solid-to-liquid ratio to 1:6；Heat up 18min, and temperature reaches 90 DEG C, heat preservation
120min；After boiling, washs and recycle black liquor and slurry of solids.After handling with this condition, the removal efficiency of lignin is
91%, cellulose yield is 92%.
4) relative to slurry of solids oven dry weight, the titanium dioxide of 0.5wt% is added into the slurry of solids that step 3) obtains
Chlorine adds water to solid-to-liquid ratio 1:9, and adjusts pH value to 2.5；It is rapidly heated to 75 DEG C, keeps the temperature 60min；After bleaching, filtering stock is extremely
Then neutrality is added the hydrogen peroxide of the NaOH and 1wt% of 2wt%, adds water to solid-to-liquid ratio 1:9, be 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 1:9, and adjust pH
It is worth to 2.5；It is rapidly heated to 75 DEG C, after keeping the temperature 60min, washing to neutrality；The NaOH for adding 2wt% repeats alkali above-mentioned and takes out
It mentions once, the DTPA of 0.15wt% is added after washing, is handled 50 minutes at 75 DEG C, is finally washed to neutrality and obtain dissolving pulp product.
The total slurry yield of dissolving pulp product is 42% (relative to original xylose residue oven dry weight), the degree of polymerization 658, Fe ion
Content 3.1ppm, hemi-cellulose content 0wt%, extract content 0.06wt%, alpha-cellulose content 96.1wt%, product reach raw
Produce the quality requirement of cellulose acetate.
Comparison example 1
A kind of preparation method of viscose rayon xylose residue dissolving pulp, the specific steps of which are as follows:
1) xylose residue is added water to solid-to-liquid ratio is 1:8, and PFI fiberizer is then added and is ground, fiberizer revolving speed
1460rpm, grinding clearance 0.22mm, revolution are 2000 turns.
2) ground xylose residue, is added water into solid-to-liquid ratio 1:10, pH value is about 2.7 at this time；Heating-up time 15min, temperature
Degree reaches 75 DEG C, and soaking time 60min is added without chelating agent and surfactant；Pre-preg after treatment passes through washing
Remove sugar remaining in xylose residue, part of ash and extract.After handling with this condition, extract removal efficiency only has 72%,
Ash content removal efficiency only has 53%, hence it is evident that lower than 86% in embodiment 1 extract removal efficiency and 67% ash content removal efficiency.
3) NaOH (relative to xylose residue oven dry weight) of 10wt%, is added into the xylose residue that step 2) obtains, and adds
Water adjusts solid-to-liquid ratio to 1:5；Heat up 18min, and temperature reaches 90 DEG C, keeps the temperature 100min, without addition cellulose protective agent
And surfactant；After boiling, washs and recycle black liquor and slurry of solids.With this condition, delignification rate only has
74%, cellulose yield only has 89%.Significantly lower than in embodiment 1 87% delignification rate and 95% cellulose obtain
Rate.
4) hydrogen peroxide of 8wt%, is added into the slurry of solids that step 3) obtains (relative to slurry of solids over dry weight
Amount), solid-to-liquid ratio 1:9 is added water to, and adjust pH value to 10.5 with NaOH；Heat up 18min, and temperature reaches 95 DEG C, keeps the temperature 120min；
After bleaching, 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 be 55wt% (relative to original xylose residue oven dry weight), the degree of polymerization 521,
Fe ion concentration 57ppm, hemi-cellulose content 1%, extract content 2.1%, alpha-cellulose content 90.3wt%, due to alpha fibre
For cellulose content less than 92%, iron ion content is greater than 40ppm, is not able to satisfy viscose rayon production requirement.This is mainly due to front ends
It is insufficient to handle extract, ash content, delignification, so subsequent processing is extremely difficult to target product requirement.
Comparative example 2
A kind of tencel (Lyocell fiber) uses the preparation process of dissolving pulp, the specific steps of which are as follows:
1), xylose residue adds water to solid-to-liquid ratio 1:10 after the processing of single hop mill, and with sulphur acid for adjusting pH value to 2.0；Heating
Time 15min, temperature reach 80 DEG C, and soaking time 60min is added without chelating agent and surfactant；Pre-preg processing knot
Shu Hou removes sugar remaining in xylose residue, part of ash and extract by washing.Extract removal efficiency only has 76%, ash content
Removal efficiency only has 57%, hence it is evident that lower than 88% in embodiment 2 extract removal efficiency and 70% ash content removal efficiency.
2) NaOH of 11wt%, is added into the xylose residue that step 1) obtains, and water is added to adjust solid-to-liquid ratio to 1:4；Heating
18min, temperature reach 95 DEG C, keep the temperature 100min, without addition cellulose protective agent and surfactant；Boiling terminates
Afterwards, it washs and recycles black liquor and slurry of solids.After the completion of processing, delignification rate only has 83%, and cellulose yield only has
87%, hence it is evident that delignification rate lower than in embodiment 2 90% and 97% cellulose yield.
3), into the slurry of solids that step 2) obtains be added 0.6% chlorine dioxide (relative to slurry of solids 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
To neutrality, the hydrogen peroxide of the NaOH and 2wt% of 2wt% is then added, adds water to solid-to-liquid ratio 1:9, is rapidly heated to 80 DEG C, protects
Warm 60min；After alkali density, 0.2% chlorine dioxide is added in filtering stock to neutrality, adds water to solid-to-liquid ratio 1:9, and adjust pH
It is worth to 2.0；It is rapidly heated to 70 DEG C, after keeping the temperature 120min, washing to neutrality；Then add the NaOH's and 2wt% of 2wt%
It is primary that hydrogen peroxide repeats alkali density above-mentioned；Removing iron ion processing is finally carried out, EDTA dosage 1wt%, locates by 85 DEG C of temperature
The reason time 1 hour obtains xylose residue dissolving pulp product after the washing that is disposed.
The total slurry yield of the dissolving pulp product is 43wt% (relative to original xylose residue oven dry weight), the degree of polymerization 503, Fe
Ion concentration 24.7ppm (is greater than 5ppm), hemi-cellulose content 0.8wt%, content of lignin 0.9wt%, extract content
1.1wt%, alpha-cellulose content 87.2wt% (less than 92%), cannot reach the quality requirement of tencel dissolving pulp.Due to preceding
End processing extract, ash content, delignification are insufficient, so subsequent processing is extremely difficult to target product requirement.
Claims (8)
1. a kind of preparation method by xylose residue production dissolving pulp, including the following steps are included:
1) pretreatment of raw material: by selectively carrying out the processing such as mechanical lapping, such as disc mill or planetary ball mill, to increase
Add raw material uniformity coefficient；
2) pre-preg is handled: being added water to solid-to-liquid ratio 1:5-1:15 into the xylose residue of homogenizing obtained in step 1), is then added
Hydrochloric acid or sulphur acid for adjusting pH add auxiliary agent A and are directly heated after mixing evenly to 40-95 DEG C of progress pre-preg processing to 1-7
20-90min 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 that pre-preg is wooden
Sugar residue is cleaned；
Wherein, relative to the absolute dry mass of xylose residue, the additional amount of the auxiliary agent A is 0.1%-2wt%.The auxiliary agent A be by
Chelating agent and surfactant composition, the chelating agent are selected from EDTA (ethylenediamine tetra-acetic acid) and/or DTPA (diethyl triamine five
Acetic acid), the surfactant is selected from neopelex, sodium lignin sulfonate, lauryl sodium sulfate, poly- second two
One or more of the surfactants such as alcohol, Tween80, Span20, empgen BB, nonylphenol polyoxyethylene ether
The mass values of mixture, the chelating agent and the surfactant are 1:10 to 1:0.5；
3) alkaline boiling is handled: being added into the pre-preg xylose residue cleaned obtained in step 2) according to solid-to-liquid ratio to 1:4-1:8
The alkali of 3-12wt% and the auxiliary agent B of 0.1%-4wt% is added relative to the absolute dry mass of xylose residue in water, and mechanical stirring 2-15 divides
Clock premixing, then carries out reaction 30-150 minutes under the conditions of 70-120 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, and after boiling, washing material is standby
With and recycle black liquor；
The wherein mixture that the auxiliary agent B 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；
4) refinement treatment: multistage bleaching refinement treatment is carried out to the crude fibre that step 3) obtains, the multistage bleaching can be used more
Section 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, it is preferable that 2-3 sections of hydrogen peroxide bleachings, fibre stuff is washed to pH neutrality after every section of bleaching, and solid-to-liquid ratio is extremely
1:6-1:12, after treatment are washed to obtain final dissolving pulp product (high pure cellulose).
2. according to claim 1 by the preparation method of xylose residue production dissolving pulp, which is characterized in that more described in step 4)
The multistage bleaching of chlorine dioxide and alkali density alternately can also be used in section bleaching, wherein relative to the absolute dry mass of fiber, two
Chlorine monoxid single hop dosage is 0.1-1wt%, and pH value=1-4, temperature is 60-100 DEG C；Relative to the absolute dry mass of fiber, alkali is taken out
Proposing middle NaOH dosage is 0.5-4wt%, the hydrogen peroxide of alternative addition 0-4wt% in alkali density, adjusting pH value to 9-12,
Single hop handles the time as 30-180min, it is preferable that using 3-4 sections of alternate treatment.
3. according to claim 1 by the preparation method of xylose residue production dissolving pulp, which is characterized in that the preparation method can
To further include steps of
5) 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 xylose residue dissolving pulp (high pure cellulose) product.
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；Preimpregnation
After the completion of stain, pre-preg liquid is squeezed out, is cleaned pre-preg xylose residue with the water of pre-preg xylose residue 8-15 times of weight of product.
4. according to claim 1 by the preparation method of xylose residue production dissolving pulp, which is characterized in that the preparation method
In step 2) after the completion of pre-preg, pre-preg liquid is squeezed out, with the water of pre-preg xylose residue 10 times of weight of product by pre-preg xylose
Wash heat is net.
5. according to claim 1 by the preparation method of xylose residue production dissolving pulp, which is characterized in that the preparation method
The mass values of chelating agent described in step 2) and the surfactant are 1:5 to 1:0.8.
6. according to claim 1 by the preparation method of xylose residue production dissolving pulp, which is characterized in that the preparation method
5-12wt%, the more preferably alkali of 10-12wt% are added in step 3).
7. according to claim 1 by the preparation method of xylose residue production dissolving pulp, which is characterized in that the preparation method
The mass values of cellulose protective agent and surfactant that auxiliary agent B is constituted described in step 3) are 1:10 to 1:5.
8. according to claim 1 by the preparation method of xylose residue production dissolving pulp, which is characterized in that the preparation method
In step 3) after reaction, waste liquid is squeezed out, with 8-15 times of product of pre-preg xylose residue, the water of most preferably 10 times weight will be remained
Remaining solid is cleaned.
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| CN113445344A (en) * | 2021-07-29 | 2021-09-28 | 陕西科技大学 | Biomass refining method for removing lignin |
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