CN105143273A - 从农业产业残余物获得羧甲基纤维素的方法和羧甲基纤维素及其用途 - Google Patents
从农业产业残余物获得羧甲基纤维素的方法和羧甲基纤维素及其用途 Download PDFInfo
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- CN105143273A CN105143273A CN201380033404.4A CN201380033404A CN105143273A CN 105143273 A CN105143273 A CN 105143273A CN 201380033404 A CN201380033404 A CN 201380033404A CN 105143273 A CN105143273 A CN 105143273A
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- carboxymethyl cellulose
- cmc
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 title claims abstract description 71
- 235000010948 carboxy methyl cellulose Nutrition 0.000 title claims abstract description 69
- 239000001768 carboxy methyl cellulose Substances 0.000 title claims abstract description 67
- 239000008112 carboxymethyl-cellulose Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 65
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 14
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 239000012153 distilled water Substances 0.000 claims abstract description 8
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- 239000000835 fiber Substances 0.000 claims description 36
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- 244000060011 Cocos nucifera Species 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 9
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- 238000000227 grinding Methods 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
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- 206010033546 Pallor Diseases 0.000 claims 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 15
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- 239000002585 base Substances 0.000 description 11
- -1 basic metal chloroacetate salt Chemical class 0.000 description 9
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- 229910052728 basic metal Inorganic materials 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 6
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- 235000019832 sodium triphosphate Nutrition 0.000 description 4
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- 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 description 2
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- 230000000877 morphologic effect Effects 0.000 description 2
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 2
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- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 235000020415 coconut juice Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 235000015243 ice cream Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000008141 laxative Substances 0.000 description 1
- 230000002475 laxative effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006194 liquid suspension Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
- A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
- A23L29/262—Cellulose; Derivatives thereof, e.g. ethers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
- A61K9/16—Agglomerates; Granulates; Microbeadlets ; Microspheres; Pellets; Solid products obtained by spray drying, spray freeze drying, spray congealing,(multiple) emulsion solvent evaporation or extraction
- A61K9/1605—Excipients; Inactive ingredients
- A61K9/1629—Organic macromolecular compounds
- A61K9/1652—Polysaccharides, e.g. alginate, cellulose derivatives; Cyclodextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/06—Rendering cellulose suitable for etherification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
- C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/26—Cellulose ethers
- C08L1/28—Alkyl ethers
- C08L1/286—Alkyl ethers substituted with acid radicals, e.g. carboxymethyl cellulose [CMC]
-
- 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
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
-
- 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
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/20—Chemically or biochemically modified fibres
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/25—Cellulose
- D21H17/26—Ethers thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Biochemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Epidemiology (AREA)
- Wood Science & Technology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Pharmacology & Pharmacy (AREA)
- Dispersion Chemistry (AREA)
- Nutrition Science (AREA)
- Food Science & Technology (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Paper (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Jellies, Jams, And Syrups (AREA)
- Medicinal Preparation (AREA)
Abstract
本发明描述了用于从农业产业残余物获得羧甲基纤维素(CMC)的有利的和有效的方法,该方法包括以下步骤:a)准备原料,其中该原料经清洗、干燥、研磨和再次清洗;b)泵送步骤,其中从步骤a)获得的产物与氢氧化钠反应;c)合成步骤,其中在于研磨浆料、在室温在搅拌下添加异丙醇和蒸馏水的溶液;添加NaOH水溶液以使混合物碱化;添加异丙醇中的一氯乙酸;过滤;在甲醇溶液中悬浮和用乙酸中和。本发明还涉及由所述方法获得的CMC,其可以用于若干工业过程中。
Description
本申请要求于2012年5月9日提交的名称为“源自农业综合产业残余物的天然纤维基粘合剂,和获得天然纤维基粘合剂的方法”的美国专利申请61/644,856,其在此整体引入以供参考。
发明领域
本发明涉及获得源自农业综合产业残余物的纤维基粘合剂的方法,和由所述方法生产的羧甲基纤维素。
相关技术说明
本领域已知用羧甲基纤维素(CMC)钠生产的一些粘合剂。以下文献显示了这种粘合剂的实例和它们相应的生产方法。
巴西专利PI0801555-4描述了用于铁矿石造粒的粘合剂。所述粘合剂含有膨润土和多糖用于粘合磨细的铁矿石。该发明还涉及制备铁矿石粒料的方法,其中将包含多糖和膨润土的组合物用作粘合剂。
US4,410,694描述了制备羧甲基纤维素的方法,包括使碱性反应液连续地循环通过装填在反应容器中的纤维素纤维,该纤维素纤维选自天然纤维素纤维和再生纤维素纤维,所述反应液的流速大于10l/min每Kg所述纤维素纤维,所述反应液包含有效量的醚化剂,该醚化剂选自一氯乙酸及其盐,溶解在基本上由乙醇和水组成的均匀的碱性溶剂中,所述循环的时间足以基本上完全将所述纤维素纤维转化为所述羧甲基纤维素纤维。
US3,900,463描述了制备具有均匀分布的置换度的碱性羧甲基纤维素的方法,该方法包括在溶剂系统的存在下用醚化剂处理纤维素,该醚化剂选自碱金属一氯乙酸盐和一氯乙酸低级烷基酯,该溶剂体系由至少一种有机溶剂和水组成,该处理直到获得醚化剂在纤维素中的均匀分布,以0.4至2.0mol每纤维素葡萄糖酸酐单位使用该醚化剂,和向得到的混合物添加碱金属,以不少于碱金属一氯乙酸盐的等克分子量或者不少于一氯乙酸低级烷基酯的两倍克分子量使用该碱金属,然后在室温至回流问题的温度进行处理,直到醚化完成。
US4,401,813描述了制备一种形式的羧甲基纤维素的方法,该羧甲基纤维素在氯化钙水溶液中展现了优异的流变和流体损失特性,该方法包括在无氧条件下,在小于350℃的温度,在含有86.9±2wt%异丙醇的水溶液中,以2至1:7.5至1的异丙醇水溶液与纤维素重量比,进行高分子量纤维素的苛化,该苛化在足量碱金属氢氧化物存在下进行以使随后碱金属纤维素的醚化期间碱金属氢氧化物与一氯乙酸的摩尔比大于2.00:1,其中所用的一氯乙酸含有小于约2wt%的二氯乙酸。
采矿业中使用的CMC,更具体地作为粘合剂矿石,负责矿石颗粒的聚结。粒料形成是造粒过程最重要的阶段之一,受到几种因素的影响,对最终的产品品质产生直接影响。
CA1,336,641描述了在水存在下用于铁矿石的粘合剂,含有10%至90%的可溶于水的羧甲基纤维素钠和10%至90%的碳酸钠。该专利还描述了在矿石中使用粘合剂的方法。
CA1,247,306描述了在水存在下使用粘合剂粘合铁矿石颗粒的方法,该粘合剂由羟乙基纤维素和碳酸钠组成。
US4,288,245描述了在糊剂存在下将金属矿石造粒的方法,该糊剂含有碱金属盐和量为至少0.01%的羧甲基纤维素,并结合有源自碱金属和酸的一种或多种盐。
US4,486,335描述了生产含铁矿石的粘合剂的方法,和该方法的产品。该发明描述了羧甲基羟乙基纤维素基粘合剂,当结合水溶液中的铝离子时,该粘合剂形成凝胶。
US4,597,797描述了在水存在下用于矿石的粘合剂,和作为粘合剂的羧甲基纤维素的碱金属盐。该组合物包含羧甲基纤维素的碱金属盐和源自碱金属和羧酸的一种或多种盐。弱酸的碱金属盐优选为源自乙酸、苯甲酸、乳酸、丙酸、酒石酸、琥珀酸、柠檬酸、亚硝酸、硼酸和碳酸的那些。
US4,863,512涉及用于在水存在下粘合精矿(concentratedore)材料的有用的粘合剂,该粘合剂包含羧甲基纤维素的碱金属盐和三聚磷酸钠,用该糊剂粘合精矿材料的方法,和从该方法得到的经粘合的产品。
US4,919,711公开了用于在包含经选择的水溶性聚合物的水存在下粘合精矿材料的有用的粘合剂,该粘合剂由羧甲基纤维素或羧甲基羟乙基纤维素的碱金属盐和三聚磷酸钠组成。除该产品之外,该专利还描述了用该糊剂粘合精矿材料的方法,和由该方法得到的经粘合的产品。
US6,497,746描述了用于粘合颗粒的方法(例如造粒)和由该方法生产的产品(即粒料)。该方法用于粘合粒状材料以生产混合物,该粒状材料包含有效量的水用于润湿,有效量的粘合的聚合物,该聚合物选自淀粉、改性淀粉、淀粉衍生物、藻酸盐、果胶及其混合物,和有效量的粘合的弱酸的盐。
巴西是农业产业(argo-industrial)废物的最大生产国之一。这些废物未经任何预先处理排放到环境中,会引起若干危害。
作为农业产业纤维残余物,椰子在这种将要大规模生产的情况中很突出。据估计,巴西的椰子从280,000公顷以上的面积收获的年产量超过15亿单位。椰子加工是一项产生废物的活动,取出有价值的固体蛋白质用于获得椰汁和椰肉之后,以外果皮、中果皮和内果皮为代表的剩余部分占果实成分的约45%。这种残余物难以清除,被送至垃圾场和填埋场,运输到这些地点提供了产业成本。
面对上述问题,本发明涉及通过使用农业产业废物来获得羧甲基纤维素的可承受的替代方案。
通过本发明所提出的方法,上述的大量废物,近二百万吨椰子纤维中果皮能够用作生产羧甲基纤维素的原料。
发明概述
鉴于上述问题和未满足的需要,本发明描述了用于从农业产业残余物获得羧甲基纤维素(CMC)的有利的和有效的方法,该方法包括以下步骤:a)准备原料,其中该原料经清洗、干燥、研磨和再次清洗;b)泵送步骤,其中从步骤a)获得的产物与氢氧化钠反应;c)合成步骤,其中在于研磨浆料、在室温在搅拌下添加异丙醇和蒸馏水的溶液;添加NaOH水溶液以使混合物碱化;添加异丙醇中的一氯乙酸;过滤;在甲醇溶液中悬浮和用乙酸中和。
本发明还涉及由所述方法获得的CMC,其可以用于若干工业过程中。
本发明这些方面的另外的益处和新颖的特征,部分将在以下说明中进行阐释,部分将在本领域技术人员经检视以下内容或者经通过实施本发明所得到的知识而变得更加清晰可见。
附图说明
本系统和方法的各种实例方面将参考以下附图详细进行描述,但是不限于此,其中:
图1是CMC基市售粘合剂的扫描显微图。
图2是市售纯CMC的扫描显微图。
图3是从没有漂白阶段的本发明方法得到的CMC的扫描显微图。
图4是从具有漂白阶段的本发明方法得到的CMC的扫描显微图。
图5是经漂白的浆料的红外光谱。
图6是获自椰子纤维的CMC的红外光谱。
图7是市售纯CMC的红外光谱。
图8是CMC基市售粘合剂的红外光谱。
图9显示了使用(a)CMC基市售粘合剂,(b)未漂白的天然纤维基组合物,和(c)经漂白的天然纤维基组合物的铁矿石粒料。
发明详述
以下详细描述不以任何方式限制本发明的范围、适用性或配置。更确切地,以下描述提供了用于实施示例性形式的必要理解。当使用这里提供的教导时,本领域技术人员将不必外推本发明的范围,即认识到可以使用的适宜替代方案。
本发明涉及获得源自农业综合产业残余物的天然CMC组分的方法,更具体地,涉及获得源自椰子纤维的天然CMC的方法。
更具体地,本发明描述了获得天然CMC组分的方法,该方法包括以下步骤:
a)准备原料;
b)制浆步骤;
c)合成CMC。
在步骤a)中,将农业产业纤维残余物,如椰子纤维,用水清洗以除去粗大杂质。该清洗之后,将纤维在30-120℃的炉中干燥4-72小时。
将纤维在磨机中研磨,和通过18至140目(1.00至0.105mm)的筛子进行筛分。
进行研磨之后,将产物用蒸馏水清洗,然后过滤。然后将沉淀物在30-120℃的炉中干燥4-72小时。
为了从获得的产物除去木质素,在步骤b)(制浆步骤)中将在步骤a)中获得的经研磨和清洁的纤维的大部分混合和搅拌,以1:10的比率与氢氧化钠5-25%(m/v)反应10-100分钟。
任选地,在搅拌反应混合物之后,它可以在111至143℃经受0.5-3.0Kgf/cm2的压力10-100分钟。
将反应混合物用中性pH值的水清洗,将沉淀物送至30-120℃的炉中约12-18小时。
依靠受控搅拌和温度,将从步骤b)获得的产物进行CMC合成(步骤c))。首先,研磨经干燥的浆料,然后添加异丙醇(1:15-1:30)和蒸馏水(1:0.5-1:3)的溶液。将该体系在室温保持搅拌10-30分钟。之后,以1:15经干燥的浆料的比率添加25-55%(w/v)的NaOH水溶液。在室温在搅拌下在30分钟内逐滴添加氢氧化钠溶液,添加之后,将混合物在室温保持搅拌60分钟。
纤维素的碱化之后,立即添加由在异丙醇(1:1-1:5)中的一氯乙酸(1:1.5-1:3.5)组成的溶液。在室温在搅拌下在10-40分钟内逐滴添加该溶液。然后,将温度升至40-70℃,使反应进行2-5小时。
合成之后,过滤产物,然后在70-90%的甲醇溶液(v/v)中悬浮,用乙酸中和,并搅拌5-20分钟。将其过滤,用60-90%的加氢清洗两次,用P.A.甲醇清洗两次,最后干燥CMC。
任选地,在制浆步骤b)之后,可以对材料进行漂白。是否进行该步骤的决定涉及最终结果:最终材料可以是经漂白的,或者不是。
将从制浆步骤b)用蒸馏水(以1:40的比率)获得的粗浆料进行搅拌,并保持在60℃的温度。实现热平衡之后,添加冰醋酸(1:0.125至1:1)和亚氯酸钠(1:0.5至1:4)。将反应混合物保持在持续搅拌下0.5至1.5小时,然后在低于10℃的冰浴中冷却。然后过滤混合物,直到滤液变得无色,pH值为中性。其后,在室温在搅拌下在氢氧化钠0.1mol/L的溶液中进行分离90分钟。然后再次过滤浆料,和用蒸馏水清洗,直到滤液实现中性pH值。
利用根据本发明的获得羧甲基纤维素的方法,能够使用比已知技术柔和的碱处理(制浆)从农业产业除去约80%的木质素,意味着比原方法节约。
此外,利用本发明方法的任选的化学漂白步骤,能够实现除去95-100%的多酚,并且在该方法期间,显然对反应时间的控制和使用回流对获得产品的品质是至关重要的。
获得的天然CMC可以用于若干工业过程中。获得的天然CMC可以用作采矿业中的天然纤维基粘合剂,所述天然纤维基粘合剂包含成分的混合物,其产生粘合最终产品的益处。
例如,用于粘合矿石颗粒,粘合剂组合物会根据种类、来源和矿石组成而不同。
这些成分可以数:
-来自农业产业纤维残余物的CMC40-65%;
碳酸钠15-40%;
-亚氯酸钠5-30%;
-其他0-20%,如柠檬酸钠、葡萄糖酸钠和氢氧化钠。氢氧化钠还可以用于活化和在造粒过程中提高效率。
这些成分的混合物可以实现为固-固混合物或固-液悬浮体,两种情况中CMC为固体部分,添加剂可以为固体或液体。
用作粘合剂矿石,源自农业产业纤维残余物的天然纤维基组合物负责矿石颗粒的聚结。粒料形成是造粒过程最重要的阶段之一,受到几种因素的影响,对最终的产品品质产生直接影响。天然纤维基组合物品质是对粒料形成最重要的要求之一,确保了适合的性能。
此外,由这里所述方法获得的CMC可以用于食品工业,作为粘度改性剂或增稠剂,和用来稳定多种产品包括冰淇淋中的乳液。它还是许多非食品产品的成分,例如个人润滑剂、牙膏、轻泻剂、膳食丸剂、水基涂料、清洁剂、织物处理和各种纸张产品。它的应用主要是因为它具有高粘度,无毒和低变应原性。
实施例1-形态学分析
使用形态学分析扫描电镜(SEM)来分析经本发明提出的处理之后的纤维的结构。
通过SEM比较CMC基市售粘合剂、市售纯CMC和本发明方法的CMC。
SEM中的形态学分析显示,CMC基市售粘合剂含有Na2CO3(图1)。此外,美国专利4,948,430还描述了在其组成中含有Na2CO3的羧甲基纤维素基粘合剂,和应用该粘合剂的方法。但是,市售纯CMC中不存在钠盐(图2)。
图3和图4显示了由本发明方法获得的产品的SEM图像。图3代表没有漂白阶段从椰子纤维获得的CMC的显微图,图4显示了具有漂白阶段的从椰子纤维获得的CMC的图像,证实了获得的纤维结构与市售产品中发现的纤维相似。
实施例2-红外分析
红外(IR)分析的主要目的是确认是否确实存在醚化反应,和对分子各振动的相应谱带进行归因。
红外分析在经漂白的浆料、从椰子纤维获得的CMC、市售纯CMC和CMC基市售粘合剂的样品中进行。
对于经漂白的浆料(图5),IR分析的目的是确认纤维素的化学结构。红外光谱显示了以下官能团的以下谱带:O-H基(谱带约3500cm-1)和烷基(谱带约2900cm-1)。
将从椰子纤维获得的CMC光谱(图6)与市售纯CMC(图7)进行比较,我们观察到在1647-1664cm-1具有相似频率的羰基(C-O)的轴向形变的峰中的相似性,对应于羧酸钠的羰基的轴向形变的振动。所有红外光谱显示了相似的特征,但是在从椰子纤维生产的样品中存在谱带的移位,这一事实可以解释为在获得过程中其他化合物的产生,或者由于纤维素的降解。
当将从椰子纤维获得的CMC与市售纯CMC和CMC基市售纤维素(图8)进行比较时,我们可以观察到红外光谱中的一些区别。一个显著的区别是更强烈地存在1770cm-1的谱带,和不存在1660-1640cm-1的吸收频率中的谱带,这种谱带的移位是由于一定比例的Na2CO3添加到CMC,前者又会产生CMC更具酸性的特征,所以羧甲基可以以羧酸和羧酸酯的性质大量地表达。CMC基市售粘合剂的红外光谱中的另一个峰,与其他不同,在1448cm-1存在强烈的峰,这可能是因为碳酸酯羰基的C-O形变。
实施例3-使用获自椰子纤维的CMC的铁矿石造粒
如上所述,经证明本发明可用于铁矿石颗粒的聚结。为了补充研究,进行测试来证明本发明的效力。
具有满意结果的造粒和燃烧罐炉排(burnpotgrate)造粒装置示于图9。
进行测试,将具有和没有漂白阶段的CMC漂白阶段应用与CMC基市售粘合剂进行比较,如表1所示。
最后,应当理解的是,附图显示的是本发明的示例性实施方案,本发明的真正范围仅由所附权利要求书来限定。
表1
Claims (13)
1.用于从农业产业残余物获得羧甲基纤维素的方法,该方法包括以下步骤:
a)准备原料,其中该原料经清洗、干燥、研磨和再次清洗;
b)泵送步骤,其中将从步骤a)获得的产物与氢氧化钠反应;
c)合成步骤,其中包括研磨浆料;在室温在搅拌下添加异丙醇和蒸馏水的溶液;添加NaOH水溶液以使混合物碱化;添加异丙醇中的一氯乙酸;过滤;在甲醇溶液中悬浮和用乙酸中和。
2.根据权利要求1所述的方法,其中步骤a)包括在30-120℃的炉中干燥4-72小时;通过18至140目(1.00至0.105mm)的筛子进行筛分;将沉淀物在30-120℃的炉中干燥4-72小时。
3.根据权利要求1所述的方法,其中步骤b)包括在10-100分钟内以1:10的比率添加浓度为5-25%(m/v)的氢氧化钠溶液。
4.根据权利要求1和3所述的方法,其中在搅拌反应混合物之后,它可以在111至143℃的温度经受0.5-3.0Kgf/cm2的压力10-100分钟。
5.根据权利要求1所述的方法,其中异丙醇溶液的浓度为1:15-1:30;添加蒸馏水;以与经干燥的浆料的1:15比率添加浓度为25-55%(w/v)的NaOH水溶液;一氯乙酸溶液在异丙醇1:1-1:5中浓度为1:1.5-1:3.5。
6.根据权利要求1所述的方法,其中在制浆步骤b)之后,对材料进行漂白步骤。
7.根据权利要求1-6所述的方法,其中所述农业产业残余物是椰子纤维。
8.由根据权利要求1-7所述的方法获得的羧甲基纤维素。
9.由根据权利要求1-7所述的方法获得的羧甲基纤维素作为矿石颗粒生产中的粘合剂的用途。
10.由根据权利要求1-7所述的方法获得的羧甲基纤维素作为食品工业中的食品添加剂的用途。
11.由根据权利要求1-7所述的方法获得的羧甲基纤维素作为制药工业中的添加剂的用途。
12.由根据权利要求1-7所述的方法获得的羧甲基纤维素作为造纸工业中的添加剂的用途。
13.由根据权利要求1-7所述的方法获得的羧甲基纤维素作为纺织工业中的添加剂的用途。
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CN115521382A (zh) * | 2022-10-19 | 2022-12-27 | 向能新型材料科技(河北)有限公司 | 一种高纯度浴浆法羧甲基纤维素钠的制备方法 |
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WO2017143439A1 (en) * | 2016-02-23 | 2017-08-31 | Matripharm International Inc. | Monolithic composition for dual-rate release with high drug loading |
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AU2013258896B2 (en) | 2016-12-15 |
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SA113340539B1 (ar) | 2016-03-27 |
BR112014028085B1 (pt) | 2021-04-13 |
KR20150058099A (ko) | 2015-05-28 |
US20130324711A1 (en) | 2013-12-05 |
DK2847232T3 (en) | 2018-12-17 |
BR112014028085A2 (pt) | 2017-12-12 |
AR091814A1 (es) | 2015-03-04 |
US9266968B2 (en) | 2016-02-23 |
EP2847232A1 (en) | 2015-03-18 |
JP2015523418A (ja) | 2015-08-13 |
WO2013166575A9 (en) | 2014-07-03 |
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AU2013258896A1 (en) | 2015-01-22 |
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