CN108978291B - Acetified pulp as well as preparation method and application thereof - Google Patents
Acetified pulp as well as preparation method and application thereof Download PDFInfo
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- CN108978291B CN108978291B CN201710397679.6A CN201710397679A CN108978291B CN 108978291 B CN108978291 B CN 108978291B CN 201710397679 A CN201710397679 A CN 201710397679A CN 108978291 B CN108978291 B CN 108978291B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 150000007524 organic acids Chemical class 0.000 claims abstract description 80
- 239000000243 solution Substances 0.000 claims abstract description 69
- 229920002522 Wood fibre Polymers 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000002253 acid Substances 0.000 claims abstract description 40
- 239000007864 aqueous solution Substances 0.000 claims abstract description 39
- 239000002994 raw material Substances 0.000 claims abstract description 37
- 238000005406 washing Methods 0.000 claims abstract description 28
- 238000010306 acid treatment Methods 0.000 claims abstract description 26
- 239000000835 fiber Substances 0.000 claims abstract description 26
- 239000010875 treated wood Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000004061 bleaching Methods 0.000 claims abstract description 18
- 239000002025 wood fiber Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 65
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 64
- 238000011282 treatment Methods 0.000 claims description 47
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims description 40
- 241000196324 Embryophyta Species 0.000 claims description 32
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 30
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 30
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000007806 chemical reaction intermediate Substances 0.000 claims description 12
- 235000019260 propionic acid Nutrition 0.000 claims description 12
- 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 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 11
- 239000010902 straw Substances 0.000 claims description 10
- 239000002028 Biomass Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 8
- 239000011654 magnesium acetate Substances 0.000 claims description 8
- 229940069446 magnesium acetate Drugs 0.000 claims description 8
- 235000011285 magnesium acetate Nutrition 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 6
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 6
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 6
- 239000011425 bamboo Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 241000609240 Ambelania acida Species 0.000 claims description 5
- 235000014676 Phragmites communis Nutrition 0.000 claims description 5
- 240000008042 Zea mays Species 0.000 claims description 5
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 5
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 5
- 239000010905 bagasse Substances 0.000 claims description 5
- 235000005822 corn Nutrition 0.000 claims description 5
- 239000011121 hardwood Substances 0.000 claims description 5
- 239000011122 softwood Substances 0.000 claims description 5
- 241000209140 Triticum Species 0.000 claims description 4
- 235000021307 Triticum Nutrition 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 235000010755 mineral Nutrition 0.000 claims description 3
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000010907 stover Substances 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 150000007522 mineralic acids Chemical class 0.000 claims 1
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 22
- 239000012153 distilled water Substances 0.000 abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 20
- 229960000583 acetic acid Drugs 0.000 description 19
- 235000011054 acetic acid Nutrition 0.000 description 18
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 10
- 235000019253 formic acid Nutrition 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002657 fibrous material Substances 0.000 description 9
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 6
- 241001330002 Bambuseae Species 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000009897 hydrogen peroxide bleaching Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- UGZICOVULPINFH-UHFFFAOYSA-N acetic acid;butanoic acid Chemical compound CC(O)=O.CCCC(O)=O UGZICOVULPINFH-UHFFFAOYSA-N 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 238000007781 pre-processing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 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
- 238000006640 acetylation reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 244000273256 Phragmites communis Species 0.000 description 1
- 244000302661 Phyllostachys pubescens Species 0.000 description 1
- 235000003570 Phyllostachys pubescens Nutrition 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 238000010514 butyrylation reaction Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect 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
- 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
- D21B1/023—Cleaning wood chips or other raw 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
- D21C3/00—Pulping cellulose-containing materials
- D21C3/04—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Paper (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to a preparation method of acetified pulp, which uses organic acid or organic acid aqueous solution to pretreat plant fiber raw materials to obtain pretreatment liquid and pretreated wood fibers; carrying out acid treatment on the obtained pretreated wood fiber by using organic acid or an organic acid aqueous solution and a catalyst to obtain an acid treatment solution and acid-treated wood fiber; washing the obtained acid-treated wood fiber by using organic acid or organic acid aqueous solution, washing by using distilled water, and bleaching the acid-treated wood fiber to obtain the acetified pulp. The acetified pulp prepared by the method has higher alpha-cellulose content, polymerization degree and whiteness, and meanwhile, the production process is simpler, the reagent can be recovered, the production cost is reduced, and the pollution is reduced.
Description
Technical Field
The invention belongs to the field of biological materials, relates to pulp and a preparation method thereof, and particularly relates to acetified pulp and a preparation method and application thereof.
Background
At present, the main preparation process method of the pulp for producing the cellulose acetate or the cellulose acetate butyrate is alkaline cooking or sulfite cooking, but the pulp is produced by adopting the two methods, so the investment is large, the production period is long, the productivity is limited, and the performance of the produced pulp is poor, so the acetification treatment is still required when the cellulose acetate or the cellulose acetate butyrate is produced, and the production cost is increased. And the raw materials adopted are mostly cotton velvet and bamboo due to the process of producing the pulp, so the production limitation is large.
The method for preparing cellulose acetate butyrate is generally divided into a homogeneous phase method and a heterogeneous phase method, wherein the homogeneous phase method adopts an ionic liquid such as DMF, DMAC and other organic solvents to dissolve pulp and then react with acetic anhydride and butyric anhydride to prepare the cellulose acetate butyrate, the used solvent is generally a toxic solvent, the solubility of the solvent to cellulose is small, the recovery is difficult, and the cost is increased.
The heterogeneous law needs to treat the pulp with acetic acid first and carry out pulp activation treatment, namely glacial acetic acid and acetic anhydride with 10-30 times of the mass of the pulp are used for soaking for more than 12 hours, the preparation takes long time, the working procedures are complex and difficult to control, the efficiency is low, the cost is high, the cellulose has high crystallinity, the accessibility is low, the reaction is difficult to occur, and the product has poor physical and chemical properties due to low acylation degree.
Therefore, it is important to research a new preparation method of the acetified pulp and a method for preparing cellulose acetate butyrate by using the prepared acetified pulp.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides the preparation method of the acetified pulp, and the acetified pulp prepared by the method has higher alpha-cellulose content, polymerization degree and whiteness, and meanwhile, the production process is simpler, the reagent can be recovered, the production steps are simplified, the production cost is reduced, and the pollution is reduced. The cellulose acetate butyrate is prepared by taking the acetified pulp as a raw material, so that the production process can be saved, the time required by production is reduced, the acid consumption is reduced, and the production cost is reduced.
In order to achieve the effect, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a preparation method of acetified pulp, which comprises the following steps:
(1) pretreating a plant fiber raw material by using organic acid or an organic acid aqueous solution to obtain a pretreatment solution and pretreated wood fibers;
(2) carrying out acid treatment on the pretreated wood fiber obtained in the step (1) by using organic acid or organic acid aqueous solution and a catalyst to obtain acid treatment solution and acid-treated wood fiber;
(3) washing the acid-treated wood fiber obtained in the step (2) by using organic acid or organic acid aqueous solution, and then washing by using water to obtain unbleached acetified pulp;
(4) bleaching the unbleached acetified pulp obtained in the step (3) to obtain the acetified pulp.
According to the invention, the plant fiber raw material is pretreated and acidified by using the organic acid, so that the hydrolysis reaction condition of the plant fiber raw material is milder, the reaction degree is higher, the prepared acetified pulp has higher alpha-cellulose content, the organic acid is simple and convenient to recover, and the reagent can be recycled, so that the pollution problem in the production process of an alkaline method and a sulfite method is avoided, and the process cost is reduced.
In a preferred embodiment of the present invention, the plant fiber material in step (1) is a plant fiber material having a particle size after pulverization larger than a 30-mesh pore size, such as 30-mesh, 50-mesh, 100-mesh, 150-mesh, 200-mesh, 300-mesh, 400-mesh, or 500-mesh, but the invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
Preferably, the plant fiber raw material comprises woody biomass or/and graminaceous biomass.
Preferably, the woody biomass comprises any one of hardwood, softwood or shrub or a combination of at least two of the following typical but non-limiting examples: a combination of hardwood and softwood, a combination of softwood and shrub, a combination of shrub and hardwood, or a combination of hardwood, softwood, and shrub, and the like.
Preferably, the graminaceous biomass comprises any one or a combination of at least two of bagasse, bamboo, straw, wheat straw, corn stover or reed, typical but non-limiting examples of which are: bagasse and bamboo, bamboo and straw, straw and wheat straw, wheat straw and corn stalk, corn stalk and reed, reed and bagasse, bamboo and straw, and the like.
Preferably, the organic acid of step (1) comprises any one of formic acid, acetic acid, propionic acid, n-butyric acid or isobutyric acid or a combination of at least two thereof, as typical but non-limiting examples: combinations of formic acid and acetic acid, acetic acid and propionic acid, formic acid and propionic acid, propionic acid and n-butyric acid, n-butyric acid and isobutyric acid, or formic acid, acetic acid and propionic acid, and the like.
Preferably, the mass concentration of the aqueous organic acid solution in step (1) is 30% to 100%, excluding 100%, such as 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 99%, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the mass ratio of the organic acid or the aqueous solution of the organic acid to the plant fiber raw material in the step (1) is (1-20): 1, such as 1:1, 2:1, 5:1, 8:1, 10:1, 12:1, 15:1, 18:1 or 20:1, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the pressure of the pretreatment in the step (1) is 1 × 105～2×105Pa, e.g. 1X 105Pa、1.1×105Pa、1.2×105Pa、1.3×105Pa、1.4×105Pa、1.5×105Pa、1.6×105Pa、1.7×105Pa、1.8×105Pa、1.9×105Pa or 2X 105Pa, etc., but are not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the temperature of the pretreatment in step (1) is 70 to 200 ℃, such as 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the time of the pretreatment in step (1) is 10 to 600min, such as 10min, 20min, 50min, 80min, 100min, 150min, 200min, 250min, 300min, 400min, 500min, or 600min, but not limited to the recited values, and other values not recited in the range of the values are also applicable, and more preferably 30 to 300 min.
As a preferred embodiment of the present invention, the organic acid in step (2) includes any one or a combination of at least two of formic acid, acetic acid, propionic acid, n-butyric acid or isobutyric acid, and the combination is exemplified by, typically but not limited to: combinations of formic acid and acetic acid, acetic acid and propionic acid, formic acid and propionic acid, propionic acid and n-butyric acid, n-butyric acid and isobutyric acid, or formic acid, acetic acid and propionic acid, and the like.
Preferably, the mass concentration of the aqueous organic acid solution in step (2) is 30% to 100%, excluding 100%, such as 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 99%, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the mass ratio of the organic acid or the aqueous solution of the organic acid to the pretreated plant fiber raw material in the step (2) is (1-20): 1, such as 1:1, 2:1, 5:1, 8:1, 10:1, 12:1, 15:1, 18:1 or 20:1, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the catalyst of step (2) comprises a mineral acid and/or hydrogen peroxide.
Preferably, the mineral acid comprises any one of hydrochloric acid, nitric acid or sulfuric acid, or a combination of at least two of these, typical but non-limiting examples being: a combination of hydrochloric acid and nitric acid, a combination of nitric acid and sulfuric acid, a combination of sulfuric acid and hydrochloric acid, or a combination of hydrochloric acid, nitric acid and sulfuric acid, and the like.
Preferably, the mass ratio of the catalyst to the pretreated plant fiber raw material in the step (2) is 1 (10-50), such as 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45 or 1:50, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the pressure of the acid treatment in the step (2) is 1X 105～2×105Pa, e.g. 1X 105Pa、1.1×105Pa、1.2×105Pa、1.3×105Pa、1.4×105Pa、1.5×105Pa、1.6×105Pa、1.7×105Pa、1.8×105Pa、1.9×105Pa or 2X 105Pa, etc., but are not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the temperature of the acid treatment in step (2) is 70 to 200 ℃, such as 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the acid treatment time in step (2) is 10 to 600min, such as 10min, 20min, 50min, 80min, 100min, 150min, 200min, 250min, 300min, 400min, 500min, or 600min, but not limited to the recited values, and other values not recited in the range of the values are also applicable, and more preferably 30 to 300 min.
As a preferable embodiment of the present invention, the step (1 ') is followed by the step (1') of evaporating and concentrating the pretreated liquid obtained in the step (1) to recover the organic acid aqueous solution.
Preferably, the pressure P of the evaporative concentration in step (1') is 0.1X 105Pa≤P＜1.0×105Pa, e.g. 0.1X 105Pa、0.2×105Pa、0.3×105Pa、0.4×105Pa、0.5×105Pa、0.6×105Pa、0.7×105Pa、0.75×105Pa、0.8×105Pa、0.85×105Pa、0.9×105Pa、0.95×105Pa or 0.99X 105Pa, etc., but are not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the temperature of the evaporation concentration in step (1') is 65 to 200 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 90 ℃, 100 ℃, 120 ℃, 150 ℃, 180 ℃, or 200 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the step (2 ') is followed by the step (2') of evaporating and concentrating the acid-treated solution obtained in the step (2) to recover the organic acid aqueous solution.
Preferably, the pressure P of the evaporative concentration in step (2') is 0.1X 105Pa≤P＜1.0×105Pa, e.g. 0.1X 105Pa、0.2×105Pa、0.3×105Pa、0.4×105Pa、0.5×105Pa、0.6×105Pa、0.7×105Pa、0.75×105Pa、0.8×105Pa、0.85×105Pa、0.9×105Pa、0.95×105Pa or 0.99X 105Pa, etc., but are not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the temperature of the evaporation concentration in step (2') is 65 to 200 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 90 ℃, 100 ℃, 120 ℃, 150 ℃, 180 ℃, or 200 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
In a preferred embodiment of the present invention, the aqueous organic acid solution in the step (3) is an aqueous organic acid solution recovered in the step (1 ') and/or the step (2').
Preferably, the mass ratio of water to the acetified pulp in the water washing in the step (3) is (1-20): 1, such as 1:1, 2:1, 5:1, 8:1, 10:1, 12:1, 15:1, 18:1 or 20:1, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the bleaching treatment in step (4) comprises any one of alkali treatment, hypochlorite treatment, hydrogen peroxide treatment, oxygen treatment or ozone treatment or a combination of at least two of them, and the combination is typically but not limited to: a combination of alkali treatment and hypochlorite treatment, a combination of hypochlorite treatment and hydrogen peroxide treatment, a combination of hydrogen peroxide treatment and oxygen treatment, a combination of oxygen treatment and ozone treatment, a combination of ozone treatment and alkali treatment or a combination of alkali treatment, hypochlorite treatment and hydrogen peroxide treatment, and the like.
Preferably, the bleaching treatment of step (4) is followed by washing and drying.
The second purpose of the invention is to provide the acetified pulp which is prepared by the preparation method.
The third purpose of the invention is to provide an application of the acetified pulp, which is characterized in that the method for preparing the cellulose acetate butyrate by taking the acetified pulp as a raw material comprises the following steps:
(a) reacting the acetified pulp with n-butyric acid, acetic anhydride and concentrated sulfuric acid to obtain a reaction intermediate solution;
(b) reacting the reaction intermediate solution obtained in the step (a) with n-butyric acid or an n-butyric acid solution, and adding magnesium acetate after the reaction to obtain a crude product solution of cellulose acetate butyrate;
(c) and (c) adding an organic acid aqueous solution into the crude cellulose acetate butyrate solution obtained in the step (b), separating out, and carrying out solid-liquid separation to obtain the cellulose acetate butyrate.
The acetified pulp prepared by the acetified pulp has partial hydroxyl which is subjected to acetylation reaction, so that the activity of cellulose is improved, the subsequent acetylation and butyrylation reaction degree is higher, the cellulose acetate butyrate produced by the acetified pulp has higher acetyl and butyryl contents, the acid activation step in the prior art can be simultaneously omitted in the process of producing the cellulose acetate butyrate, the acid consumption is reduced, the process is simplified, and the cost is reduced.
In a preferred embodiment of the present invention, the mass ratio of n-butyric acid to the acetylated pulp in step (a) is (5 to 10:1, for example, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1 or 10:1, but the present invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable.
Preferably, the mass ratio of the acetic anhydride of step (a) to the acetylated pulp is (2-3: 1, such as 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, or 3:1, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the mass ratio of the concentrated sulfuric acid to the acetylated pulp of step (a) is (0.01-0.1): 1, such as 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, or 0.1:1, but not limited to the recited values, and other values not recited in this range of values are equally applicable.
Preferably, the reaction temperature in step (a) is 40 to 80 ℃, such as 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the reaction time in step (a) is 1 to 4 hours, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours or 4 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
In a preferred embodiment of the present invention, the n-butanol solution in step (b) has a mass concentration of 60 to 100%, excluding 100%, such as 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99%, but not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the mass ratio of the n-butyric acid or n-butyric acid solution in step (b) to the acetylated pulp is (2-10: 1), such as 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, but not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the reaction temperature in step (b) is 40 to 80 ℃, such as 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the reaction time in step (b) is 1 to 4 hours, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours or 4 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the mass ratio of magnesium acetate to concentrated sulfuric acid in step (b) is (1-3): 1, such as 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.2:1, 2.5:1, 2.8:1 or 3:1, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
As a preferred embodiment of the present invention, the organic acid in step (c) comprises any one or a combination of at least two of n-butyric acid, isobutyric acid or acetic acid, and typical but non-limiting examples of the combination are: combinations of n-butyric acid and isobutyric acid, combinations of isobutyric acid and acetic acid, combinations of acetic acid and n-butyric acid, or combinations of n-butyric acid, isobutyric acid and acetic acid, and the like.
Preferably, the mass concentration of the aqueous organic acid solution in step (c) is 10 to 50%, such as 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the mass ratio of the aqueous organic acid solution to the acetylated pulp in step (c) is (15-30: 1, such as 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, 21:1, 22:1, 23:1, 24:1, 25:1, 26:1, 27:1, 28:1, 29:1 or 30:1, but not limited to the recited values, and other values not recited in this range are equally applicable.
Preferably, after the solid-liquid separation in step (c), the cellulose acetate butyrate obtained is washed and dried.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the invention provides a preparation method of acetified pulp, the content of alpha-cellulose in the acetified pulp prepared by the method is more than 90 percent and can reach 99.0 percent at most;
(2) the invention provides a preparation method of acetified pulp, which adopts organic acid or an organic acid aqueous solution for pretreatment and acidification, simplifies production steps, reduces production cost and reduces pollution;
(3) the invention provides a method for preparing acetate butyrate fibers by adopting the acetified pulp raw material prepared by the preparation method, wherein the content of acetyl in the acetate butyrate fibers prepared by the method is up to 21.1 wt%, and the content of butyryl is up to 45.8 wt%;
(4) the invention provides a method for preparing acetate butyrate by adopting the acetified pulp raw material prepared by the preparation method, which reduces the time required by production, reduces the acid consumption and reduces the production cost.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A method of making an acetylated grade pulp, the method comprising the steps of:
(1) using 20 times of acetic acid solution (30 wt%) of plant fiber raw material at 70 deg.C and 2 × 105Pretreating bagasse for 10min under the condition of Pa to obtain pretreatment liquid and pretreated wood fiber;
(2) make itUsing 20 times of acetic acid solution (30 wt%) and 10% hydrochloric acid at 70 deg.C, 2 × 105Carrying out acid treatment on the pretreated wood fiber obtained in the step (1) for 10min under the condition of Pa to obtain acid treatment liquid and acid-treated wood fiber;
(3) washing the acid-treated wood fiber obtained in the step (2) by using organic acid or organic acid aqueous solution, and then washing by using distilled water which is 20 times of the acid-treated wood fiber to obtain unbleached acetified pulp;
(4) and (4) carrying out hydrogen peroxide bleaching treatment and alkali bleaching treatment on the unbleached acetified pulp obtained in the step (3), washing and drying to obtain the acetified pulp.
Example 2
A method of making an acetylated grade pulp, the method comprising the steps of:
(1) formic acid 1 times the mass of the plant fiber raw material is used at 200 ℃ and 1 × 105Pretreating the moso bamboo for 600min under the condition of Pa to obtain pretreatment liquid and pretreated wood fiber;
(2) formic acid 1 time of the mass of the pretreated plant fiber raw material and sulfuric acid 2 percent of the mass of the pretreated plant fiber raw material are used at 200 ℃ and 1 multiplied by 105Carrying out acid treatment on the pretreated wood fiber obtained in the step (1) for 600min under the condition of Pa to obtain acid treatment liquid and acid-treated wood fiber;
(3) washing the acid-treated wood fiber obtained in the step (2) by using organic acid or organic acid aqueous solution, and then washing by using distilled water which is 1 time of that of the acid-treated wood fiber to obtain unbleached acetified pulp;
(4) and (4) carrying out oxygen bleaching treatment and ozone bleaching treatment on the unbleached acetified pulp obtained in the step (3), washing and drying to obtain the acetified pulp.
Example 3
A method of making an acetylated grade pulp, the method comprising the steps of:
(1) using a propionic acid solution (60 wt%) 10 times the weight of the plant fiber raw material at 150 deg.C and 1.5 × 105Straw is treated under the condition of PaPretreating for 60min to obtain pretreatment solution and pretreated wood fiber;
(2) using propionic acid solution (60 wt%) 10 times of the mass of the pretreated plant fiber raw material and nitric acid 5% of the mass of the pretreated plant fiber raw material at 150 ℃ and 1.5X 105Carrying out acid treatment on the pretreated wood fiber obtained in the step (1) for 60min under the condition of Pa to obtain acid treatment liquid and acid-treated wood fiber;
(3) washing the acid-treated wood fiber obtained in the step (2) by using organic acid or organic acid aqueous solution, and then washing by using distilled water which is 10 times of that of the acid-treated wood fiber to obtain unbleached acetified pulp;
(4) and (4) carrying out oxygen bleaching treatment and hypochlorite bleaching treatment, washing and drying on the unbleached acetified pulp obtained in the step (3) to obtain the acetified pulp.
Example 4
A method of making an acetylated grade pulp, the method comprising the steps of:
(1) using an n-butyric acid solution (60 wt%) 10 times the mass of the plant fiber raw material at 150 deg.C and 1.5X 105Pretreating corn stalks for 60min under the condition of Pa to obtain pretreatment liquid and pretreatment wood fibers;
(1') treating the pretreatment solution obtained in the step (1) at 0.1X 105Evaporating and concentrating under the conditions of Pa and 65 ℃, and recovering an organic acid aqueous solution;
(2) using n-butanol solution (60 wt%) 10 times of the mass of the pretreated plant fiber material and hydrogen peroxide 6% of the mass of the pretreated plant fiber material at 150 deg.C and 1.5 × 105Carrying out acid treatment on the pretreated wood fiber obtained in the step (1) for 60min under the condition of Pa to obtain acid treatment liquid and acid-treated wood fiber;
(2') subjecting the acid-treated liquid obtained in the step (2) to a treatment at 0.1X 105Evaporating and concentrating under the conditions of Pa and 65 ℃, and recovering an organic acid aqueous solution;
(3) washing the acid-treated wood fiber obtained in the step (2) by using the organic acid aqueous solution recovered in the step (1 ') and the step (2'), and then washing by using distilled water which is 10 times of that of the acid-treated wood fiber to obtain unbleached acetified pulp;
(4) and (4) carrying out hydrogen peroxide bleaching treatment, oxygen bleaching treatment and ozone bleaching treatment on the unbleached acetified pulp obtained in the step (3), washing and drying to obtain the acetified pulp.
Example 5
A method of making an acetylated grade pulp, the method comprising the steps of:
(1) an isobutyric acid solution (60 wt%) 10 times the mass of the plant fiber material was used at 150 ℃ and 1.5X 105Preprocessing the reeds for 60min under the condition of Pa to obtain preprocessing liquid and preprocessing wood fibers;
(1') treating the pretreatment solution obtained in the step (1) at 0.9X 105Evaporating and concentrating at Pa and 200 ℃, and recovering an organic acid aqueous solution;
(2) using an isobutyric acid solution (60 wt%) 10 times the mass of the pretreated plant fiber material and hydrochloric acid 5% of the mass of the pretreated plant fiber material at 150 ℃ and 1.5X 105Carrying out acid treatment on the pretreated wood fiber obtained in the step (1) for 60min under the condition of Pa to obtain acid treatment liquid and acid-treated wood fiber;
(2') subjecting the acid-treated liquid obtained in the step (2) to a treatment at 0.9X 105Evaporating and concentrating at Pa and 200 ℃, and recovering an organic acid aqueous solution;
(3) washing the acid-treated wood fiber obtained in the step (2) by using the organic acid aqueous solution recovered in the step (1 ') and the step (2'), and then washing by using distilled water which is 10 times of that of the acid-treated wood fiber to obtain unbleached acetified pulp;
(4) and (4) carrying out hydrogen peroxide bleaching treatment, alkali bleaching treatment and hypochlorite bleaching treatment, washing and drying on the unbleached acetified pulp obtained in the step (3) to obtain the acetified pulp.
Example 6
A method of making an acetylated grade pulp, the method comprising the steps of:
(1) using an acetic acid solution (60 wt%) 10 times the weight of the plant fiber raw material at 150 deg.C and 1.5 × 105Treating poplar under PaPretreating for 60min to obtain pretreatment solution and pretreated wood fiber;
(1') treating the pretreatment solution obtained in the step (1) at 0.5X 105Evaporating and concentrating at the temperature of Pa and 100 ℃, and recovering an organic acid aqueous solution;
(2) using an acetic acid solution (60 wt%) 10 times the mass of the pretreated plant fiber material and hydrogen peroxide 5% of the mass of the pretreated plant fiber material at 150 deg.C and 1.5X 105Carrying out acid treatment on the pretreated wood fiber obtained in the step (1) for 60min under the condition of Pa to obtain acid treatment liquid and acid-treated wood fiber;
(2') subjecting the acid-treated liquid obtained in the step (2) to a treatment at 0.5X 105Evaporating and concentrating under the conditions of Pa and 100 ℃, and recovering an organic acid aqueous solution;
(3) washing the acid-treated wood fiber obtained in the step (2) by using the organic acid aqueous solution recovered in the step (1 ') and the step (2'), and then washing by using distilled water which is 10 times of that of the acid-treated wood fiber to obtain unbleached acetified pulp;
(4) and (4) carrying out hydrogen peroxide bleaching treatment, alkali bleaching treatment and hypochlorite bleaching treatment, washing and drying on the unbleached acetified pulp obtained in the step (3) to obtain the acetified pulp.
Example 7
A process for producing an acetylated wood pulp, which comprises the same steps as those conducted in example 3 except that the concentration of the organic acid in step (1) is 10% by weight.
Example 8
A process for producing an acetylated wood pulp, which comprises the same steps as those conducted in example 3 except that the concentration of the organic acid in step (2) is 10% by weight.
Example 9
The cellulose acetate butyrate is prepared by taking the acetified pulp prepared in the embodiment 6 as a raw material, and the preparation method comprises the following steps:
(a) reacting the acetified pulp with n-butyric acid which is 5 times of the mass of the acetified pulp, acetic anhydride which is 2 times of the mass of the acetified pulp and concentrated sulfuric acid which is 0.01 time of the mass of the acetified pulp at 40 ℃ for 4 hours to obtain a reaction intermediate solution;
(b) reacting the reaction intermediate solution obtained in the step (a) with n-butyric acid of 2 times of the mass of the acetified pulp at 40 ℃ for 4 hours, and adding magnesium acetate of 1 time of the mass of concentrated sulfuric acid after the reaction to obtain a crude cellulose acetate butyrate product solution;
(c) adding a n-butyl acid solution (50 wt%) 15 times of the mass of the acetified pulp into the crude product solution of the cellulose acetate butyrate obtained in the step (b), separating out, and carrying out solid-liquid separation to obtain the cellulose acetate butyrate.
Example 10
The cellulose acetate butyrate is prepared by taking the acetified pulp prepared in the embodiment 6 as a raw material, and the preparation method comprises the following steps:
(a) reacting the acetified pulp with n-butyric acid which is 10 times of the mass of the acetified pulp, acetic anhydride which is 3 times of the mass of the acetified pulp and concentrated sulfuric acid which is 0.1 time of the mass of the acetified pulp at 80 ℃ for 1 hour to obtain a reaction intermediate solution;
(b) reacting the reaction intermediate solution obtained in the step (a) with an n-butyric acid solution (60 wt%) which is 10 times of the mass of the acetified pulp at 80 ℃ for 1h, and adding magnesium acetate which is 3 times of the mass of concentrated sulfuric acid after the reaction to obtain a crude product solution of cellulose acetate butyrate;
(c) and (c) adding an isobutyric acid solution (10 wt%) which is 30 times of the mass of the acetified pulp into the crude product solution of the cellulose acetate butyrate obtained in the step (b), separating out, and carrying out solid-liquid separation to obtain the cellulose acetate butyrate.
Example 11
The cellulose acetate butyrate is prepared by taking the acetified pulp prepared in the embodiment 6 as a raw material, and the preparation method comprises the following steps:
(a) reacting the acetified pulp with n-butyric acid which is 8 times of the mass of the acetified pulp, acetic anhydride which is 1.5 times of the mass of the acetified pulp and concentrated sulfuric acid which is 0.05 times of the mass of the acetified pulp at the temperature of 80 ℃ for 1 hour to obtain a reaction intermediate solution;
(b) reacting the reaction intermediate solution obtained in the step (a) with a n-butyl acid solution (80 wt%) 5 times of the mass of the acetified pulp at 60 ℃ for 2 hours, and adding magnesium acetate 2 times of the mass of concentrated sulfuric acid after the reaction to obtain a crude product solution of cellulose acetate butyrate;
(c) adding an acetic acid solution (40 wt%) which is 20 times of the mass of the acetified pulp into the crude product solution of the cellulose acetate butyrate obtained in the step (b), separating out, and carrying out solid-liquid separation to obtain the cellulose acetate butyrate.
Example 12
The cellulose acetate butyrate is prepared by taking the acetified pulp prepared in the embodiment 6 as a raw material, and the preparation method comprises the following steps:
(a) reacting the acetified pulp with n-butyric acid with the mass of 6 times of that of the acetified pulp, acetic anhydride with the mass of 1.2 times of that of the acetified pulp and concentrated sulfuric acid with the mass of 0.03 time of that of the acetified pulp at the temperature of 70 ℃ for 1.5 hours to obtain a reaction intermediate solution;
(b) reacting the reaction intermediate solution obtained in the step (a) with a n-butyl acid solution (60 wt%) 8 times of the mass of the acetified pulp at 70 ℃ for 1.5h, and adding magnesium acetate 3 times of the mass of concentrated sulfuric acid after the reaction to obtain a crude cellulose acetate butyrate product solution;
(c) and (c) adding an isobutyric acid solution (20 wt%) which is 25 times of the mass of the acetified pulp into the crude product solution of the cellulose acetate butyrate obtained in the step (b), separating out, and carrying out solid-liquid separation to obtain the cellulose acetate butyrate.
Comparative example 1
A process for producing an acetified-grade pulp, under the same conditions as in example 3, except that the organic acid or the aqueous solution of an organic acid used in the pretreatment in step (1) was replaced with a sodium sulfite solution.
Comparative example 2
A process for producing an acetified-grade pulp, which comprises the same procedures as in example 3 except that the organic acid or the aqueous solution of an organic acid in the step (2) is replaced with a sodium sulfite solution.
Comparative example 3
A process for producing an acetified-grade pulp, which comprises replacing the organic acid or aqueous solution of an organic acid in the steps (1) and (2) with a sodium sulfite solution, was carried out under the same conditions as in example 3.
Comparative example 4
A cellulose acetate butyrate was prepared under the same conditions as in example 12, except that the starting material was a commercially available acetylated pulp.
The content of alpha-cellulose in the acetylated grade pulps prepared in examples 1-8 and comparative examples 1-3 was measured and the results are shown in Table 1.
TABLE 1
The cellulose acetate butyrate prepared in examples 9-12 and comparative example 4 was tested for acetyl and butyryl content, and the results are shown in Table 2.
TABLE 2
| Item | Example 9 | Example 10 | Example 11 | Example 12 | Comparative example 4 |
| Acetyl content/wt% | 17.9 | 20.5 | 19.8 | 18.8 | 12.2 |
| Butyryl content/wt% | 38.9 | 39.7 | 39.5 | 38.7 | 31.1 |
As can be seen from Table 1, the process of pre-treating an acetylated pulp with an organic acid and treating the pulp with an organic acid provided by the present invention resulted in the preparation of an acetylated pulp having an alpha-cellulose content of greater than 90 wt%, while the comparative examples 1-3 resulted in an acetylated pulp having an alpha-cellulose content of less than 90.2 wt% prepared using sodium sulfite instead of an organic acid in step (1) and/or step (2).
As can be seen from Table 2, the pulp from the acetification stage prepared by the present invention was used as a raw material to prepare cellulose acetate butyrate, and the prepared cellulose acetate butyrate had an acetyl group content of 17 wt% or more and a butyryl group content of 38 wt% or more, whereas comparative example 1 used a commercially available acetification stage pulp as a raw material, and the prepared cellulose acetate butyrate had an acetyl group content of 12.2 wt% and a butyryl group content of 31.1 wt%.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (32)
1. The application of the acetified pulp with the alpha-cellulose content of more than 90 wt% is characterized in that the acetified pulp is used as a raw material to prepare cellulose acetate butyrate, and the preparation method comprises the following steps:
(a) reacting the acetified pulp with n-butyric acid and acetic anhydride, and taking concentrated sulfuric acid as a catalyst to obtain a reaction intermediate solution;
(b) carrying out hydrolysis reaction on the reaction intermediate solution obtained in the step (a) and n-butyric acid or an n-butyric acid solution, and adding magnesium acetate after the reaction to obtain a crude product solution of cellulose acetate butyrate;
(c) adding an organic acid aqueous solution into the crude cellulose acetate butyrate solution obtained in the step (b), separating out, and carrying out solid-liquid separation to obtain cellulose acetate butyrate;
the mass ratio of the n-butyric acid to the acetified pulp in the step (a) is (5-10) to 1;
the mass ratio of the acetic anhydride to the acetified pulp in the step (a) is (2-3) to 1;
the mass ratio of the n-butyric acid or n-butyric acid solution to the acetified pulp in the step (b) is (2-10) to 1;
the mass ratio of the organic acid aqueous solution to the acetified pulp in the step (c) is (15-30) to 1;
the prepared cellulose acetate butyrate has an acetyl content of more than 17 wt% and a butyryl content of more than 38 wt%;
the acetified pulp is prepared by adopting the following method, and the method comprises the following steps:
(1) pretreating a plant fiber raw material by using organic acid or an organic acid aqueous solution to obtain a pretreatment solution and pretreated wood fibers; the organic acid comprises any one or combination of at least two of acetic acid, propionic acid, n-butyric acid or isobutyric acid, and the pressure of the pretreatment is 1 x 105～2×105Pa；
(2) Carrying out acid treatment on the pretreated wood fiber obtained in the step (1) by using organic acid or organic acid aqueous solution and a catalyst to obtain acid treatment solution and acid-treated wood fiber; the organic acid comprises any one or combination of at least two of acetic acid, propionic acid, n-butyric acid or isobutyric acid, and the pressure of acid treatment is 1 x 105～2×105Pa；
(3) Washing the acid-treated wood fiber obtained in the step (2) by using organic acid or organic acid aqueous solution, and then washing by using water to obtain unbleached acetified pulp;
(4) bleaching the unbleached acetified pulp obtained in the step (3) to obtain acetified pulp;
after the step (1), carrying out a step (1') of evaporating and concentrating the pretreatment solution obtained in the step (1) and recovering an organic acid aqueous solution;
step (2') is carried out after step (2), the acid treatment solution obtained in step (2) is evaporated and concentrated, and an organic acid aqueous solution is recovered;
the mass concentration of the organic acid aqueous solution in the step (1) is 30-100%, excluding 100%;
the mass ratio of the organic acid or the organic acid aqueous solution to the plant fiber raw material in the step (1) is (1-20) to 1;
the organic acid aqueous solution in the step (3) is the organic acid aqueous solution recovered in the step (1 ') and/or the step (2');
the mass ratio of the washing water to the acetified pulp in the step (3) is (1-20): 1.
2. The use according to claim 1, wherein the plant fiber raw material in step (1) is a plant fiber raw material with a particle size larger than 30 mesh after being crushed.
3. Use according to claim 1, wherein the plant fiber raw material is woody biomass or/and graminaceous biomass.
4. The use of claim 3, wherein the woody biomass comprises any one of hardwood or softwood or a combination of at least two thereof.
5. The use according to claim 3, wherein the graminaceous biomass comprises any one or a combination of at least two of bagasse, bamboo, straw, wheat straw, corn stover, or reed.
6. The use according to claim 1, wherein the temperature of the pretreatment in step (1) is 70 to 200 ℃.
7. The use of claim 1, wherein the pretreatment time in step (1) is 10-600 min.
8. The use of claim 7, wherein the pretreatment time in step (1) is 30-300 min.
9. The use according to claim 1, wherein the mass concentration of the aqueous organic acid solution in the step (2) is 30-100%, excluding 100%.
10. The application of the method as claimed in claim 1, wherein the mass ratio of the organic acid or the aqueous solution of the organic acid in the step (2) to the pretreated plant fiber raw material is (1-20): 1.
11. Use according to claim 1, wherein the catalyst of step (2) comprises a mineral acid and/or hydrogen peroxide.
12. Use according to claim 11, wherein the inorganic acid comprises any one of hydrochloric acid, nitric acid or sulphuric acid, or a combination of at least two thereof.
13. The application of the catalyst as claimed in claim 1, wherein the mass ratio of the catalyst in the step (2) to the pretreated plant fiber raw material is 1 (10-50).
14. The use according to claim 1, wherein the temperature of the acid treatment in step (2) is 70 to 200 ℃.
15. The use according to claim 1, wherein the acid treatment time in step (2) is 10-600 min.
16. The use according to claim 15, wherein the acid treatment time in step (2) is 30 to 300 min.
17. According to the claimsThe use according to claim 1, wherein the pressure P of the evaporative concentration in step (1') is 0.1X 105≤P＜1.0×105Pa。
18. The use according to claim 1, wherein the temperature of the evaporative concentration in step (1') is 65-200 ℃.
19. Use according to claim 1, wherein the pressure P of the evaporative concentration of step (2') is 0.1 x 105≤P＜1.0×105Pa。
20. The use according to claim 19, wherein the temperature of the evaporative concentration in step (2') is 65-200 ℃.
21. The use of claim 1, wherein the bleaching treatment of step (4) comprises any one of alkali treatment, hypochlorite treatment, hydrogen peroxide treatment, oxygen treatment or ozone treatment or a combination of at least two of them.
22. Use according to claim 1, characterized in that the bleaching treatment of step (4) is followed by washing and drying.
23. The use according to claim 1, wherein the mass ratio of the concentrated sulfuric acid of step (a) to the acetylated grade pulp is (0.01-0.1): 1.
24. The use according to claim 1, wherein the temperature of the reaction in step (a) is 40 to 80 ℃.
25. The use according to claim 1, wherein the reaction time in step (a) is 1-4 h.
26. The use according to claim 1, wherein the n-butyl acid solution in step (b) has a mass concentration of 60-100%, excluding 100%.
27. The use according to claim 1, wherein the temperature of the reaction in step (b) is 40 to 80 ℃.
28. The use of claim 1, wherein the reaction time in step (b) is 1-4 h.
29. The use of claim 1, wherein the mass ratio of the magnesium acetate to the concentrated sulfuric acid in the step (b) is (1-3): 1.
30. The use of claim 1, wherein the organic acid of step (c) comprises any one of n-butyric acid, isobutyric acid or acetic acid or a combination of at least two thereof.
31. The use according to claim 1, wherein the mass concentration of the aqueous organic acid solution in the step (c) is 10-50%.
32. Use according to claim 1, wherein after the solid-liquid separation in step (c), the cellulose acetate butyrate obtained is washed and dried.
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| CN114349871B (en) * | 2022-01-11 | 2022-11-08 | 万华化学集团股份有限公司 | Method for decoloring and decontaminating cellulose acetate butyrate |
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| CN102212974A (en) * | 2011-05-27 | 2011-10-12 | 中国制浆造纸研究院 | Method for producing dissolving pulp |
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