JPH09268201A - Production of cellulose acetate - Google Patents
Production of cellulose acetateInfo
- Publication number
- JPH09268201A JPH09268201A JP7869996A JP7869996A JPH09268201A JP H09268201 A JPH09268201 A JP H09268201A JP 7869996 A JP7869996 A JP 7869996A JP 7869996 A JP7869996 A JP 7869996A JP H09268201 A JPH09268201 A JP H09268201A
- Authority
- JP
- Japan
- Prior art keywords
- pulp
- enzyme
- cellulose acetate
- treatment
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002301 cellulose acetate Polymers 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 108090000790 Enzymes Proteins 0.000 claims abstract description 28
- 102000004190 Enzymes Human genes 0.000 claims abstract description 28
- 238000006640 acetylation reaction Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 102100032487 Beta-mannosidase Human genes 0.000 claims abstract description 6
- 101710121765 Endo-1,4-beta-xylanase Proteins 0.000 claims abstract description 6
- 108010055059 beta-Mannosidase Proteins 0.000 claims abstract description 6
- 229920002678 cellulose Polymers 0.000 claims abstract description 5
- 239000001913 cellulose Substances 0.000 claims abstract description 5
- 229930182470 glycoside Natural products 0.000 claims abstract description 4
- 229920000057 Mannan Polymers 0.000 claims abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 3
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 3
- 239000005017 polysaccharide Substances 0.000 claims abstract description 3
- 150000004804 polysaccharides Chemical class 0.000 claims abstract description 3
- 229920001221 xylan Polymers 0.000 claims abstract description 3
- 150000004823 xylans Chemical class 0.000 claims abstract description 3
- 229920002488 Hemicellulose Polymers 0.000 abstract description 16
- 239000007864 aqueous solution Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract description 5
- 230000000397 acetylating effect Effects 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 abstract description 2
- 238000002203 pretreatment Methods 0.000 abstract 4
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000021736 acetylation Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000012345 acetylating agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 238000012691 depolymerization reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- -1 organic acid esters Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は酢酸セルロースの製
造方法に関し、より詳しくは、有機溶媒中での不溶解物
が少なく、濾過性の良好な高品質酢酸セルロースを製造
する方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing cellulose acetate, and more particularly to a method for producing high-quality cellulose acetate having a small insoluble matter in an organic solvent and good filterability.
【０００２】[0002]
【従来の技術】酢酸セルロースはセルロース有機酸エス
テルの１つであり、その用途は、衣料繊維、医療材料、
タバコフィルターチップ、プラスチックス、フィルム、
塗料等多岐にわたっており、セルロース誘導体の中で最
も生産量が多く、工業的にも重要なものである。一般的
な酢酸セルロースの製造方法としては、無水酢酸を酢化
剤、酢酸を希釈剤、硫酸を触媒とするいわゆる酢酸法が
挙げられる。酢酸法の概略は以下の通りである。即ち、
（１）原料パルプの反応性を高めるためにフラッフ状に
する解砕工程、（２）酢酸等を散布混合する前処理工
程、（３）無水酢酸、酢酸及び酸性触媒（通常は硫酸）
より成る混酸で前処理パルプの酢化反応を行なう酢化工
程、（４）所望の酢化度となるように脱アセチル反応を
行なう熟成工程及び（５）熟成の終了した反応溶液から
酢酸セルロースを沈殿分離、精製、安定化及び乾燥する
後処理工程から成り立っている。かくして生成した酢酸
セルロースは、例えばタバコフィルターチップとして使
用するためには、通常、アセトンに溶解し、アセトンド
ープとした後、紡糸に供される。2. Description of the Related Art Cellulose acetate is one of the organic acid esters of cellulose, and its applications are clothing fibers, medical materials,
Cigarette filter chips, plastics, films,
There are a wide variety of paints and the like, and it is the most produced amount of cellulose derivatives and is industrially important. As a general method for producing cellulose acetate, there is a so-called acetic acid method using acetic anhydride as an acetylating agent, acetic acid as a diluent, and sulfuric acid as a catalyst. The outline of the acetic acid method is as follows. That is,
(1) A fluffing crushing step for increasing the reactivity of the raw material pulp, (2) a pretreatment step of sprinkling and mixing acetic acid, etc. (3) acetic anhydride, acetic acid and an acidic catalyst (usually sulfuric acid)
The acetylation step of acetylating the pretreated pulp with a mixed acid consisting of (4) the aging step of performing a deacetylation reaction to obtain a desired degree of acetylation, and (5) the addition of cellulose acetate from the reaction solution after aging. It consists of post-treatment steps of precipitation, purification, stabilization and drying. For use as a tobacco filter chip, for example, the thus-produced cellulose acetate is usually dissolved in acetone to form an acetone dope, which is then subjected to spinning.
【０００３】[0003]
【発明が解決しようとする課題】酢酸セルロースの品質
を左右する重要な因子の１つとして、原料パルプ中に不
純物として存在するヘミセルロースの含量及びその性状
を挙げることが出来る（例えば、上田ら、木材学会誌、
３４巻、４号、ｐ．３４６−３５３（１９８８））。即
ち、原料パルプ中に存在したヘミセルロースがそのまま
酢化され、溶媒に対する溶解性が低いヘミセルロースア
セテートが生成すると、紡糸性やプラスチックとしての
透明性等を著しく損なうことになる。そのため、通常に
用いられている酢酸セルロース用原料パルプは、その製
造過程において、パルプ中に存在するヘミセルロース含
量が非常に少なくなるように高度に精製されたものが好
適に用いられている。かくして精製されたパルプはシー
ト化の後、乾燥過程を経て酢酸セルロースの原料製品と
なる。しかしながら、パルプを高純度化するためには、
アルカリ抽出等の洗浄上工程を強化する必要があるた
め、結果としてコストの増大につながる。One of the important factors that influence the quality of cellulose acetate is the content and properties of hemicellulose present as impurities in the raw pulp (for example, Ueda et al., Wood). Academic journal,
Volume 34, Issue 4, p. 346-353 (1988)). That is, when hemicellulose existing in the raw material pulp is acetylated as it is and hemicellulose acetate having low solubility in a solvent is produced, spinnability and transparency as a plastic are significantly impaired. Therefore, the commonly used raw material pulp for cellulose acetate is preferably highly refined so that the content of hemicellulose present in the pulp is extremely small in the production process. The pulp thus refined is made into a sheet and then dried to be a raw material product of cellulose acetate. However, in order to highly purify the pulp,
Since it is necessary to enhance the washing process such as alkali extraction, the cost is increased as a result.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、品質の優
れた酢酸セルロースを得ることを目的として鋭意検討を
行なった。その結果、酢化反応に先立つ前処理として、
パルプ中に残存するヘミセルロースに対して選択的に加
水分解活性を有する酵素で処理することにより、反応性
の向上及び酢酸セルロースの品質向上をはかれることを
見出し、本発明を完成するに至った。即ち、本発明は原
料パルプの酢化反応の前処理としてパルプ中に存在する
ヘミセルロースのグリコシド結合を選択的に加水分解す
る酵素を含む水溶液をパルプに噴霧もしくは該水溶液中
にパルプを懸濁させ、酵素をヘミセルロースに作用させ
るプロセスを含むことを特徴とする酢酸セルロースの製
造方法を提供するものである。本発明によれば、パルプ
の酢化反応性を損なうことなくヘミセルロースを除去・
無害化し、その結果、得られる酢酸セルロースの濾過性
や透明度等の品質を向上させることが出来る。これは酵
素がヘミセルロースの選択的な解重合反応を進行させる
結果、ヘミセルロースが可溶化しパルプから除去される
こと、また、ヘミセルロースが除去された後の空隙が反
応試薬の浸透性を向上させること、更に、酢化反応物中
に残存したヘミセルロースアセテートもある程度の解重
合を受けているため溶媒への溶解性が向上し、不溶解物
の生成量が減少しているためであると考えられる。本発
明の製造方法は、ヘミセルロース含量が多いために、従
来の方法では満足な品質が得られなかった低純度パルプ
（αーセルロース含量９３％以下）から、不溶解物の少
ない高品質な酢酸セルロースを製造するのに特に有効な
方法である。[Means for Solving the Problems] The present inventors have conducted extensive studies for the purpose of obtaining cellulose acetate of excellent quality. As a result, as a pretreatment prior to the acetylation reaction,
The inventors have found that treatment with an enzyme having a selective hydrolyzing activity on hemicellulose remaining in pulp can improve reactivity and quality of cellulose acetate, and have completed the present invention. That is, the present invention sprays an aqueous solution containing an enzyme that selectively hydrolyzes glycoside bonds of hemicellulose present in the pulp as a pretreatment for the acetylation reaction of the raw pulp or suspends the pulp in the aqueous solution, The present invention provides a method for producing cellulose acetate, which comprises a process of causing an enzyme to act on hemicellulose. According to the present invention, hemicellulose is removed without impairing the acetylation reactivity of pulp.
It is rendered harmless, and as a result, the quality of the resulting cellulose acetate such as filterability and transparency can be improved. This is because the enzyme progresses the selective depolymerization reaction of hemicellulose, that hemicellulose is solubilized and removed from the pulp, and that the voids after hemicellulose are removed improve the permeability of the reaction reagent, Further, it is considered that the hemicellulose acetate remaining in the acetylation reaction product has also undergone depolymerization to some extent, so that the solubility in a solvent is improved and the amount of insoluble matter formed is reduced. Since the production method of the present invention has a high hemicellulose content, a high-quality cellulose acetate with a small amount of insoluble matter can be obtained from a low-purity pulp (α-cellulose content of 93% or less) which cannot be obtained with a conventional method in a satisfactory quality. It is a particularly effective method for manufacturing.
【０００５】[0005]
【発明の実施の形態】本発明で使用される酵素はセルロ
ース以外の多糖のグリコシド結合の加水分解反応を触媒
する活性を有するものであれば特に限定しないが、木材
パルプ中に存在する主要なヘミセルロースであるキシラ
ンに作用するキシラナーゼ及びマンナンに作用するマン
ナーゼを単独もしくは混合して用いるのが好適である。
また、酵素の起源は特にこれを限定するものではない
が、例えば、腐朽菌やある種のバクテリアが産生するキ
シラナーゼやマンナーゼ等を好適に用いることが出来
る。酵素前処理の具体的方法は先ず、酵素を含む水溶
液を調製する。この際、必要に応じてｐＨを調整し、使
用する酵素の至適ｐＨとすることが好ましい。又、使用
する酵素量は処理時間に応じて自由に変えることが可能
であるが、一般的にはパルプ１ｋｇあたり１００ｕｎｉ
ｔ以上、好ましくは３００ｕｎｉｔ以上である。なお、
１ｕｎｉｔとは処理条件下において１分間に１μｍｏｌ
のグリコシド結合を切断するのに必要な酵素量のことで
ある。又、酵素を含む水溶液の量としては、パルプ１ｋ
ｇに対して５００ｇ以上、好ましくは１ｋｇ以上、更に
好ましくは５ｋｇ以上である。該酵素水溶液を原料パ
ルプに噴霧するか、該酵素水溶液に原料パルプを浸漬し
てパルプ中のヘミセルロース加水分解する。噴霧後の温
度、時間或いは浸漬時の温度、時間は使用する酵素の特
性に合わせて設定されるべきであるが、通常採用される
温度は２５〜５５℃（好ましくは３５〜４５℃）、通常
採用される時間は１〜５時間（好ましくは２〜４時間）
である。酵素処理時のパルプはフラッフ状又は粉末状に
しておくと効果的である。酵素処理終了後のパルプか
ら濾過等によって酵素液を除去した後、通常の方法で乾
燥して水分含量を５〜１０重量％として次の酢化反応に
供する。酢化反応以降は通常の方法で実施する。BEST MODE FOR CARRYING OUT THE INVENTION The enzyme used in the present invention is not particularly limited as long as it has an activity to catalyze the hydrolysis reaction of glycoside bonds of polysaccharides other than cellulose, but it is a major hemicellulose present in wood pulp. The xylanase acting on xylan and the mannase acting on mannan are preferably used alone or in combination.
Although the origin of the enzyme is not particularly limited, for example, xylanase, mannase, etc. produced by decay fungi or certain bacteria can be preferably used. The specific method of the enzyme pretreatment is to first prepare an aqueous solution containing the enzyme. At this time, it is preferable to adjust the pH as necessary to obtain the optimum pH of the enzyme to be used. The amount of enzyme used can be freely changed according to the treatment time, but generally 100 uni per kg of pulp.
It is t or more, preferably 300 unit or more. In addition,
1 unit is 1 μmol / min under the treatment condition
It is the amount of enzyme required to cleave the glycosidic bond of. Also, the amount of the aqueous solution containing the enzyme is 1k of pulp.
The amount is 500 g or more, preferably 1 kg or more, and more preferably 5 kg or more with respect to g. The enzyme aqueous solution is sprayed on the raw material pulp, or the raw material pulp is immersed in the enzyme aqueous solution to hydrolyze hemicellulose in the pulp. The temperature after spraying, the time or the temperature during immersion, and the time should be set according to the characteristics of the enzyme used, but the temperature usually adopted is 25 to 55 ° C (preferably 35 to 45 ° C), usually The time used is 1 to 5 hours (preferably 2 to 4 hours)
It is. It is effective to fluff or powder the pulp during the enzyme treatment. After the enzyme solution is removed from the pulp after the enzyme treatment by filtration or the like, the pulp is dried by a usual method to give a water content of 5 to 10% by weight and then subjected to the next acetylation reaction. After the acetylation reaction, it is carried out by a usual method.
【０００６】[0006]
【発明の効果】本発明によれば、低純度の原料パルプか
ら濾過性や透明性等に優れた酢酸セルロースを提供する
ことが出来る。EFFECTS OF THE INVENTION According to the present invention, it is possible to provide cellulose acetate excellent in filterability and transparency from low-purity raw material pulp.
【０００７】[0007]
【実施例】以下に本発明を具体的に説明するための実施
例を示すが、本発明は以下に示す実施例に限定されるも
のではない。なお、例中、部は重量部を、％は重量％を
意味する。実施例から明らかなように、本発明により、
不溶物量を６〜７割程度にまで減少させることが出来
る。EXAMPLES Examples for specifically explaining the present invention will be shown below, but the present invention is not limited to the examples shown below. In addition, in an example, a part means a weight part and% means weight%. As is clear from the examples, according to the present invention,
The amount of insoluble matter can be reduced to about 60 to 70%.
【０００８】[0008]
【実施例１】針葉樹サルファイトパルプ（α−セルロー
ス含量８７％）を家庭用ミキサーで水解砕後、アセトン
置換して乾燥した。得られたフラッフ状パルプ５００ｇ
をキシラナーゼ（ノボ ノルディスク社製ＳＰ ４７
３）３ｇを含む１０ｌの水中に懸濁し、４０℃で３時間
処理した。得られた処理パルプは濾過により酵素液を除
去した後、乾燥して水分含量を５％としてから酢化反応
に供した。酢化反応は酵素処理パルプ１００部に対し、
５００部の酢酸を均一に散布し６０℃にて２時間混合し
た後、予め１２℃に冷却した無水酢酸２５０部及び硫酸
４部をニ−ダ−中に準備しておき、上述のパルプを投入
撹袢混合した。内容物は、原料パルプが同伴する水と無
水酢酸との反応により発熱するが、初期の１６℃前後よ
り６０分かかって７７℃に到達するように、外部冷却・
加熱により調節し、更に７７℃にて１２分間保持して酢
化反応を行なった。ついで１０部の２０％硫酸マグネシ
ウム水溶液を添加混合し、系内の硫酸を完全に中和しか
つ過剰とした。かくして中和された反応混合物をオート
クレーブに移し、密閉容器中でゲージ圧５ｋｇ／ｃｍ２
の水蒸気を撹袢下に吹き込み、約６０分かけて１５０℃
に到達させた。１５０℃で５０分間保持した後、反応物
を徐々に大気中にフラッシュさせて、反応混合物の温度
を１００℃とした。反応混合物は激しい撹袢下に希酢酸
水溶液を加えて、酢酸セルロースのフレークを生成さ
せ、充分に洗浄した後、乾燥した。得られた酢酸セルロ
ースの酢化度は５６．０、重合度は１８１であった。以
上のように調製した酢酸セルロースの品質を評価するた
めに、コールターカウンターを用いて、該酢酸セルロー
スのアセトン溶液中の不溶解物のうち、粒子経５０μｍ
以上の不溶物の体積を測定した。結果を表１に示す。な
お、測定結果は試料溶液２ｍｌ中の不溶物体積の合計値
として算出した。測定条件は以下の通り。Example 1 Softwood sulfite pulp (α-cellulose content 87%) was hydrolyzed with a household mixer, replaced with acetone and dried. 500 g of fluffy pulp obtained
Xylanase (Novo Nordisk SP 47
3) Suspended in 10 l of water containing 3 g and treated at 40 ° C for 3 hours. The resulting treated pulp was filtered to remove the enzyme solution and then dried to have a water content of 5%, and then subjected to an acetylation reaction. The acetylation reaction is based on 100 parts of enzyme-treated pulp,
After 500 parts of acetic acid was evenly sprayed and mixed at 60 ° C. for 2 hours, 250 parts of acetic anhydride and 4 parts of sulfuric acid preliminarily cooled to 12 ° C. were prepared in a kneader, and the above pulp was added. The mixture was stirred. The contents generate heat due to the reaction of acetic anhydride with the water entrained by the raw material pulp.
The temperature was adjusted by heating, and the mixture was kept at 77 ° C. for 12 minutes to carry out an acetylation reaction. Then, 10 parts of 20% magnesium sulfate aqueous solution was added and mixed to completely neutralize the sulfuric acid in the system and make it excessive. The reaction mixture thus neutralized was transferred to an autoclave, and the gauge pressure was 5 kg / cm 2 in a closed container.
Of water vapor is blown into the mixture under agitation for about 60 minutes at 150 ℃
Was reached. After holding at 150 ° C for 50 minutes, the reaction was gradually flushed into the atmosphere to bring the temperature of the reaction mixture to 100 ° C. The reaction mixture was added with dilute aqueous acetic acid under vigorous stirring to form flakes of cellulose acetate, thoroughly washed, and then dried. The obtained cellulose acetate had an acetylation degree of 56.0 and a polymerization degree of 181. In order to evaluate the quality of the cellulose acetate prepared as described above, a Coulter counter was used to calculate the particle size of 50 μm of the insoluble matter in the acetone solution of the cellulose acetate.
The volume of the above insoluble matter was measured. The results are shown in Table 1. The measurement result was calculated as the total value of the insoluble matter volume in 2 ml of the sample solution. The measurement conditions are as follows.
【０００９】 測定機器； コールターカウンターマルチサイザーＩＩ型 試料溶液組成； 酢酸セルロース試料 １．０ｗｔ％ アセトン ８９．４ 々 ＮＨ４ＳＣＮ ４．９ 々 Ｈ２Ｏ ４．７ 々Measuring instrument; Coulter Counter Multisizer type II Sample solution composition: Cellulose acetate sample 1.0 wt% Acetone 89.4 each NH 4 SCN 4.9 each H 2 O 4.7 each
【００１０】[0010]
【実施例２】前処理に用いる酵素をノボノルディスク社
製ガマナーゼ（マンナーゼ）とした以外は実施例１と同
様に酢酸セルロースを調製した。得られた酢酸セルロー
スの酢化度、重合度、及び不溶解物量を表１に示す。Example 2 Cellulose acetate was prepared in the same manner as in Example 1 except that the enzyme used for the pretreatment was Gamanase (mannase) manufactured by Novo Nordisk. Table 1 shows the degree of acetylation, the degree of polymerization, and the amount of insoluble matter of the obtained cellulose acetate.
【００１１】[0011]
【実施例３】前処理に用いる酵素として、実施例１に記
載したキシラナーゼ３ｇと実施例２に記載したマンナー
ゼ３ｇを合わせて（計６ｇ）用いたこと以外は実施例１
と同様に酢酸セルロースを調製した。得られた酢酸セル
ロースの酢化度、重合度、及び不溶解物量を表１に示
す。Example 3 Example 1 was repeated except that 3 g of xylanase described in Example 1 and 3 g of mannase described in Example 2 were combined (6 g in total) as the enzyme used for pretreatment.
Cellulose acetate was prepared in the same manner as in. Table 1 shows the degree of acetylation, the degree of polymerization, and the amount of insoluble matter of the obtained cellulose acetate.
【００１２】[0012]
【比較例１】前処理に酵素を全く使用しないこと以外は
実施例１に記載した方法と全く同様に酢酸セルロースを
調製した。得られた酢酸セルロースの酢化度、重合度、
及び不溶物量を表１に示す。Comparative Example 1 Cellulose acetate was prepared in exactly the same manner as in Example 1 except that no enzyme was used for the pretreatment. Acetation degree of the obtained cellulose acetate, degree of polymerization,
The amount of insoluble matter is shown in Table 1.
【００１３】[0013]
【表１】 [Table 1]
Claims (2)
反応を行なうための前処理として、セルロース以外の多
糖成分のグリコシド結合に対して選択的な加水分解反応
を触媒する酵素で、原料パルプを処理することを特徴と
する酢酸セルロースの製造方法。1. In a method for producing cellulose acetate, as a pretreatment for carrying out an acetylation reaction, a raw material pulp is treated with an enzyme which catalyzes a hydrolysis reaction selective for a glycoside bond of a polysaccharide component other than cellulose. A method for producing cellulose acetate, comprising:
反応するキシラナーゼ及びマンナンに選択的に反応する
マンナーゼのどちらか一方、もしくは両者をあわせて使
用することを特徴とする請求項１．に記載の酢酸セルロ
ース製造方法。2. An enzyme to be used, wherein either one of xylanase selectively reacting with xylan and mannase selectively reacting with mannan, or both of them are used together. The method for producing cellulose acetate according to 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7869996A JPH09268201A (en) | 1996-04-01 | 1996-04-01 | Production of cellulose acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7869996A JPH09268201A (en) | 1996-04-01 | 1996-04-01 | Production of cellulose acetate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09268201A true JPH09268201A (en) | 1997-10-14 |
Family
ID=13669125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7869996A Pending JPH09268201A (en) | 1996-04-01 | 1996-04-01 | Production of cellulose acetate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09268201A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000154202A (en) * | 1998-11-19 | 2000-06-06 | Daicel Chem Ind Ltd | Cellulose triacetate and method for producing the same |
| EP1247840A4 (en) * | 1999-12-08 | 2003-08-13 | Nat Inst Of Advanced Ind Scien | BIO-DEGRADABLE RESIN COMPOSITION |
| JP2010163737A (en) * | 2010-02-23 | 2010-07-29 | Daicel Chem Ind Ltd | Cellulose triacetate |
| CN101864608A (en) * | 2010-06-04 | 2010-10-20 | 焦作市卷烟材料有限公司 | Production method for regenerating secondary acetate filament bundles by waste cellulore filament bundles |
| US20110312033A1 (en) * | 2010-06-16 | 2011-12-22 | Johnway Gao | Methods of spraying saccharification enzymes and fermentation organisms onto lignocellulosic biomass for hydrolysis and fermentation processes |
-
1996
- 1996-04-01 JP JP7869996A patent/JPH09268201A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000154202A (en) * | 1998-11-19 | 2000-06-06 | Daicel Chem Ind Ltd | Cellulose triacetate and method for producing the same |
| EP1247840A4 (en) * | 1999-12-08 | 2003-08-13 | Nat Inst Of Advanced Ind Scien | BIO-DEGRADABLE RESIN COMPOSITION |
| US6669771B2 (en) | 1999-12-08 | 2003-12-30 | National Institute Of Advanced Industrial Science And Technology | Biodegradable resin compositions |
| JP4857421B2 (en) * | 1999-12-08 | 2012-01-18 | 独立行政法人産業技術総合研究所 | Biodegradable resin composition |
| JP2010163737A (en) * | 2010-02-23 | 2010-07-29 | Daicel Chem Ind Ltd | Cellulose triacetate |
| CN101864608A (en) * | 2010-06-04 | 2010-10-20 | 焦作市卷烟材料有限公司 | Production method for regenerating secondary acetate filament bundles by waste cellulore filament bundles |
| US20110312033A1 (en) * | 2010-06-16 | 2011-12-22 | Johnway Gao | Methods of spraying saccharification enzymes and fermentation organisms onto lignocellulosic biomass for hydrolysis and fermentation processes |
| US8389243B2 (en) * | 2010-06-16 | 2013-03-05 | Catchlight Energy Llc | Methods of spraying saccharification enzymes and fermentation organisms onto lignocellulosic biomass for hydrolysis and fermentation processes |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4435086B2 (en) | Cellulose esters with improved wet heat stability | |
| CN103097447B (en) | Based on cellulosic matrix material | |
| JP5171859B2 (en) | Cellulose acetate and method for producing the same | |
| WO1999016960A1 (en) | Cellulose treatment and the resulting product | |
| US9522991B2 (en) | Cellulose solution manufacturing method, cellulose precipitate manufacturing method, cellulose saccharification method, cellulose solution, and cellulose precipitate | |
| US3870703A (en) | Production of cellulose esters | |
| JPH09268201A (en) | Production of cellulose acetate | |
| JPS61174414A (en) | Production of spinnable solution for artificial fiber | |
| JP3046441B2 (en) | Method for producing cellulose acetate | |
| US3505313A (en) | Process for producing bleached and purified cellulose acetate | |
| KR100323253B1 (en) | The chitosan fiber having high degree of strength and elasticity | |
| US3846403A (en) | Production of cellulose esters from partially purified wood pulp by hemicellulose removal | |
| CN115651084B (en) | Preparation method of high-viscosity cellulose acetate butyrate | |
| JP4187797B2 (en) | Viscose production method | |
| US2847411A (en) | Process for producing hydroxyethoxycellulose | |
| Steele et al. | Cellulose Studies: XIII. The Heterogeneous Hydrolysis of Trimethyl Cellulose | |
| US3041329A (en) | Manufacture of cellulose esters of aliphatic acids | |
| US3549617A (en) | Brightening water-soluble cellulose derivatives | |
| US2074339A (en) | Preparation of cellulosic material | |
| JPS62501A (en) | Production of cellulose acetate | |
| JPH082312B2 (en) | Method for producing cellooligosaccharide | |
| US2072260A (en) | Chemical stabilization of cellulose | |
| US1916273A (en) | Process of making organic esters of cellulose | |
| KR102921707B1 (en) | Hemp cellulose acetate and method for producing same | |
| WO2001030855A1 (en) | Process for producing modified cellulose pulp |