JPH02101093A - Purification of levoglucosan - Google Patents
Purification of levoglucosanInfo
- Publication number
- JPH02101093A JPH02101093A JP25442988A JP25442988A JPH02101093A JP H02101093 A JPH02101093 A JP H02101093A JP 25442988 A JP25442988 A JP 25442988A JP 25442988 A JP25442988 A JP 25442988A JP H02101093 A JPH02101093 A JP H02101093A
- Authority
- JP
- Japan
- Prior art keywords
- raw material
- levoglucosan
- organic solvent
- pressure
- material containing
- 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
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 title claims description 18
- 238000000746 purification Methods 0.000 title 1
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- -1 alicyclic ketone Chemical class 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 229920000742 Cotton Polymers 0.000 claims abstract description 4
- 239000010893 paper waste Substances 0.000 claims abstract description 4
- 239000010902 straw Substances 0.000 claims abstract description 3
- 239000002023 wood Substances 0.000 claims abstract description 3
- 229920002678 cellulose Polymers 0.000 claims description 12
- 239000001913 cellulose Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 241000609240 Ambelania acida Species 0.000 claims description 2
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 2
- 241000219146 Gossypium Species 0.000 claims description 2
- 239000010905 bagasse Substances 0.000 claims description 2
- 235000009120 camo Nutrition 0.000 claims description 2
- 235000005607 chanvre indien Nutrition 0.000 claims description 2
- 239000011487 hemp Substances 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 abstract 1
- 240000008564 Boehmeria nivea Species 0.000 abstract 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000005979 thermal decomposition reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229920001542 oligosaccharide Polymers 0.000 description 2
- 150000002482 oligosaccharides Chemical class 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- QQCVUTANJCNOMT-UHFFFAOYSA-N OC.CCO.CC(C)=O.CCC(C)=O Chemical compound OC.CCO.CC(C)=O.CCC(C)=O QQCVUTANJCNOMT-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Saccharide Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はセルロースおよびセルロース含有物質から、熱
分解によってレボグルコサンを製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing levoglucosan from cellulose and cellulose-containing materials by pyrolysis.
近年、医薬品、農薬品などのファインケミカル分野で、
オリゴ糖、ポリサッカライドが注目されている。そして
、これらの合成原料の一つとして重要視されているもの
にレボグルコサンがある。In recent years, in the fine chemical field such as pharmaceuticals and agrochemicals,
Oligosaccharides and polysaccharides are attracting attention. Levoglucosan is considered important as one of these synthetic raw materials.
ところで従来、レボグルコサンの製造方法としては、Ａ
、高真空下に２００〜４００°Ｃでセルロスを熱分解し
、生成するレボグルコサンを昇華させて反応系外に取り
出す方法、およびＡ法の改良法としてのＢ、超臨界アセ
トンを耐圧容器内に連続して高圧ポンプで送入しながら
（２５０パール、２５０〜３４０℃）熱分解する方法が
知られているＣＰｅｔｅｒ Ｋｏｌｌら、Ａｎｇｅｗ、
Ｃｈｅｍ、 、、 ９０．８０２〜８０３（１９７８）
）。By the way, the conventional method for producing levoglucosan is A.
, A method of thermally decomposing cellulose at 200 to 400°C under high vacuum, sublimating the produced levoglucosan and taking it out of the reaction system, and B as an improved method of method A. Continuous supercritical acetone in a pressure container. Peter Koll et al., Angew et al.
Chem, 90.802-803 (1978)
).
上記Ａ法では、生成レボグルコサンが昇華できるように
、反応系を高真空に保つことが必須の条件であるが、熱
分解に伴う分解ガスのために、反応系を高真空に保つこ
とは極めて困難であり、また高真空のために熱分解に必
要な熱の伝導が極めて悪い欠点があった。In method A, it is essential to maintain the reaction system in a high vacuum so that the produced levoglucosan can sublimate, but it is extremely difficult to maintain the reaction system in a high vacuum due to the decomposition gas that accompanies thermal decomposition. Moreover, due to the high vacuum, conduction of the heat necessary for thermal decomposition was extremely poor.
またＢ法では、アセトンを供給するための高圧流体圧入
系が必要になるので、装置全体が大きくなる欠点があり
、またＡ法のセルロースに比較して大量のアセトンを使
用するので、低濃度の生成レボグルコサンを含む反応液
しか得られない。In addition, Method B requires a high-pressure fluid injection system to supply acetone, which has the disadvantage of increasing the size of the entire device.Also, since it uses a large amount of acetone compared to Method A, it requires a high-pressure fluid injection system to supply acetone. Only a reaction solution containing the produced levoglucosan can be obtained.
本発明は、高圧流体圧大系、すなわち高圧ポンプ、減圧
パルプ、圧力針、流量計などを必要としない、より簡便
をレボグルコサンの製造方法を提供することを目的とし
ている。An object of the present invention is to provide a simpler method for producing levoglucosan that does not require a large high-pressure fluid system, ie, a high-pressure pump, vacuum pulp, pressure needle, flow meter, etc.
（課題を解決するための手段〕
上記目的を達成するため、本発明のレボグルコサンの製
造方法は、セルロース成分を含む原料を有機溶媒と共に
耐圧容器に入れ、２５０〜３５０℃に加熱することを特
徴とするものである。(Means for Solving the Problems) In order to achieve the above object, the method for producing levoglucosan of the present invention is characterized in that a raw material containing a cellulose component is placed in a pressure container together with an organic solvent and heated to 250 to 350°C. It is something to do.
すなわち本発明においては、耐圧容器、例えばオートク
レーブにセルロース成分を含む原料および有機溶媒を入
れ、常圧で密閉し、２５０〜３５０℃に一定時間保つこ
とによって溶媒蒸気が熱分解媒体として機能し、セルロ
ース成分を含む原料を高圧下で熱分解し、その後放冷し
て反応を終了させる。That is, in the present invention, a raw material containing a cellulose component and an organic solvent are placed in a pressure-resistant container, such as an autoclave, sealed at normal pressure, and kept at 250 to 350°C for a certain period of time, so that the solvent vapor functions as a thermal decomposition medium, and the cellulose The raw material containing the components is thermally decomposed under high pressure, and then allowed to cool to complete the reaction.
反応終了後、耐圧容器から反応物を取り出し、不溶解部
分を濾別すると、レボグルコサンの溶媒溶液が得られる
。After the reaction is completed, the reactant is taken out from the pressure container and the undissolved portion is filtered off to obtain a solvent solution of levoglucosan.
本発明におけるセルロース成分を含む原料としては、特
に限定されないが、アビセル、リンク−、パルプ、木綿
、麻、バガス、古紙、木材および藁などを使用すること
ができ、特にセルロース含量の高いアビセル、リンター
、パルプ、木綿および古紙の使用が好ましい。The raw material containing the cellulose component in the present invention is not particularly limited, but can be used such as Avicel, link, pulp, cotton, hemp, bagasse, waste paper, wood, and straw. Preference is given to using pulp, cotton and waste paper.
また、セルロース成分を含む原料の熱分解媒体として機
能する有機溶媒としては、レボグルコサンを溶解する溶
媒であれば使用することができるが、温度と蒸気圧との
関係から、アセトン、メチルエチルケトン、メチルイソ
ブチルケトン等の脂肪族ケトン、シクロヘキサノン等の
脂環族ケトン、メタノール、エタノール、プロパツール
、メタノール等の脂肪族アルコールが好ましく、アセト
ン、メチルエチルケトンが特に好ましい。In addition, as an organic solvent that functions as a thermal decomposition medium for raw materials containing cellulose components, any solvent that dissolves levoglucosan can be used, but due to the relationship between temperature and vapor pressure, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Aliphatic ketones such as cyclohexanone, alicyclic ketones such as cyclohexanone, aliphatic alcohols such as methanol, ethanol, propatool, and methanol are preferred, and acetone and methyl ethyl ketone are particularly preferred.
これら溶媒は蒸気圧の関係から混合使用することもでき
る。These solvents can also be used in combination in view of vapor pressure.
加熱温度および加熱時間は、セルロース原料および用い
る溶媒の種類、仕込み量によって最適の条件を設定する
ことができるが、通常では２５０〜３５０℃、３０分〜
３時間で十分であり、レボグルコサンの生成速度、二次
分解反応等の副反応の起こりやすさの関係から３００〜
３３０’Ｃ。The optimal heating temperature and heating time can be set depending on the type and amount of the cellulose raw material and solvent used, but usually 250 to 350°C, 30 minutes to
3 hours is sufficient, and considering the production rate of levoglucosan and the likelihood of side reactions such as secondary decomposition reactions,
330'C.
３０分〜２時間で行うのが好ましい。It is preferable to carry out for 30 minutes to 2 hours.
以下、本発明の実施例を述べる。Examples of the present invention will be described below.
実施例１
５０ｍ１容積のステンレス製耐圧容器に３０ｍ１のアセ
トン、アビセル１．８ｇおよび攪拌用の５７８インチス
テンレス製ポールを入れて密閉した。Example 1 30 ml of acetone, 1.8 g of Avicel, and a 578 inch stainless steel pole for stirring were placed in a 50 ml volume stainless steel pressure vessel and sealed.
この耐圧容器を加熱炉を用いて３０分間で３３０“Ｃに
昇温させ、１時間熱分解を行った。This pressure-resistant container was heated to 330"C in 30 minutes using a heating furnace, and thermal decomposition was performed for 1 hour.
その間、１０分毎に容器を振とうし、内容物を混合した
。During this time, the container was shaken every 10 minutes to mix the contents.
反応終了後、放冷し、内容物をろ過してレボグルコサン
８１０ｍｇを含むアセトン溶液を得た。After the reaction was completed, the mixture was allowed to cool and the contents were filtered to obtain an acetone solution containing 810 mg of levoglucosan.
実施例２〜５
実施例１と同様の操作によって、種々の条件で熱分解を
行った。Examples 2 to 5 Thermal decomposition was carried out under various conditions in the same manner as in Example 1.
結果を下記表に示す。The results are shown in the table below.
（以下、本頁余白）
分解時間 ３ １ ０．５ １．５レボグルコ
サン収量
（ｍ ）
注：ＭＥＫ
Ｎ
Ｎ
Ｃ
〔発明の効果〕
以上述べたように本発明によれば、セルロス成分を含む
原料が有機溶媒と共に耐圧容器中で加熱されるので、有
機溶媒の蒸気がセルロス成分を含む原料を熱分解する媒
体として機能メチルエチルケトン
メタノール
エタノール
アセトン
するようになる。従って、二酸化炭素などの熱分解に伴
う分解ガスを発生することが全くなく、耐圧容器を放冷
した後は、容器内は完全に常圧に戻っており、操作上極
めて安全である。(Hereinafter, the margin of this page) Decomposition time 3 1 0.5 1.5 Levoglucosan yield (m ) Note: MEK N N C [Effects of the invention] As described above, according to the present invention, raw materials containing cellulose components are Since it is heated in a pressure vessel together with an organic solvent, the vapor of the organic solvent becomes methyl ethyl ketone methanol ethanol acetone which acts as a medium to thermally decompose the raw materials containing cellulosic components. Therefore, no decomposition gas such as carbon dioxide is generated due to thermal decomposition, and after the pressure-resistant container is allowed to cool, the pressure inside the container completely returns to normal pressure, making it extremely safe to operate.
また、耐圧容器以外の高圧ポンプや減圧バルブ等の設備
を全く必要としないので、装置を著しく簡便化すること
ができる。Further, since no equipment such as a high-pressure pump or a pressure-reducing valve is required other than the pressure-resistant container, the apparatus can be significantly simplified.
本発明によって得られたレボグルコサンは、医薬品、農
薬品などファインケミカルとしてのオリゴ糖、ポリサッ
カライドの合成原料として重要視されている化合物であ
り、本発明によってその製造が容易になり、更に工業原
料としての応用発展が期待される。The levoglucosan obtained by the present invention is a compound that is considered important as a raw material for the synthesis of oligosaccharides and polysaccharides as fine chemicals such as pharmaceuticals and agricultural products. Application development is expected.
特許出願人 工業技術院長 飯 塚 幸 三指定代理
人 工業技術院大阪工業技術試験所長速水諒三Patent applicant Kozo Iizuka, Director of the Agency of Industrial Science and Technology Designated agent: Ryozo Hayami, Director of the Osaka Institute of Industrial Science and Technology, Agency of Industrial Science and Technology
Claims (1)
器に入れ、２５０〜３５０℃に加熱することを特徴とす
るレボグルコサンの製造方法。 ２、前記セルロース成分を含む原料が、アビセル、リン
ター、パルプ、木綿、麻、バガス、古紙、木材および藁
から選ばれる請求項１記載のレボグルコサンの製造方法
。 ３、前記有機溶媒が、脂肪族ケトン、脂環族ケトンおよ
び脂肪族アルコールから選ばれた少なくとも１種である
請求項１記載のレボグルコサンの製造方法。[Claims] 1. A method for producing levoglucosan, which comprises placing a raw material containing a cellulose component together with an organic solvent in a pressure-resistant container and heating it to 250 to 350°C. 2. The method for producing levoglucosan according to claim 1, wherein the raw material containing the cellulose component is selected from Avicel, linter, pulp, cotton, hemp, bagasse, waste paper, wood, and straw. 3. The method for producing levoglucosan according to claim 1, wherein the organic solvent is at least one selected from aliphatic ketones, alicyclic ketones, and aliphatic alcohols.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25442988A JPH02101093A (en) | 1988-10-07 | 1988-10-07 | Purification of levoglucosan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25442988A JPH02101093A (en) | 1988-10-07 | 1988-10-07 | Purification of levoglucosan |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02101093A true JPH02101093A (en) | 1990-04-12 |
Family
ID=17264862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25442988A Pending JPH02101093A (en) | 1988-10-07 | 1988-10-07 | Purification of levoglucosan |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02101093A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009005168A1 (en) | 2007-07-03 | 2009-01-08 | Takashi Kawasaki | Process for production of monosaccharide and process for production of ethanol both utilizing cellulose-based substance |
| JP2010202626A (en) * | 2009-03-06 | 2010-09-16 | Japan Advanced Institute Of Science & Technology Hokuriku | Method for producing anhydrosugar |
-
1988
- 1988-10-07 JP JP25442988A patent/JPH02101093A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| ANGEWANTE CHEMIE=1978 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009005168A1 (en) | 2007-07-03 | 2009-01-08 | Takashi Kawasaki | Process for production of monosaccharide and process for production of ethanol both utilizing cellulose-based substance |
| US8324374B2 (en) | 2007-07-03 | 2012-12-04 | Taiyu Kensetsu Kabushiki Kaisha | Process for production of monosaccharide and process for production of ethanol both utilizing cellulose-based substance |
| JP2010202626A (en) * | 2009-03-06 | 2010-09-16 | Japan Advanced Institute Of Science & Technology Hokuriku | Method for producing anhydrosugar |
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