JPH0243522B2 - - Google Patents
Info
- Publication number
- JPH0243522B2 JPH0243522B2 JP59165731A JP16573184A JPH0243522B2 JP H0243522 B2 JPH0243522 B2 JP H0243522B2 JP 59165731 A JP59165731 A JP 59165731A JP 16573184 A JP16573184 A JP 16573184A JP H0243522 B2 JPH0243522 B2 JP H0243522B2
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- carbon dioxide
- drying
- substance
- contained
- 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.)
- Expired - Lifetime
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 116
- 239000002904 solvent Substances 0.000 claims description 82
- 239000001569 carbon dioxide Substances 0.000 claims description 58
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 58
- 239000000126 substance Substances 0.000 claims description 56
- 238000001035 drying Methods 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000002994 raw material Substances 0.000 description 9
- 238000000605 extraction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 108010058846 Ovalbumin Proteins 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000003505 heat denaturation Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229940092253 ovalbumin Drugs 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Description
（産業上の利用分野）
本発明は、難乾燥性物質または熱感受性物質
（以下単に「物質」と示うことがある）中に含ま
れる水または有機溶媒などの溶剤を液体状態また
は超臨界状態の二酸化炭素を用いて抽出し、該物
質を乾燥せしめる方法に関する。
（従来の技術）
従来泥状物、ゼラチン、チーズなどの膠状物質
または抗生物質などの乾燥の困難な物質の乾燥法
として、
(i) 微粒子懸濁液、溶液またはスラリーから一挙
に乾燥製品を得るために、液滴を噴霧にして熱
風中に分散させ、熱風と材料を並流または向流
もしくは並向流の複合流に接触させ乾燥するス
プレードライング法、
(ii) 真空中でドラム乾燥器などを用いて乾燥する
真空乾燥法、
(iii) 水分を比較的多く含有する材料を凍結させ、
これを操作圧力1Torr程度の真空中で氷点以下
の温度で昇華乾燥し多孔質の製品を得る凍結乾
燥法、
(iv) 長時間自然状態で乾燥する自然乾燥法、など
が採用されており、特に食品、医薬品などの乾
燥が困難であり、また熱に対し変性し易い難乾
燥性物質または熱感受性物質には、後者の３方
法（〜）が採用されている。
（発明が解決しようとする問題点）
しかしながらこれらの難乾燥性物質または熱感
受性物質に前記乾燥方法を採用しても、
これらの物質特有の性質として、急激な条件
下での乾燥ではその表面のみを乾燥させガラス
様膜を形成し、乾燥が途中で進まなくなると示
う問題点があり、その防止のため湿度調整など
を行い、緩やかな条件下で長時間の乾燥を行わ
ざるを得ない、
長時間の乾燥時間を必要とするため、その間
の製品の変質が避けられない、
前記の如く部分的な乾燥現象が生起し易く、
製品の不均質化を生じ易く、また完全な乾燥が
困難であり製品内部に溶剤が残存し易い、
などの欠点を有する。
本発明は従来の技術的課題を背景になされたも
ので、その目的とするところは、難乾燥性物質ま
たは熱感受性物質の乾燥に際し、乾燥時間を短縮
し、低温において熱変性を与えることなく乾燥
し、更に均一かつ完全に乾燥せしめる乾燥方法を
提供することにある。
（問題点を解決するための手段）
即ち本発明は、難乾燥性物質または熱感受性物
質を液体状態または超臨界状態の二酸化炭素を用
い該物質中に含まれる溶剤Ａを抽出することによ
り乾燥せしめる難乾燥性物質または熱感受性物質
の乾燥方法において、該物質中に含まれる溶剤Ａ
に溶解しかつ溶剤Ａより前記二酸化炭素に抽出さ
れ易い低級アルコール（以下「溶剤Ｂ」と称す
る）を前記二酸化炭素または該物質のいずれか一
方に含有せしめ、まず溶剤Ａを置換した後、次い
で前記二酸化炭素のみを用いて溶剤Ｂを抽出せし
めることを特徴とする難乾燥性物質または熱感受
性物質の乾燥方法である。
液体状態または超臨界状態（温度31℃以上、圧
力72.8Kg／cm2Ｇ以上）の二酸化炭素（以下単に
「二酸化炭素」と云うことがある）、特に超臨界状
態の二酸化炭素には、水あるいはメタノール、エ
タノール、酢酸エチル、酢酸ブチル、アセトン、
イソプロピルアルコールなどの有機溶媒（以下こ
れらを単に「溶剤」と云うことがある）が可溶で
あり、本発明はかかる二酸化炭素の抽出溶媒とし
ての性質、高い蒸気圧、高い物質移動速度、無毒
性に着目してなされたものである。
ここで二酸化炭素の圧力は30〜200Kg／cm2Ｇ、
好ましくは40〜100Kg／cm2Ｇ、温度は−10〜100
℃、好ましくは０〜50℃である。特に超臨界状態
の場合には、その温度はなるべく臨界温度に近
く、一方その圧力は臨界圧力を越えてなるべく高
い方が溶剤を抽出し易い。
二酸化炭素によつて物質中に含有される溶剤を
抽出した後、該溶剤を二酸化炭素相から回収する
には、二酸化炭素相の圧力を臨界圧力以下の気体
とすることなどにより、容易に該溶剤を分離する
ことができる。
本発明において、低級アルコールとしては、メ
タノール、エタノール、プロパノールが好適に使
用される。
かくて二酸化炭素により物質中に含有される溶
剤が抽出され、該物質は乾燥される。
なお本発明の一つの実施態様として、物質中に
含まれる溶剤Ａに溶解しかつ該溶剤Ａより二酸化
炭素に抽出され易い溶剤Ｂを二酸化炭素に含有せ
しめまず溶剤Ａを置換した後、次いで二酸化炭素
のみを用いて溶剤Ｂを抽出せしめることにより物
質を乾燥してもよく、また別の実施態様として、
物質中に含まれる溶剤Ａに溶解しかつ該溶剤Ａよ
り二酸化炭素に抽出され易い溶剤Ｂをまず該物質
に添加し溶剤Ａを置換した後、次いで二酸化炭素
のみを用いて溶剤Ｂを抽出せしめ物質を乾燥せし
めてもよい。
以下図面を用いて本発明を更に詳細に説明す
る。
第１図は本発明に使用される抽出・乾燥装置の
フローチヤート、第２図は乾燥時間と溶剤残留率
との関係を示すモデル乾燥曲線図である。
まず第１図について述べると、原料（物質）は
乾燥塔１に充填される。乾燥塔１は、充填塔で示
してあるが、移動層、流動層などの他の形式であ
つても構わない。二酸化炭素は昇圧機５により圧
力30〜200Kg／cm2Ｇ、好ましくは40〜100Kg／cm2Ｇ
に昇圧させ、かつ熱交換器６により温度−10〜
100℃、好ましくは０〜50℃に調整され、乾燥器
１に供給される。
この際の二酸化炭素の圧力および温度は、原料
および乾燥除去すべき溶剤の種類、運転効率を考
慮して適宜選択される。
乾燥塔１中において、原料中に含有される溶剤
が二酸化炭素によつて抽出され、溶剤を含む二酸
化炭素相は、乾燥塔１を出て加熱器２における気
化、または減圧弁３における圧力減少により該溶
剤が析出し、溶剤回収塔４で溶剤が回収される。
二酸化炭素と溶剤との分離は、必要に応じ溶剤回
収塔４に代え、または該塔４と併用して吸着槽も
しくは洗浄槽８またはこれらの組合せを使用する
こともできる。
分離された二酸化炭素は再び昇圧機５、熱交換
器６を経て乾燥塔１へ供給される。
本発明は、以上のように難乾燥性物質または熱
感受性物質を二酸化炭素を用いて該物質中に含有
される溶剤を抽出せしめることをその骨子とする
ものであるが、乾燥の非常に困難な物質の乾燥、
溶剤残留率が非常に厳しく抑えられている場合、
人体に有害な溶剤Ａを含む物質の乾燥の場合に
は、本発明の次の二つの実施態様が更に有効であ
る。
即ち、一つの実施態様としては、第１図におい
て、まず原料中に含有される溶剤（溶剤Ａ）に可
溶でありかつ溶剤Ａよりも二酸化炭素に抽出、乾
燥され易い溶剤（溶剤Ｂ）を溶剤添加ポンプ７に
より二酸化炭素に対し５〜50重量％、好ましくは
５〜30重量％添加し、二酸化炭素と溶剤Ｂとの混
合物を乾燥器１に供給し、以下前記と同様の操作
を行い、溶剤Ａを置換する。かくて原料中の溶剤
Ａは、溶剤Ｂにより置換されながら二酸化炭素に
より抽出、除去される。溶剤Ａが抽出、除去され
た後、溶剤添加ポンプ７による溶剤Ｂの添加を止
め、以後二酸化炭素のみを乾燥塔１に供給するこ
とにより、原料中に置換、含有された溶剤Ｂを抽
出、除去すればよい。
この場合、溶剤Ｂは、第２図のモデル乾燥曲線
図により適宜選択される。
即ち第２図は、物質中に含有される溶剤を二酸
化炭素を乾燥媒体をして抽出、乾燥した場合の乾
燥時間に対する該物質中の溶剤残留率との関係を
モデル乾燥曲線として示したもので、例えば同一
物質（抗生物質）における二酸化炭素による溶剤
の抽出速度（乾燥速度）の大きさは、エタノー
ル、メタノール、水の順である。従つて、例えば
物質中にメタノールが含有されており、これを乾
燥、除去したい場合は、エタノールが溶剤Ｂとし
て選択される。また物質中に水が含有されてお
り、これを乾燥、除去したい場合はメタノール、
エタノールが溶剤Ｂとして選択されるのである。
また本発明の他の実施態様では、前記実施態様
で選択された溶剤Ｂのみをまず予め溶剤添加ポン
プ７により乾燥塔１に供給し、物質中の溶剤Ａと
置換した後、以後本発明の前記骨子に準じ、二酸
化炭素のみを用いて溶剤Ｂを抽出すればよい。
（作用）
従来の乾燥機構は、物質中に含有される乾燥、
除去すべき溶剤の移動が伝熱を伴う蒸発によつて
行われるのに対し、本発明は、物質に液体または
超臨界状態の二酸化炭素を作用させ、該物質中に
含有される溶剤を二酸化炭素中に溶剤させること
により溶剤を抽出、除去し、物質を乾燥させるも
のを骨子としたものである。抽出、乾燥後の物質
中には二酸化炭素が残留している場合があるが、
二酸化炭素は蒸気圧が高いので、物質中から容易
に気化して消失する。
（実施例）
以下実施例を挙げ、本発明を更に具体的に説明
する。
実施例 １
卵白アルブミンをPH調整により沈澱せしめ、溶
剤Ｂのエタノールにて洗浄して溶剤Ａの水分を置
換し、得られた濾過ケーキを圧力60Torr、温度
15℃で通常の真空乾燥を行なつた場合および第１
図に示す装置を用い、圧力100Kg／cm2Ｇ、温度15
℃の二酸化炭素のみを抽出溶媒として使用して乾
燥した場合の結果を第３図に示す。
第３図から明らかなように、通常の真空乾燥に
よれば20時間以上乾燥を行つても溶剤（Ａ＋Ｂ）
の残留率が10重量％以上であり、かつそれ以後で
も残留率が横ばいとなつているのに対し、本発明
のように二酸化炭素を乾燥媒体として抽出すれば
乾燥時間５時間で溶剤（Ａ＋Ｂ）の残留率を５重
量％以下とすることができることが分かる。
実施例 ２
医薬品原料（抗生物質）中に含まれるメタール
を乾燥除去するのに、第２図から明らかにされた
ようにエタノールがメタノールよりも二酸化炭素
に抽出され易いことに着目し、第１図の装置を用
い、かつ溶剤Ｂとしてエタノールを採用し、溶剤
添加ポンプ７より二酸化炭素中にエタノールを20
重量％添加し、圧力60Kg／cm2Ｇ温度10℃で１時間
供給し、メタノールの抽出・置換を行つたのち、
エタノールの供給を止め、さらに４時間二酸化炭
素のみで原料に含まれるエタノール・メタノール
を乾燥除去した。
また前記メタノールを含む医薬品原料を前記条
件の二酸化炭素のみを用いて５時間抽出除去した
結果を併せ第１表に示す。
(Industrial Application Field) The present invention is directed to converting a solvent such as water or an organic solvent contained in a difficult-to-dry substance or a heat-sensitive substance (hereinafter sometimes simply referred to as "substance") into a liquid state or a supercritical state. A method for extracting the substance using carbon dioxide and drying the substance. (Prior art) As a conventional method for drying slurry, glue substances such as gelatin and cheese, or substances that are difficult to dry such as antibiotics, (i) dry products are produced from fine particle suspensions, solutions or slurries all at once; (ii) a drum dryer in vacuum; (iii) Freezing materials containing a relatively large amount of water;
Freeze-drying, in which this is sublimated and dried at temperatures below the freezing point in a vacuum with an operating pressure of about 1 Torr, and (iv) natural drying, in which it is dried in natural conditions for a long period of time, are used. The latter three methods (-) are adopted for difficult-to-dry substances or heat-sensitive substances that are difficult to dry, such as foods and medicines, and that are easily denatured by heat. (Problem to be Solved by the Invention) However, even if the above-mentioned drying method is applied to these difficult-to-dry substances or heat-sensitive substances, due to the peculiar properties of these substances, only the surface of the substance will dry when dried under rapid conditions. There is a problem in that when dried, a glass-like film is formed, and the drying process stops midway through.To prevent this, humidity must be adjusted and drying must be carried out for a long time under mild conditions. Since a long drying time is required, deterioration of the product during that time is unavoidable, and the partial drying phenomenon described above is likely to occur.
Disadvantages include that the product tends to become non-homogeneous, that it is difficult to dry completely, and that solvents tend to remain inside the product. The present invention was made against the background of conventional technical problems, and its purpose is to shorten the drying time when drying difficult-to-dry substances or heat-sensitive substances, and to dry them at low temperatures without causing heat denaturation. Furthermore, it is an object of the present invention to provide a drying method that enables uniform and complete drying. (Means for solving the problem) That is, the present invention dries a difficult-to-dry substance or a heat-sensitive substance by extracting the solvent A contained in the substance using liquid or supercritical carbon dioxide. In a method for drying a difficult-to-dry substance or a heat-sensitive substance, the solvent A contained in the substance
A lower alcohol (hereinafter referred to as "solvent B") that is soluble in carbon dioxide and easily extracted by solvent A into the carbon dioxide is contained in either the carbon dioxide or the substance, and after first replacing the solvent A, then the This is a method for drying a difficult-to-dry substance or a heat-sensitive substance, which is characterized in that solvent B is extracted using only carbon dioxide. Carbon dioxide (hereinafter sometimes simply referred to as "carbon dioxide") in a liquid state or supercritical state (temperature 31°C or higher, pressure 72.8 Kg/cm 2 G or higher), especially carbon dioxide in a supercritical state, contains water or methanol, ethanol, ethyl acetate, butyl acetate, acetone,
Organic solvents such as isopropyl alcohol (hereinafter sometimes simply referred to as "solvents") are soluble, and the present invention utilizes the properties of such carbon dioxide as an extraction solvent, high vapor pressure, high mass transfer rate, and non-toxicity. This was done with a focus on Here, the pressure of carbon dioxide is 30-200Kg/cm 2 G,
Preferably 40-100Kg/cm 2 G, temperature -10-100
℃, preferably 0 to 50℃. Particularly in the case of a supercritical state, it is easier to extract the solvent if the temperature is as close to the critical temperature as possible, while the pressure is as high as possible above the critical pressure. After extracting the solvent contained in a substance with carbon dioxide, in order to recover the solvent from the carbon dioxide phase, the solvent can be easily recovered by reducing the pressure of the carbon dioxide phase to a gas below the critical pressure. can be separated. In the present invention, methanol, ethanol, and propanol are preferably used as the lower alcohol. The carbon dioxide thus extracts the solvent contained in the material and the material is dried. In one embodiment of the present invention, carbon dioxide contains a solvent B that dissolves in solvent A contained in the substance and is easily extracted by carbon dioxide from the solvent A, first replaces solvent A, and then replaces carbon dioxide with carbon dioxide. The material may be dried by extracting the solvent B using only a
Solvent B, which is soluble in solvent A contained in the substance and is more easily extracted by carbon dioxide than solvent A, is first added to the substance to replace solvent A, and then solvent B is extracted using only carbon dioxide. may be dried. The present invention will be explained in more detail below using the drawings. FIG. 1 is a flowchart of the extraction/drying apparatus used in the present invention, and FIG. 2 is a model drying curve diagram showing the relationship between drying time and solvent residual rate. First, referring to FIG. 1, raw materials (substances) are charged into a drying tower 1. Although the drying tower 1 is shown as a packed tower, it may be in other formats such as a moving bed or a fluidized bed. Carbon dioxide is heated to a pressure of 30 to 200 Kg/cm 2 G, preferably 40 to 100 Kg/cm 2 G by a pressure booster 5.
The pressure is increased to -10~ by the heat exchanger 6.
The temperature is adjusted to 100°C, preferably 0 to 50°C, and then supplied to the dryer 1. The pressure and temperature of carbon dioxide at this time are appropriately selected in consideration of the raw materials and the type of solvent to be dried and removed, and the operating efficiency. In the drying tower 1, the solvent contained in the raw material is extracted with carbon dioxide, and the carbon dioxide phase containing the solvent leaves the drying tower 1 and is vaporized in the heater 2 or by pressure reduction in the pressure reducing valve 3. The solvent is precipitated and recovered in the solvent recovery tower 4.
For separation of carbon dioxide and solvent, an adsorption tank, a washing tank 8, or a combination thereof may be used instead of the solvent recovery column 4 or in combination with the column 4, if necessary. The separated carbon dioxide is again supplied to the drying tower 1 via the booster 5 and the heat exchanger 6. As described above, the gist of the present invention is to extract the solvent contained in a difficult-to-dry substance or a heat-sensitive substance using carbon dioxide. drying of substances;
When the solvent residual rate is very strictly controlled,
In the case of drying substances containing solvent A that is harmful to the human body, the following two embodiments of the present invention are more effective. That is, in one embodiment, in FIG. 1, first, a solvent (solvent B) that is soluble in the solvent (solvent A) contained in the raw material and is more easily extracted and dried by carbon dioxide than solvent A is used. 5 to 50% by weight, preferably 5 to 30% by weight of carbon dioxide is added using the solvent addition pump 7, and the mixture of carbon dioxide and solvent B is supplied to the dryer 1, and the same operation as described above is performed. Replace solvent A. In this way, solvent A in the raw material is extracted and removed by carbon dioxide while being replaced by solvent B. After the solvent A is extracted and removed, the addition of the solvent B by the solvent addition pump 7 is stopped, and only carbon dioxide is then supplied to the drying tower 1, thereby extracting and removing the solvent B substituted and contained in the raw material. do it. In this case, the solvent B is appropriately selected according to the model drying curve diagram shown in FIG. In other words, Figure 2 shows the relationship between the solvent residual rate in the substance and the drying time when the solvent contained in the substance is extracted and dried using carbon dioxide as a drying medium, as a model drying curve. For example, the extraction rate (drying rate) of a solvent by carbon dioxide for the same substance (antibiotic) is in the order of ethanol, methanol, and water. Therefore, for example, if a substance contains methanol and it is desired to dry and remove it, ethanol is selected as the solvent B. In addition, if water is contained in the substance and you want to dry or remove it, use methanol,
Ethanol is chosen as solvent B. In another embodiment of the present invention, only the solvent B selected in the above embodiment is first supplied in advance to the drying tower 1 by the solvent addition pump 7 to replace the solvent A in the substance. According to the outline, solvent B may be extracted using only carbon dioxide. (Function) The conventional drying mechanism uses dryness contained in substances,
While the movement of the solvent to be removed is carried out by evaporation accompanied by heat transfer, the present invention allows liquid or supercritical carbon dioxide to act on a substance to convert the solvent contained in the substance into carbon dioxide. The main idea is to extract and remove the solvent by introducing a solvent into it, and then drying the substance. Carbon dioxide may remain in the material after extraction and drying, but
Carbon dioxide has a high vapor pressure, so it easily vaporizes and disappears from substances. (Example) The present invention will be described in more detail with reference to Examples below. Example 1 Ovalbumin was precipitated by adjusting the pH, washed with ethanol as solvent B and replaced with water in solvent A, and the resulting filter cake was heated at a pressure of 60 Torr and a temperature of 60 Torr.
When normal vacuum drying is carried out at 15℃ and the first
Using the equipment shown in the figure, pressure 100Kg/cm 2 G, temperature 15
FIG. 3 shows the results obtained when drying using only carbon dioxide at 0.degree. C. as an extraction solvent. As is clear from Figure 3, in normal vacuum drying, even after drying for more than 20 hours, the solvent (A+B)
However, if carbon dioxide is extracted as the drying medium as in the present invention, the solvent (A+B) can be extracted in 5 hours after drying. It can be seen that the residual rate of can be reduced to 5% by weight or less. Example 2 To remove metals contained in pharmaceutical raw materials (antibiotics) by drying, we focused on the fact that ethanol is more easily extracted by carbon dioxide than methanol, as shown in Figure 2, and used Figure 1. Using the same equipment, and using ethanol as solvent B, 20% of ethanol was added to carbon dioxide from the solvent addition pump 7.
After adding % by weight and supplying at a pressure of 60 kg/cm 2 G and a temperature of 10°C for 1 hour to extract and replace methanol,
The supply of ethanol was stopped, and the ethanol and methanol contained in the raw materials were dried and removed using only carbon dioxide for another 4 hours. Table 1 also shows the results of extracting and removing the pharmaceutical raw material containing methanol for 5 hours using only carbon dioxide under the conditions described above.
【表】
（発明の効果）
以上のように本発明によれば、物質中に含有さ
れる溶剤の二酸化炭素への移動が溶解により行わ
れるため、乾燥時に高温度を必要としないこと、
また二酸化炭素が高い物質移動速度を有すること
により物質内部での溶剤の移動が速やかに行われ
ことなどにより、従来技術で問題となつている物
質表面のみの乾燥によるガラス膜化、製品の不均
質化が生起しない。
また本発明は、従来技術の熱移動が必要な乾燥
機構とは異なり、物質中に含有される溶剤を二酸
化炭素を用い置換あるいは抽出作用により除去せ
しめるものであるので、二酸化炭素のみの処理に
より充分な乾燥が可能であるが、前記の如く溶剤
Ｂの併用により更に短時間かつ完全乾燥が可能で
ある。
このように本発明では、難乾燥性物質または熱
感受性物質を短時間に乾燥することができ、かつ
二酸化炭素が化学的に不活性であるため製品の変
質がなく、また二酸化炭素が高い蒸気圧を有する
ため抽出処理後も製品に該二酸化炭素が残留せ
ず、微量残留したとしても人体に無害であり、何
ら問題を生起しないと云う利点を有する。[Table] (Effects of the Invention) As described above, according to the present invention, since the solvent contained in the substance is transferred to carbon dioxide by dissolution, high temperature is not required during drying.
In addition, due to the high mass transfer rate of carbon dioxide, the movement of the solvent within the material occurs quickly, resulting in the formation of a glass film due to drying of only the surface of the material, which has been a problem with conventional technology, and the non-uniformity of the product. No change occurs. Furthermore, unlike the conventional drying mechanism that requires heat transfer, the present invention uses carbon dioxide to remove the solvent contained in the substance by displacement or extraction, so treatment with carbon dioxide alone is sufficient. However, by using solvent B in combination as described above, complete drying can be achieved in a shorter time. As described above, in the present invention, difficult-to-dry substances or heat-sensitive substances can be dried in a short time, and since carbon dioxide is chemically inert, there is no deterioration of the product, and carbon dioxide has a high vapor pressure. It has the advantage that the carbon dioxide does not remain in the product even after the extraction process, and even if a small amount remains, it is harmless to the human body and does not cause any problems.
第１図は本発明に使用される抽出・乾燥装置の
フローチヤート、第２図は乾燥時間と溶剤残留率
との関係を示すモデル乾燥曲線図、第３図は乾燥
時間と溶剤残留率との関係を示す乾燥曲線図であ
る。
第１図において、１は乾燥塔、２は加熱器、３
は減圧弁、４は溶剤回収塔、５は昇圧器、６は熱
交換器、７は溶剤添加ポンプ、８は吸着塔または
洗浄塔である。
Figure 1 is a flowchart of the extraction/drying apparatus used in the present invention, Figure 2 is a model drying curve diagram showing the relationship between drying time and solvent residual rate, and Figure 3 is a diagram showing the relationship between drying time and solvent residual rate. It is a drying curve diagram showing the relationship. In Figure 1, 1 is a drying tower, 2 is a heater, 3
4 is a pressure reducing valve, 4 is a solvent recovery tower, 5 is a pressure booster, 6 is a heat exchanger, 7 is a solvent addition pump, and 8 is an adsorption tower or a washing tower.
Claims (1)
または超臨界状態の二酸化炭素を用い該物質中に
含まれる溶剤Ａを抽出することにより乾燥せしめ
る難乾燥物質または熱感受性物質の乾燥方法にお
いて、該物質中に含まれる溶剤Ａに溶解しかつ溶
剤Ａより前記二酸化炭素に抽出され易い低級アル
コールを前記二酸化炭素または該物質のいずれか
一方に含有せしめ、まず溶剤Ａを置換した後、次
いで前記二酸化炭素のみを用いて低級アルコール
を抽出せしめることを特徴とする難乾燥性物質ま
たは熱感受性物質の乾燥方法。1. A method for drying a difficult-to-dry substance or a heat-sensitive substance, in which a difficult-to-dry substance or a heat-sensitive substance is dried by extracting solvent A contained in the substance using carbon dioxide in a liquid state or a supercritical state. Either the carbon dioxide or the substance contains a lower alcohol that dissolves in the solvent A contained in the carbon dioxide and is easily extracted by the carbon dioxide, and after first replacing the solvent A, only the carbon dioxide is added. A method for drying a difficult-to-dry substance or a heat-sensitive substance, the method comprising extracting a lower alcohol using a
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16573184A JPS6146202A (en) | 1984-08-09 | 1984-08-09 | Drying method of difficult-to-dry substance or heat-sensitive substance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16573184A JPS6146202A (en) | 1984-08-09 | 1984-08-09 | Drying method of difficult-to-dry substance or heat-sensitive substance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6146202A JPS6146202A (en) | 1986-03-06 |
| JPH0243522B2 true JPH0243522B2 (en) | 1990-09-28 |
Family
ID=15817998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16573184A Granted JPS6146202A (en) | 1984-08-09 | 1984-08-09 | Drying method of difficult-to-dry substance or heat-sensitive substance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6146202A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4946965A (en) * | 1989-02-22 | 1990-08-07 | Eastman Kodak Company | Process for drying solid photographic addenda |
| CN100350996C (en) | 2002-06-03 | 2007-11-28 | 财团法人电力中央研究所 | Method for removing water contained in solid using liquid material |
| NZ551265A (en) * | 2006-11-10 | 2010-03-26 | Nz Forest Research Inst Ltd | Wood drying in the presence of supercritical carbon dioxide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5633395A (en) * | 1979-08-23 | 1981-04-03 | Uemura Koichi | Continuous traction method and its device |
-
1984
- 1984-08-09 JP JP16573184A patent/JPS6146202A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5633395A (en) * | 1979-08-23 | 1981-04-03 | Uemura Koichi | Continuous traction method and its device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6146202A (en) | 1986-03-06 |
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