JPH0728719B2 - Continuous ester synthesizer and its continuous synthesis method - Google Patents
Continuous ester synthesizer and its continuous synthesis methodInfo
- Publication number
- JPH0728719B2 JPH0728719B2 JP3337502A JP33750291A JPH0728719B2 JP H0728719 B2 JPH0728719 B2 JP H0728719B2 JP 3337502 A JP3337502 A JP 3337502A JP 33750291 A JP33750291 A JP 33750291A JP H0728719 B2 JPH0728719 B2 JP H0728719B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction system
- reaction
- ester
- continuous
- synthesis
- 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
- 150000002148 esters Chemical class 0.000 title claims description 47
- 238000001308 synthesis method Methods 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims description 134
- 108090001060 Lipase Proteins 0.000 claims description 38
- 102000004882 Lipase Human genes 0.000 claims description 38
- 239000004367 Lipase Substances 0.000 claims description 38
- 235000019421 lipase Nutrition 0.000 claims description 38
- 230000015572 biosynthetic process Effects 0.000 claims description 29
- 238000003786 synthesis reaction Methods 0.000 claims description 29
- 230000018044 dehydration Effects 0.000 claims description 26
- 238000006297 dehydration reaction Methods 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 20
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 208000005156 Dehydration Diseases 0.000 description 25
- 239000011261 inert gas Substances 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000001035 drying Methods 0.000 description 12
- 238000005886 esterification reaction Methods 0.000 description 12
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 10
- 239000012295 chemical reaction liquid Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 230000032050 esterification Effects 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 150000005846 sugar alcohols Polymers 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 241000235395 Mucor Species 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 3
- 239000003957 anion exchange resin Substances 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003925 fat Substances 0.000 description 3
- 235000019197 fats Nutrition 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108010048733 Lipozyme Proteins 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 235000019774 Rice Bran oil Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 229940110456 cocoa butter Drugs 0.000 description 1
- 235000019868 cocoa butter Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000010701 ester synthesis reaction Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- FCCDDURTIIUXBY-UHFFFAOYSA-N lipoamide Chemical compound NC(=O)CCCCC1CCSS1 FCCDDURTIIUXBY-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000008165 rice bran oil Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】本発明は、固定化リパーゼを用い
てアルコール、特にグリセリン、グリコール類、糖類な
どの多価アルコールと酸とのエステル化反応を段階的に
進行させてエステルの連続合成を行うに特に好ましく使
用し得る装置及び方法に関するもので、油化学工業、食
品工業、製薬工業などに利用される。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the continuous synthesis of an ester by using an immobilized lipase to stepwisely perform an esterification reaction of an alcohol, particularly a polyhydric alcohol such as glycerin, glycols and sugars with an acid. The present invention relates to an apparatus and a method which can be particularly preferably used, and is used in the oil chemical industry, food industry, pharmaceutical industry and the like.
【０００２】[0002]
【従来の技術】従来、固定化リパーゼを用いてエステル
を連続的に合成する方法として、複数個の固定化リパー
ゼカラムに、水分を０〜０．０２％と低く抑えたオレイ
ック油脂とステアリン酸をメリーゴーランドのように通
過させてカカオバター脂用油脂を製造することが報告さ
れている。〔橋本征雄：油脂、４１（１０）６２（１９
８８）〕。又、固定床型連続反応を行う場合、固定床リ
アクターから排出される水分濃度の上昇した反応油を、
反応器外で脱水剤充填塔、減圧脱水槽、不活性ガス脱水
塔のいずれか１つ又は２つ以上を組合わせて用いて脱水
してリアクター入口に戻しリサイクルさせてエステルを
合成する方法は公知である。（特開昭６４−２５８
８）。2. Description of the Related Art Conventionally, as a method for continuously synthesizing an ester using immobilized lipase, oleic oil and stearic acid and stearic acid whose water content has been kept as low as 0 to 0.02% are used in a plurality of immobilized lipase columns. It has been reported to produce a fat for cocoa butter fat such as merry-go-round. [Hashimoto, Seio: Fats, 41 (10) 62 (19)
88)]. When performing a fixed bed type continuous reaction, the reaction oil with an increased water concentration discharged from the fixed bed reactor is
A method for synthesizing an ester by dehydrating it outside the reactor by using any one or a combination of a dehydrating agent packed tower, a reduced pressure dehydrating tank, and an inert gas dehydrating tower and returning it to the reactor inlet for recycling is known. Is. (JP-A 64-258
8).
【０００３】[0003]
【発明が解決しようとする課題】上記従来の前者の合成
法では、水を生成しないエステル交換反応には有効であ
るが、反応と同時に水を生成するエステル合成には収率
が極めて悪い。上記従来の後者の合成法では、脱水はで
きるが、１つの固定床リアクターでエステル合成を行う
ため、即ち、１種類のリパーゼでエステル化反応を行う
必要があるため、その１つのリアクターに反応液を長時
間に亘り多数回リサイクルしなければならず、相当の時
間がかゝり、特に多段階反応を行う場合、生産性が悪い
ばかりでなく又リパーゼに相当の負担がかゝり、活性の
低下が早くおこるなどの不都合をもたらす。The former synthetic method described above is effective for the transesterification reaction which does not produce water, but the yield is extremely poor for the ester synthesis which produces water at the same time as the reaction. In the latter latter conventional synthesis method described above, dehydration is possible, but since the ester synthesis is carried out in one fixed bed reactor, that is, the esterification reaction needs to be carried out with one type of lipase, the reaction solution Has to be recycled many times over a long period of time, and it takes a considerable amount of time. Especially, when carrying out a multi-step reaction, not only the productivity is poor, but also the lipase has a considerable burden and the activity is low. This causes inconveniences such as a rapid decline.
【０００４】[0004]
【課題を解決するための手段】本願の第１発明は、上記
の従来の事情に鑑み、上記の不都合を解消すると共に、
固定化リパーゼの負担を軽減し得られ、且つ収率を向上
し得る生産性の高いエステルの連続合成装置を提供する
もので、固定化リパーゼを内蔵した固定床リアクターと
脱水槽とを循環用ポンプを介してループ状に連結して成
る反応系を少なくとも２段に配設すると共に、相隣る反
応系を転送用ポンプを介入した転送パイプにより接続
し、酸とアルコールの供給源を第１反応系に接続し、最
終の反応系に生産物の取出口を備えて成る。更に、本願
の第２発明は、上記の本発明装置を利用し、高収率にエ
ステルの連続合成を行うことができるエステルの連続合
成法を提供するもので、上記の第１発明の装置によりエ
ステルの連続合成を行うに当たり、その夫々の段階の反
応系に用いる夫々の固定化リパーゼを適当に選択するこ
とを特徴とする。更に、本願の第３発明は、上記の本発
明装置を利用し、高収率にエステルの連続合成を行うこ
とができるエステルの連続合成法を提供するもので、上
記の第１発明の装置によりエステルの連続合成を行うに
当たり、夫々の反応系における反応条件を至適に調節す
ることを特徴とする。In view of the above-mentioned conventional circumstances, the first invention of the present application eliminates the above-mentioned inconvenience, and
A continuous ester synthesizer with high productivity that can reduce the burden of immobilized lipase and improve the yield. A pump for circulating a fixed bed reactor containing immobilized lipase and a dehydration tank. At least two stages of reaction systems connected in a loop form are arranged, and adjacent reaction systems are connected by a transfer pipe interposing a transfer pump, and the acid and alcohol supply sources are the first reaction. It is connected to the system and comprises a product outlet in the final reaction system. Further, a second invention of the present application provides a continuous ester synthesis method capable of performing continuous ester synthesis in high yield by utilizing the above-mentioned apparatus of the present invention. When carrying out continuous ester synthesis, each immobilized lipase used in the reaction system at each stage is appropriately selected. Furthermore, a third invention of the present application provides a continuous ester synthesis method capable of performing continuous ester synthesis in high yield by utilizing the above-mentioned apparatus of the present invention. It is characterized in that the reaction conditions in each reaction system are optimally adjusted in carrying out the continuous synthesis of the ester.
【０００５】[0005]
【作用】本装置を用いエステルの連続合成を行うには、
アルコールと酸とを第１反応系に供給し、これらの基質
を循環用ポンプを駆動してループ状にリサイクルして固
定床リアクターとによるエステル化反応と脱水槽による
脱水処理とを繰り返し、かくして得られた反応液を転送
用ポンプにより次の段階の追加の反応系に転送し、該反
応系において、反応液につき循環用ポンプを駆動して、
前記と同様に固定床リアクターによるエステル化と脱水
槽による脱水処理を繰り返し行い、最終の反応液即ち、
生産物を第２反応系より或いはその後の反応系より該生
産物を取り出す。このように、各反応系においてエステ
ル合成反応により副生する水は、夫々の反応系で反応系
外に除去されるので、エステル合成を段階的に進行させ
ることができ、各反応系の反応液組成はほぼ一定となり
反応管理が容易になるばかりでなく、最終の反応系から
目的とするエステルを連続的に取得することができる。
かくして、本装置は、複数段に反応系を設けたので、一
定量の酸とアルコールからエステル合成するに当たり、
複数段の固定床リアクターで夫々エステル化を行うこと
が可能であり、各固定化リパーゼの負担量は軽減し、長
期に亘り良好な活性を維持することができる。更に又、
夫々の反応系の反応条件を最適状態に夫々設定すること
が可能となる。而して、第２発明のように、その夫々の
反応系の固定床リアクターに内蔵せしめる固定化リパー
ゼの種類を適宜選択して使用することにより、例えば、
多価アルコールと酸とのエステル合成に当たっては、夫
々の反応段階に適した特性を有するもの及び量を選択使
用し、或いは、第３発明のように、夫々の反応系におけ
る反応液の水分含有量、脱水処理条件、反応温度などの
反応条件を、夫々の固定床リアクターの固定化リパーゼ
に合せたものに夫々調節するときは、生産物、例えばト
リグリセリドを高収率に得ることができる。[Function] To carry out continuous ester synthesis using this apparatus,
Alcohol and acid are supplied to the first reaction system, and these substrates are recycled into a loop by driving a circulation pump to repeat the esterification reaction with the fixed bed reactor and the dehydration treatment with the dehydration tank, thus obtaining The reaction liquid thus obtained is transferred to an additional reaction system of the next stage by a transfer pump, and in the reaction system, a circulation pump is driven for the reaction liquid,
Repeated esterification by a fixed bed reactor and dehydration treatment by a dehydration tank in the same manner as described above, the final reaction solution, that is,
The product is taken out from the second reaction system or the subsequent reaction system. In this way, since the water by-produced by the ester synthesis reaction in each reaction system is removed to the outside of the reaction system in each reaction system, the ester synthesis can be progressed stepwise, and the reaction liquid of each reaction system Not only does the composition become almost constant and the reaction management becomes easier, but the target ester can be continuously obtained from the final reaction system.
In this way, since the present apparatus was provided with reaction systems in multiple stages, when synthesizing an ester from a fixed amount of acid and alcohol,
Esterification can be carried out in each of a plurality of fixed bed reactors, the burden of each immobilized lipase can be reduced, and good activity can be maintained for a long period of time. Furthermore,
It is possible to set the reaction conditions of each reaction system to the optimum state. Thus, as in the second invention, by appropriately selecting and using the type of the immobilized lipase to be incorporated in the fixed bed reactor of each reaction system, for example,
In the ester synthesis of a polyhydric alcohol and an acid, those having properties and amounts suitable for each reaction step are selected and used, or, as in the third invention, the water content of the reaction liquid in each reaction system. When the reaction conditions such as the dehydration treatment condition and the reaction temperature are adjusted to those suitable for the immobilized lipase of each fixed bed reactor, a product, for example, triglyceride can be obtained in high yield.
【０００６】[0006]
【実施例】次に、本発明のエステル連続合成装置とその
連続合成法の実施例を添付図面に基いて説明する。Embodiments of the continuous ester synthesis apparatus and continuous synthesis method of the present invention will be described below with reference to the accompanying drawings.
【０００７】図１は、本発明実施の１例のエステル化連
続合成装置を示し、固定化リパーゼを内蔵した固定床リ
アクター１と脱水槽２とを循環用ポンプ３を介入した循
環用接続管３ａを介してループ状に連結して成る反応系
を少なくとも２個に配設し、相隣る反応系を転送用ポン
プ４を介入した転送用パイプ５により接続する。図示の
例では、２段の反応系Ａ，Ｂを設置した場合を示し、そ
の第１反応系Ａの流入口、図示の例では、該脱水槽２の
上端蓋板に設けた流入口６，７に、酸とアルコール供給
源として、例えば、酸と多価アルコールの供給源タンク
８，９を夫々の接続管１０，１１を介し接続し、最終の
反応系、即ち図示の例では、第２反応系Ｂに生産物の取
出口１２として該固定床１の下部に接読する管状取出口
１２を備えたものである。FIG. 1 shows an esterification continuous synthesizing apparatus according to one embodiment of the present invention, in which a fixed bed reactor 1 containing an immobilized lipase and a dehydration tank 2 are connected to a circulation connecting pipe 3a with a circulation pump 3 interposed. At least two reaction systems which are connected in a loop form through are arranged, and adjacent reaction systems are connected by a transfer pipe 5 with a transfer pump 4 interposed. In the illustrated example, a case where two stages of reaction systems A and B are installed is shown. In the illustrated example, the inlet port of the first reaction system A, in the illustrated example, the inlet port 6 provided in the upper end cover plate of the dehydration tank 2 7, acid and alcohol supply sources, for example, acid and polyhydric alcohol supply source tanks 8 and 9 are connected via respective connecting pipes 10 and 11, and the final reaction system, that is, the second The reaction system B is equipped with a tubular outlet 12 as a product outlet 12 which is read below the fixed bed 1.
【０００８】該装置には、その第１反応系Ａと第２反応
系Ｂとの中間に、その夫々の脱水槽２，２に共通の不活
性ガス乾燥塔１３を設け、その上端から導出したガス供
給管１４に循環用エアポンプ１５を介入すると共に、そ
の基部から左右に分岐したガス供給管１４ａ，１４ｂの
先端をその左右の脱水槽２，２の下部に接続し、且つそ
のガス供給管１４ａ，１４ｂにニードル式流量調節バル
ブ１５ａ，１５ｂを介入せしめ、夫々の脱水槽２，２へ
の不活性ガス供給量を夫々各別に調節し得るようにし
た。該不活性ガス乾燥塔１３の下端は、Ｎ２ガスボンベ
などから成る不活性ガス供給源１６に接続管１７を介し
て接続されている。尚、該接続管１７には、コールドラ
ップ作用をもつ不活性ガス集積容器１８を介入させ、左
右の脱水槽２，２から排出される不活性ガスを、夫々の
接続管１９，１９を介して該容器１８に集積せしめ、凝
固水の捕集を行い、再び該不活性ガス乾燥塔１３に戻
り、リサイクル使用できるようにした。２０は酸供給用
液送ポンプ、２１はアルコール供給用液送ポンプ、２２
は生産物取出用調節バルブ、２３は左右の各循環用接続
管１９に介入させた三方コックを示す。尚、転送用パイ
プ５には、その転送用ポンプ４の上流に調節用バルブ５
ａを介入させることが好ましい。In the apparatus, an inert gas drying tower 13 common to the dehydration tanks 2 and 2 is provided in the middle of the first reaction system A and the second reaction system B, and it is led out from the upper end thereof. The air pump 15 for circulation is intervened in the gas supply pipe 14, and the tips of the gas supply pipes 14a and 14b branched left and right from the base are connected to the lower portions of the dehydration tanks 2 and 2 on the left and right, and the gas supply pipe 14a is also connected. , 14b by interposing needle type flow rate control valves 15a, 15b so that the amount of inert gas supplied to the dehydration tanks 2, 2 can be adjusted individually. The lower end of the inert gas drying tower 13 is connected to an inert gas supply source 16 such as an N 2 gas cylinder via a connecting pipe 17. In addition, an inert gas accumulating container 18 having a cold wrap action is interposed in the connecting pipe 17, and the inert gas discharged from the left and right dehydration tanks 2 and 2 is passed through the connecting pipes 19 and 19, respectively. The water was collected in the container 18, the coagulated water was collected, and returned to the inert gas drying tower 13 again so that it could be recycled. 20 is a liquid supply pump for acid supply, 21 is a liquid supply pump for alcohol supply, 22
Is a product take-out control valve, and 23 is a three-way cock intervening in each of the left and right circulation connecting pipes 19. The transfer pipe 5 has an adjusting valve 5 upstream of the transfer pump 4.
It is preferable to intervene a.
【０００９】このように構成した本発明のエステル連続
合成装置は、次のように作動させエステルの連続合成を
行う。即ち、供給源タンク８，９内の例えば酸及び多価
アルコールを夫々の液送ポンプ２０，２１を駆動し、エ
ステル合成に必要な化学量論量又はその近傍の配合割合
で第１反応系Ａに供給すると共に、該循環用ポンプ３と
転送用ポンプ４、第２反応系Ｂの循環用ポンプ３を駆動
して供給された酸及び多価アルコールの基質で反応系Ａ
及びＢを満たした後、転送用ポンプ４を止め、この状態
で反応系Ａ，Ｂの夫々の循環用ポンプ３，３を駆動して
夫々の反応系の基質をループ状に連結された該固定床リ
アクター１と該脱水槽２を通し循環させて該リアクター
１内の固定化リパーゼによりエステル化反応を行わせる
一方、三方弁２３，２３を一旦、図示の循環用接属管１
９，１９を外気に連通するように切換えて、不活性ガス
供給源１６からの不活性ガスを、該不活性ガス集積容器
１８を介し不活性ガス乾燥塔１３、ガス供給管１４ａ，
１４ｂ、脱水塔２，２を通して該三方弁２３，２３から
反応系Ａ，Ｂ外に排出させ、該系Ａ，Ｂ内の空気を該不
活性ガスと置換させた後、該三方弁２３，２３を図示の
ように切換えて、その後は不活性乾燥ガスを循環用接続
管１９，１９内を循環させるようにして、その夫々の脱
水槽２，２内に、該不活性ガス乾燥塔１３から乾燥不活
性ガスを連続的に吹き込み、夫々の脱水槽２，２内の反
応液と接触させてバブリング脱水処理を行い、エステル
化を進行させ、夫々の第１，第２反応系Ａ，Ｂ内のほぼ
滞留時間に相当する時間、バッチ法でエステル合成を行
った後、該酸及びアルコール原料を一定速度で該第１反
応系に供給すると共に、転送用ポンプ４を駆動して該第
１反応系の反応液を、該基質の供給量に見合つた転送量
で該第２反応系に転送すると同時に、該生産物取出用調
節バルブ２２を開いて、第２反応系Ｂ内の反応液、即ち
エステル生産物を前記の転送量に見合う量取出すように
し、以後は、本発明に従い第１反応系と第２反応系に夫
々設定した定常状態でエステル化が段階的に進行して目
的とするエステルの連続合成が得られるようにした。The continuous ester synthesizer of the present invention thus constructed operates as follows to perform continuous ester synthesis. That is, for example, acids and polyhydric alcohols in the supply source tanks 8 and 9 are driven by the liquid feed pumps 20 and 21, respectively, and the first reaction system A is supplied at a stoichiometric amount necessary for ester synthesis or a mixing ratio in the vicinity thereof. To the reaction system A using the substrate of the acid and polyhydric alcohol supplied by driving the circulation pump 3, the transfer pump 4, and the circulation pump 3 of the second reaction system B.
And B are filled, the transfer pump 4 is stopped, and in this state, the circulation pumps 3 and 3 of the reaction systems A and B are driven to fix the substrates of the respective reaction systems in a loop. While circulating through the bed reactor 1 and the dehydration tank 2 to carry out the esterification reaction by the immobilized lipase in the reactor 1, the three-way valves 23, 23 are temporarily turned on to the circulation connecting pipe 1 shown in the figure.
9 and 19 are switched so as to communicate with the outside air, and the inert gas from the inert gas supply source 16 is passed through the inert gas accumulation container 18 to the inert gas drying tower 13, the gas supply pipe 14a,
14b and the dehydration towers 2 and 2 to discharge from the three-way valves 23 and 23 to the outside of the reaction systems A and B to replace the air in the systems A and B with the inert gas, and then the three-way valves 23 and 23. As shown in the drawing, and thereafter, the inert dry gas is circulated in the circulation connecting pipes 19 and 19 to be dried in the respective dehydrating tanks 2 and 2 from the inert gas drying tower 13. Bubbling dehydration treatment is carried out by continuously blowing an inert gas into contact with the reaction liquids in the respective dehydration tanks 2 and 2 to progress the esterification, and the reaction in each of the first and second reaction systems A and B is performed. After the ester synthesis is carried out by a batch method for a time substantially corresponding to the residence time, the acid and alcohol raw materials are supplied to the first reaction system at a constant rate, and the transfer pump 4 is driven to drive the first reaction system. To the second reaction system at a transfer rate commensurate with the supply rate of the substrate. At the same time as the feeding, the control valve 22 for taking out the product is opened to take out the reaction liquid in the second reaction system B, that is, the ester product in an amount corresponding to the above-mentioned transfer amount. The esterification proceeded stepwise in the steady state set for the reaction system and the second reaction system, respectively, so that the desired continuous synthesis of the ester was obtained.
【００１０】図示の実施例は、２段の反応系Ａ，Ｂを通
してエステル合成、例えばトリグリセリドの合成を完了
するようにしたが、勿論、３段又はそれ以上の反応系を
配設して、順次、エステル化反応を段階的に進行させ、
その第１反応系には所定の供給速度で酸及び多価アルコ
ールの供給を行いつゝ最終の反応系からは所定の流出速
度でエステル生産物を取り出すようにエステルの連絖合
成を行うことができることは勿論である。In the illustrated embodiment, the ester synthesis, for example, the synthesis of triglyceride is completed through the two-step reaction systems A and B, but of course, three-step or more reaction systems are provided and the steps are sequentially performed. , The esterification reaction proceeds stepwise,
Acid and polyhydric alcohol are supplied to the first reaction system at a predetermined supply rate, and continuous ester synthesis is carried out so that the ester product is taken out from the final reaction system at a predetermined outflow rate. Of course you can.
【００１１】従って、本発明の上記装置は、上記構成の
反応系を複数段に具備しているので、従来１つの固定化
リパーゼを内蔵した固定床リアクターによりエステルの
合成を行っていたものに比し、一定量の酸・アルコール
のエステル合成を行う場合に、夫々の固定化リパーゼに
分担させることができ、各固定化リパーゼに対する負担
処理量を軽減することができ、生産物中に、反応にあず
からない酸やアルコールが混入することを防止できて有
利である。更に、本発明の上記装置は、反応系を複数段
に設けてあるので、その夫々の反応系に、必ずしも同じ
種類の固定化リパーゼを用いることなく、夫々のエステ
ル化特性を有する異種或いは異量の固定化リパーゼを選
択して夫々の各段の反応に適した夫々の固定床リアクタ
ーを構成でき、この場合、その夫々の反応条件も又種々
のものが選択できるため、迅速且つ高能率にエステルの
連続合成が得られる。Therefore, since the above-mentioned apparatus of the present invention is equipped with the reaction system having the above-mentioned constitution in a plurality of stages, it is compared with a conventional apparatus which synthesizes an ester by a fixed bed reactor containing one immobilized lipase. However, when performing ester synthesis of a fixed amount of acid / alcohol, each immobilized lipase can be shared, and the burden processing amount for each immobilized lipase can be reduced. This is advantageous because it can prevent unwanted acid and alcohol from entering. Further, since the above-mentioned apparatus of the present invention is provided with the reaction system in a plurality of stages, it is not always necessary to use the same type of immobilized lipase in each reaction system, and different or different amounts having different esterification characteristics can be obtained. Immobilized lipases can be selected to construct respective fixed bed reactors suitable for the reaction of each stage. In this case, various reaction conditions can also be selected, so that the esterification can be performed rapidly and with high efficiency. A continuous synthesis of is obtained.
【００１２】次に、上記の装置の構成を有効に利用した
本発明のエステルの連続合成法につき詳述する。即ち、
第２発明の合成法に従い、夫々の反応系に適したリパー
ゼを使用することである。即ち、例えば、前記の第１反
応系の固定床リアクター１としては、反応液の水分含有
量が１００ｐｐｍ以下で活性を維持できるリパーゼ、例
えば１，３グリセリドに特異性を有するムコール属のリ
パーゼを弱塩基性陰イオン交換樹脂に固定化したものを
使用し、第２反応系の固定床リアクター１としては、
１，３特異性を有しないキャンディダ属のリパーゼをア
クリル樹脂に固定化したものを使用することである。こ
れにより、第１反応系でジグリセリドを主成分とする反
応液が得られ、第２反応系でトリグリセリドを高濃度に
含む生産物を効率良く生産できる。Next, the method for continuously synthesizing the ester of the present invention, which effectively utilizes the constitution of the above apparatus, will be described in detail. That is,
According to the synthetic method of the second invention, a lipase suitable for each reaction system is used. That is, for example, as the fixed bed reactor 1 of the first reaction system, a lipase capable of maintaining the activity when the water content of the reaction solution is 100 ppm or less, for example, a Mucor lipase having specificity for 1,3 glyceride is weak. The fixed bed reactor 1 of the second reaction system, which is immobilized on a basic anion exchange resin, is used.
This is to use a Candida lipase having no 1,3 specificity immobilized on an acrylic resin. As a result, a reaction liquid containing diglyceride as a main component is obtained in the first reaction system, and a product containing triglyceride in a high concentration can be efficiently produced in the second reaction system.
【００１３】又、第３発明の合成法に従い、第１反応系
の反応条件と第２反応系の反応条件を変える方法であ
る。即ち、例えば、ムコール属のリパーゼを用いてトリ
グリセリド合成を行う場合、第１反応系の反応液の水分
濃度を１００〜１０００ｐｐｍ、好ましくは１５０〜３
００ｐｐｍに定常維持し、最後の反応系、即ち、図示の
例では第２反応系の反応液の水分濃度を１００ｐｐｍ以
下に定常維持することにより、効率良く連続的にトリグ
リセリドのエステル合成ができる。更に他の夫々の反応
系の反応条件を夫々設定する例として、第１反応系のム
コール属のリパーゼを内蔵した固定床リアクター１を６
０℃の温度で使用し、最終の反応系である第２反応系に
キャンディダ属のリパーゼを内蔵した固定床リアクター
１を７０℃の温度で使用することにより、夫々の酵素の
至適温度を保つので、効率良く且つ高収率トリグリセリ
ド生産物を得ることができる。According to the synthetic method of the third invention, the reaction conditions of the first reaction system and the reaction conditions of the second reaction system are changed. That is, for example, in the case of performing triglyceride synthesis using a lipase of the genus Mucor, the water concentration of the reaction solution in the first reaction system is 100 to 1000 ppm, preferably 150 to 3
By constantly maintaining the water concentration in the final reaction system, that is, the reaction solution in the second reaction system in the example shown in the drawing, at 100 ppm or less, the ester synthesis of triglyceride can be efficiently and continuously performed. As an example of setting the reaction conditions of each of the other reaction systems, a fixed bed reactor 1 containing a Mucor lipase in the first reaction system was used.
By using the fixed bed reactor 1 in which the Candida lipase is incorporated in the second reaction system, which is the final reaction system, at a temperature of 70 ° C., the optimum temperature of each enzyme is determined. Since this is maintained, a triglyceride product with high yield can be obtained efficiently.
【００１４】図１の装置において、該不活性ガス乾燥塔
１３からの左右のガス供給管１４ａ，１４ｂに介在させ
た夫々の調節弁１５ａ，１５ｂの開度を異にさせ、夫々
の左右の脱水槽２，２への不活性ガスの吹込み量をその
夫々の反応系エステル合成に最適となるように調節する
ことにより、夫々の反応系の反応液の水分濃度を変える
ことができる。In the apparatus shown in FIG. 1, the left and right control valves 15a and 15b interposed between the left and right gas supply pipes 14a and 14b from the inert gas drying tower 13 are made different in opening degree. By adjusting the amount of the inert gas blown into the water tanks 2 and 2 so as to be optimal for the synthesis of the respective reaction system esters, the water concentration of the reaction solution of each reaction system can be changed.
【００１５】尚、酸とアルコールの供給速度は、回分処
理時に、本エステルの連続合成装置内における固定化リ
パーゼがエステルを合成するための時間をほぼ滞留時間
にすることを基本とする。尚、酸或いはアルコールが不
安定な場合、反応中に失われる量を換算し、その量だけ
余分に供給するようにすれば、収率が向上する。The acid and alcohol are supplied at a rate such that the time required for the immobilized lipase to synthesize the ester in the continuous ester synthesizer during the batch treatment is approximately the residence time. When the acid or alcohol is unstable, the yield is improved by converting the amount lost during the reaction and supplying an extra amount.
【００１６】次に、更に詳細な実施例を説明する。図１
に示す本装置を、３５℃の恒温室に設置し、アルコール
供給源タンク８にはグリセリンを用意し、酸供給源タン
ク９には精製米ぬか油とオレイン酸を１；１に混合した
モデル高酸価油を用意した。第１反応系Ａの固定化リパ
ーゼ固定床リアクター１は、カラムに、ムコール属のリ
パーゼを陰イオン交換樹脂に固定化したリポザイムＩＭ
６０ １．２５ｇを充填したものを使用し、これを６０
℃に維持した。第２反応系Ｂ、こゝでは最終の反応系Ｂ
の固定化リパーゼ固定床リアクター１は、カラムに、キ
ャンディダ属のリパーゼを陰イオン交換樹脂に固定化し
たもの５．００ｇを使用し、これを６０℃に維持した。
第１反応系Ａの脱水槽２は直径２０ｍｍ、高さ２５０ｍ
ｍで約２５ｃｃ、６０℃の第１反応液に該不活性ガス乾
燥塔１３からのＮ２ガスを吹き込みバブリング脱水し
た。第２反応系Ｂの脱水槽２は、直径３５ｍｍ、高さ２
５０ｍｍで約１００ｃｃ、６０℃の第２反応液に、該不
活性ガス乾燥塔１３からのＮ２ガスを吹き込みバブリン
グ脱水した。この場合、ガス流量調節バルブ１５ｂの開
度を該バルブ１５ａの開度に比し大きくし、第２反応系
の脱水槽２への吹込み量を大きくした。該不活性ガス乾
燥塔１３は、約２５０ｇのモレキュラーシーブ５Ａを充
填したもので、これによりＮ２ガスを乾燥するようにし
た。グリセリンは、液送ポンプ２０で０．２２８ｇ／時
間の割合で、モデル高酸価油は、液送ポンプ１１で４．
２ｇ／時間の割合で夫々第１反応系Ａに供給した。第１
反応系Ａの循環ポンプ３は、６ｍｌ／分で第１反応液を
循環する一方、転送ポンプ４は４．２２ｇ／時間で該第
１反応系Ａよりの反応液を第２反応系Ｂに転送した。該
第２反応系Ｂの流出口１２から生産物回収用バルブ２２
を開き、４．２２ｇ／時間でエステル生産物、即ち、ト
リグリセリド生産物を連続的に取得した。作動中、点線
示の不活性ガス循環系全体は、Ｎ２ガスの陽圧下に維持
した。上記の試験の結果、第１反応系において、反応液
の水分含有量１５０〜２００ｐｐｍとしたときに、２Ｆ
Ａ（脂肪酸）＋Ｇ（グリセリン）→ＤＧ（ジグリセリ
ド）の主反応が急速に進み、ジグリセリドが２５〜３０
％生成され、その反応液は、第２反応系において、反応
系の水分含有量１５０ｐｐｍ以下とするとき、ＤＧ＋Ｆ
Ａ→ＴＧ（トリグリセリド）の主反応が促進され、定常
状態が保たれていることが認められた。かくして、第１
反応系Ａと第２反応系Ｂにおいて夫々の段階に適した固
定化リパーゼを使用すると共に、夫々の反応系に適した
上記の水分含有量を維持することにより、夫々の反応系
の組成を一定に保つことができ、トリグリセリドを高収
率に連続製造することができた。その結果は、トリグリ
セリド８０％近傍乃至それ以上を含む生産物を連続的に
得ることができた。Next, a more detailed embodiment will be described. Figure 1
The apparatus shown in Figure 3 is installed in a thermostatic chamber at 35 ° C, glycerin is prepared in the alcohol source tank 8, and refined rice bran oil and oleic acid are mixed in a ratio of 1; Valuable oil was prepared. The immobilized lipase fixed bed reactor 1 of the first reaction system A is a lipozyme IM in which a Mucor lipase is immobilized on an anion exchange resin in a column.
60 1.25g was used and
Maintained at 0 ° C. Second reaction system B, here final reaction system B
The immobilized lipase fixed bed reactor 1 of 1. used 5.00 g of immobilized Candida lipase on an anion exchange resin in the column and maintained it at 60 ° C.
The dehydration tank 2 of the first reaction system A has a diameter of 20 mm and a height of 250 m.
Bubbling dehydration was performed by blowing N 2 gas from the inert gas drying tower 13 into the first reaction liquid at m of about 25 cc and 60 ° C. The dehydration tank 2 of the second reaction system B has a diameter of 35 mm and a height of 2
Bubbling dehydration was carried out by blowing N 2 gas from the inert gas drying tower 13 into the second reaction liquid of 50 mm at about 100 cc and 60 ° C. In this case, the opening of the gas flow rate control valve 15b was made larger than that of the valve 15a, and the amount of the second reaction system blown into the dehydration tank 2 was increased. The inert gas drying tower 13 was filled with about 250 g of the molecular sieve 5A, so that the N 2 gas was dried. The glycerin is 0.228 g / hour in the liquid feed pump 20, and the model high acid value oil is 4.28 in the liquid feed pump 11.
It was supplied to the first reaction system A at a rate of 2 g / hour, respectively. First
The circulation pump 3 of the reaction system A circulates the first reaction solution at 6 ml / min, while the transfer pump 4 transfers the reaction solution from the first reaction system A to the second reaction system B at 4.22 g / hour. did. Product recovery valve 22 from the outlet 12 of the second reaction system B
Was opened, and the ester product, ie, triglyceride product, was continuously obtained at 4.22 g / hour. During operation, the entire inert gas circulation system indicated by the dotted line was maintained under a positive pressure of N 2 gas. As a result of the above test, in the first reaction system, when the water content of the reaction solution was set to 150 to 200 ppm, 2F
The main reaction of A (fatty acid) + G (glycerin) → DG (diglyceride) rapidly progresses, and diglyceride is 25-30.
%, And when the water content of the reaction system in the second reaction system is 150 ppm or less, DG + F
It was confirmed that the main reaction of A → TG (triglyceride) was promoted and the steady state was maintained. Thus, the first
In the reaction system A and the second reaction system B, immobilized lipase suitable for each stage is used, and by maintaining the above water content suitable for each reaction system, the composition of each reaction system is kept constant. The triglyceride could be continuously produced in high yield. As a result, a product containing about 80% or more of triglyceride could be continuously obtained.
【００１７】図２は、本発明の他の実施例の装置を示
す。この場合は、先の実施例と相異する点は、第１反応
系Ａと第２反応系Ｂには、夫々独立した不活性ガス乾燥
塔１３を具備し且つ各一対の乾燥塔１３を用意し、その
いずれか一方を使用している間に、その他方を２００〜
３５０℃に加熱して再生ができるようにし、連続運転を
可能としたこと、夫々のガス供給管１４，１４に不活性
ガス流量計２４，２４を介入させたこと、第２反応系の
循環ポンプ３とは別個に生産物回収用のポンプ２５を設
けたことであり、第１並に第２反応系Ａ，Ｂのリアクタ
ー１、脱水槽２の大きさを同一にしたことである。２６
は、開閉弁を示す。実施例と同じ構成部材には同じ参照
番号を付した。FIG. 2 shows an apparatus according to another embodiment of the present invention. In this case, the point different from the previous example is that the first reaction system A and the second reaction system B are equipped with independent inert gas drying towers 13 and each pair of drying towers 13 is prepared. And while using one of them, the other 200-
Regeneration by heating to 350 ° C. was made possible, continuous operation was possible, inert gas flowmeters 24, 24 were intervened in the respective gas supply pipes 14, 14, circulation pump of the second reaction system 3 is that a pump 25 for recovering the product is provided separately, and that the reactors 1 and the dehydration tanks 2 of the second reaction systems A and B are the same size as the first. 26
Indicates an on-off valve. The same components as those in the example have the same reference numerals.
【００１８】この装置を用いて第１反応系Ａと第２反応
系Ｂの夫々の固定床リアクター２，２に内蔵する固定化
リパーゼ及びその夫々の反応系Ａ，Ｂの夫々を最適の条
件下に保つように、乾燥ガス吹込み量、リアクターの温
度、供給量、循環速度、転送量などを適当に撰択して運
転する。Using this apparatus, the immobilized lipase contained in the fixed bed reactors 2 and 2 of the first reaction system A and the second reaction system B and the respective reaction systems A and B are optimized under optimum conditions. In order to maintain the above, the dry gas injection rate, reactor temperature, supply rate, circulation rate, transfer rate, etc. are appropriately selected for operation.
【００１９】[0019]
【発明の効果】このように本発明によるときは、固定化
リパーゼを内蔵した固定床リアクターと脱水槽とを循環
用ポンプを介してルーブ状に連続して成る反応系を複数
段を配設すると共に相隣る反応系を転送用ポンプを介入
した転送パイプにより接続し、酸とアルコールの供給源
を該第１反応系に接続し、最終の反応系に生産物の取出
口を備えたエステルの連続合成装置を構成したので、各
段階における各固定化リパーゼのエステル合成の負担を
軽減でき、その使用寿命を延長でき、長期に亘り良好な
エステルの連続合成がなし得られるばかりでなく、夫々
の反応系に所望の固定化リパーゼを選択使用でき、或い
は、夫々の反応系における反応条件を適当に設定できる
便利をもたらす。As described above, according to the present invention, a plurality of stages of reaction systems are provided in which a fixed bed reactor containing an immobilized lipase and a dehydration tank are continuously connected in a lube shape via a circulation pump. And the adjacent reaction systems are connected by a transfer pipe with a transfer pump interposed, the acid and alcohol sources are connected to the first reaction system, and the final reaction system is provided with a product outlet. Since a continuous synthesizer was constructed, the burden of ester synthesis of each immobilized lipase at each stage can be reduced, its service life can be extended, and good ester continuous synthesis can be achieved over a long period of time. A desired immobilized lipase can be selectively used in the reaction system, or the reaction conditions in each reaction system can be appropriately set, which is convenient.
【００２０】而して、該装置の夫々の反応系に最適の固
定化リパーゼを使用し或いは最適の反応条件を設定する
ときは、目的とするエステルを高収率に合成できる効果
をもたらす。Thus, when the optimum immobilized lipase is used in each reaction system of the apparatus or the optimum reaction conditions are set, the desired ester can be synthesized in a high yield.
【図１】本発明の実施の１例のエステルの連続合成装置
の全体図である。FIG. 1 is an overall view of a continuous ester synthesis apparatus according to an embodiment of the present invention.
【図２】本発明の変形例のエステルの連続合成装置の全
体図である。FIG. 2 is an overall view of a continuous ester synthesis apparatus according to a modified example of the present invention.
Ａ 第１反応系 Ｂ 追加の反応
系、第２反応系 １ 固定床リアクター ２ 脱水槽 ３ 循環用ポンプ ３ａ ループ状
接続管 ４ 転送用ポンプ ５ 転送用接続
管 ６，７ 流入口 ８ アルコール
供給源 ９ 酸供給源 １２ 流出口 １３ 不活性ガス乾燥塔 １４，１４
ａ，１４ｂ ガス供給管 １６ 不活性ガス供給源 １９ 循環用
接続管A 1st reaction system B Additional reaction system, 2nd reaction system 1 Fixed bed reactor 2 Dehydration tank 3 Circulation pump 3a Loop connection pipe 4 Transfer pump 5 Transfer connection pipe 6,7 Inlet port 8 Alcohol supply source 9 Acid supply source 12 Outlet 13 Inert gas drying tower 14, 14
a, 14b Gas supply pipe 16 Inert gas supply source 19 Circulation connection pipe
フロントページの続き (72)発明者 東 直輝 千葉県船橋市日の出２丁目17番１号 ボー ソー油脂株式会社内 審査官 加藤 浩 (56)参考文献 特開 平４−335881（ＪＰ，Ａ) 特開 平２−142485（ＪＰ，Ａ)Front page continuation (72) Inventor Naoki Higashi, 2-17-1, Hinode 2-chome, Funabashi City, Chiba, Inspector, Bo So Oil & Fat Co., Ltd. Hiroshi Kato (56) Reference JP-A-4-335881 (JP, A) Flat 2-142485 (JP, A)
Claims (3)
ターと脱水槽とを循環用ポンプを介してループ状に連結
して成る反応系を少なくとも２段に配設すると共に、相
隣る反応系を転送用ポンプを介入した転送用パイプによ
り接続し、酸とアルコールの供給源を第１反応系に接続
し、最終の反応系に生産物の取出口を備えて成るエステ
ルの連続合成装置。1. A reaction system comprising a fixed bed reactor containing an immobilized lipase and a dehydration tank connected in a loop through a circulation pump is provided in at least two stages, and adjacent reaction systems are A continuous ester synthesizer comprising a transfer pipe connected with a transfer pump, a source of acid and alcohol connected to the first reaction system, and a product outlet in the final reaction system.
続合成を行うに当たり、その夫々の段階の反応系に用い
る夫々の固定化リパーゼを適当に選択することを特徴と
するエステルの連続合成装置。2. A continuous ester synthesis apparatus, wherein each immobilized lipase used in the reaction system at each stage is appropriately selected when performing continuous ester synthesis by the apparatus according to claim 1.
によりエステルの連続合成を行うに当たり、夫々の反応
系における反応条件を至適に調節することを特徴とする
エステルの連続合成法。3. A method for continuously synthesizing an ester, which comprises optimally adjusting reaction conditions in each reaction system when the ester is continuously synthesized by the apparatus for continuously synthesizing an ester according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3337502A JPH0728719B2 (en) | 1991-10-22 | 1991-10-22 | Continuous ester synthesizer and its continuous synthesis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3337502A JPH0728719B2 (en) | 1991-10-22 | 1991-10-22 | Continuous ester synthesizer and its continuous synthesis method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05328962A JPH05328962A (en) | 1993-12-14 |
| JPH0728719B2 true JPH0728719B2 (en) | 1995-04-05 |
Family
ID=18309261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3337502A Expired - Lifetime JPH0728719B2 (en) | 1991-10-22 | 1991-10-22 | Continuous ester synthesizer and its continuous synthesis method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0728719B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7473539B2 (en) * | 2004-09-20 | 2009-01-06 | Sunho Biodiesel Corporation | Methods for producing alkyl esters |
| WO2008069251A1 (en) * | 2006-12-05 | 2008-06-12 | Nagasaki Institute Of Applied Science | Apparatus and process for production of liquid fuel from biomass |
-
1991
- 1991-10-22 JP JP3337502A patent/JPH0728719B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05328962A (en) | 1993-12-14 |
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