JP5048957B2 - Ester synthesis catalyst, method for producing the same, and method for producing biofuel using the catalyst - Google Patents
Ester synthesis catalyst, method for producing the same, and method for producing biofuel using the catalyst Download PDFInfo
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- 150000002148 esters Chemical class 0.000 title claims description 109
- 239000003054 catalyst Substances 0.000 title claims description 64
- 230000015572 biosynthetic process Effects 0.000 title claims description 60
- 238000003786 synthesis reaction Methods 0.000 title claims description 60
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 239000002551 biofuel Substances 0.000 title claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 130
- 239000004367 Lipase Substances 0.000 claims description 112
- 102000004882 Lipase Human genes 0.000 claims description 112
- 108090001060 Lipase Proteins 0.000 claims description 112
- 235000019421 lipase Nutrition 0.000 claims description 112
- 239000002245 particle Substances 0.000 claims description 53
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- 235000014113 dietary fatty acids Nutrition 0.000 claims description 24
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- 238000010306 acid treatment Methods 0.000 claims description 14
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- 238000006243 chemical reaction Methods 0.000 description 94
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- 239000000377 silicon dioxide Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- 150000001298 alcohols Chemical class 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
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- 125000005624 silicic acid group Chemical group 0.000 description 3
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 241000588810 Alcaligenes sp. Species 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 241000134731 Phycomyces nitens Species 0.000 description 1
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- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
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- 229910052793 cadmium Inorganic materials 0.000 description 1
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
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- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003622 immobilized catalyst Substances 0.000 description 1
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- 238000000691 measurement method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
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- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Catalysts (AREA)
Description
本発明はエステル合成触媒に関するものであり、より詳細にはバイオ燃料の製造に適したエステル合成触媒及びその製造方法、並びに、該触媒を用いたバイオ燃料の製造方法に関する。 The present invention relates to an ester synthesis catalyst, and more particularly to an ester synthesis catalyst suitable for biofuel production, a production method thereof, and a biofuel production method using the catalyst.
油脂を利用した環境に優しい燃料が、バイオ燃料、バイオディーゼル燃料（ＢＤＦ）などの名称で知られている。このバイオディーゼル燃料の典型的な製造例は、植物油に苛性ソーダ等のアルカリとメタノールとを作用させてメチルエステルとしたものである。即ち、エステル交換反応により、脂肪酸トリグリセリドをメチルエステルに転換させることによりバイオ燃料となるメチルエステルを合成するというものであり、アルカリはエステル交換触媒として作用する。 Environment-friendly fuels using fats and oils are known under names such as biofuels and biodiesel fuels (BDF). A typical production example of this biodiesel fuel is a methyl ester produced by reacting vegetable oil with an alkali such as caustic soda and methanol. That is, a fatty acid triglyceride is converted to a methyl ester by a transesterification reaction to synthesize a methyl ester as a biofuel, and the alkali acts as a transesterification catalyst.
上記のような触媒として、酵素をシリカ等の多孔質担体に担持させた酵素固定化触媒も広く知られており、例えば特許文献１や２には、リパーゼをシリカ等に担持させた固定化リパーゼを触媒として用いてのエステル交換反応により、油脂から脂肪酸エステルを合成することが開示されている。
リパーゼは、エステル交換或いはエステル化に対して極めて大きな活性作用を有するものであり、特許文献１や２では、極めて大きな転換効率でバイオ燃料となる脂肪酸エステルを合成できることが期待される。 Lipase has a very large activity for transesterification or esterification, and Patent Documents 1 and 2 are expected to be able to synthesize fatty acid esters serving as biofuels with extremely high conversion efficiency.
しかしながら、特許文献１や２で開示されている固定化リパーゼでは、予想されるほど高い転換効率を得ることが困難であり、また、高い転換効率を示すものでも、活性寿命が極めて短く、実際にエステル合成を行うと、短時間で触媒活性が損なわれてしまうという問題がある。 However, with the immobilized lipase disclosed in Patent Documents 1 and 2, it is difficult to obtain a high conversion efficiency as expected, and even those exhibiting a high conversion efficiency have an extremely short active life, When ester synthesis is performed, there is a problem that the catalytic activity is impaired in a short time.
従って、本発明の目的は、高い触媒活性を示し且つ高い触媒活性を持続して示すエステル合成触媒及びその製造方法を提供することにある。
本発明の他の目的は、上記エステル合成触媒を用いて油脂もしくは脂肪酸からバイオ燃料を製造する方法を提供することにある。
Accordingly, an object of the present invention is to provide an ester synthesis catalyst that exhibits high catalytic activity and continues to exhibit high catalytic activity, and a method for producing the same.
Another object of the present invention is to provide a method for producing biofuel from fats or fatty acids using the ester synthesis catalyst.
本発明によれば、ＢＥＴ比表面積が２０乃至３８０ｍ２／ｇ以下、細孔半径が２５Å以上及び導電率が２０００μS／ｃｍ以下のシリカ粒子にリパーゼを担持させてなることを特徴とするエステル合成触媒が提供される。 According to the present invention, an ester synthesis catalyst comprising a lipase supported on silica particles having a BET specific surface area of 20 to 380 m 2 / g or less, a pore radius of 25 mm or more, and a conductivity of 2000 μS / cm or less. Is provided.
上記エステル合成触媒においては、
（１）前記シリカ粒子は、１７０℃〜９００℃での温度領域での加熱減量が、１７０℃乾燥品当り３．５重量％未満であること、
（２）前記シリカ粒子は、バーミキュライトの酸処理により得られたＳｉＯ２の薄層が積層された劈開性積層体粒子からなること、
（３）シリカ粒子の中位径が０．５μm乃至２mmであること、
（４）１１０℃の乾燥物に換算したシリカ粒子１００重量部当り１乃至３０重量部のリパーゼを担持させてなること、
（５）加水分解活性が２×１０４ＩＵ／ｇ以上のリパーゼを用いること、
が好ましい。
In the ester synthesis catalyst,
(1) The silica particles have a heating loss in a temperature range of 170 ° C. to 900 ° C. of less than 3.5% by weight per 170 ° C. dry product,
(2) The silica particles are composed of cleaved laminate particles in which thin layers of SiO 2 obtained by acid treatment of vermiculite are laminated,
(3) The median diameter of the silica particles is 0.5 μm to 2 mm,
(4) carrying 1 to 30 parts by weight of lipase per 100 parts by weight of silica particles converted to a dried product at 110 ° C;
(5) using a lipase having a hydrolytic activity of 2 × 10 4 IU / g or more,
Is preferred.
本発明によれば、また、ＢＥＴ比表面積が２０乃至３８０ｍ２／ｇ、細孔半径が２５Å及以上及び導電率が２０００μS／ｃｍ以下のシリカ粒子を、濃度が０．１乃至１５重量％のリパーゼ水分散液に混合し、該混合液をリパーゼの失活温度未満で乾燥することを特徴とするエステル化触媒の製造方法が提供される。 According to the present invention, silica particles having a BET specific surface area of 20 to 380 m 2 / g, a pore radius of 25 mm or more, and a conductivity of 2000 μS / cm or less are converted into lipase having a concentration of 0.1 to 15% by weight. There is provided a method for producing an esterification catalyst, which is mixed with an aqueous dispersion and dried at a temperature lower than the deactivation temperature of lipase.
本発明の製造方法によれば、
（１）前記混合液のpHが６乃至８の範囲であること、
（２）前記製造方法において、混合液に溶解している塩類が、１１０℃の乾燥物に換算したシリカ粒子１００重量部に対して０．５重量部以下であること、
が好ましい。
本発明によれば、さらに上記エステル合成触媒の存在下に、低級アルコールと油脂もしくは脂肪酸とを反応させて脂肪酸エステルとすることを特徴とするバイオ燃料の製造方法が提供される。
According to the production method of the present invention,
(1) The pH of the mixed solution is in the range of 6 to 8,
(2) In the said manufacturing method, the salts which are melt | dissolving in a liquid mixture are 0.5 weight part or less with respect to 100 weight part of silica particles converted into the dried material of 110 degreeC,
Is preferred.
According to the present invention, there is further provided a method for producing a biofuel, characterized in that a fatty alcohol is produced by reacting a lower alcohol with fat or fatty acid in the presence of the ester synthesis catalyst.
上記の製造方法においては、
（１）低級アルコールと油脂もしくは脂肪酸とを有機溶媒と共に、前記エステル合成触媒が充填された固定床に連続的に供給すること、
（２）油脂として植物油を使用すること、
が好ましい。
In the above manufacturing method,
(1) Continuously supplying lower alcohol and fat or fatty acid together with an organic solvent to a fixed bed filled with the ester synthesis catalyst;
(2) Use vegetable oils as fats and oils,
Is preferred.
本発明のエステル合成触媒は、リパーゼを多孔質担体に保持せしめたものであるが、特に重要な特徴は、リパーゼを担持する多孔質担体として、ＢＥＴ比表面積が２０乃至３８０ｍ２／ｇ、細孔半径が２５Å以上及び導電率が２０００μS／ｃｍ以下のシリカ粒子を用いた点にある。即ち、従来公知の固定化リパーゼについて検討した結果、本発明者等は、リパーゼを担持させる多孔質担体の物性がリパーゼの触媒活性に大きな影響を与え、上記のように特定の性状を示すシリカ粒子にリパーゼを担持させることにより、高い触媒活性を確保し且つ高い触媒活性を持続して維持させることに成功したものである。 The ester synthesis catalyst of the present invention is obtained by holding a lipase on a porous carrier, and the particularly important feature is that the porous carrier carrying the lipase has a BET specific surface area of 20 to 380 m 2 / g, pores. This is because silica particles having a radius of 25 mm or more and an electric conductivity of 2000 μS / cm or less are used. That is, as a result of studying conventionally known immobilized lipases, the present inventors have found that silica particles exhibiting specific properties as described above because the physical properties of the porous carrier on which the lipase is supported greatly affect the catalytic activity of the lipase. By supporting lipase on the surface, high catalytic activity was ensured and high catalytic activity was sustained and maintained.
本発明において、上記のような性状の担体を用いることにより、高い触媒活性とその持続性が得られることの理由は正確に解明されたわけではないが、本発明者等は次のように推定している。即ち、担体のＢＥＴ比表面積及び細孔半径が上記範囲内にあるものは、十分な量のリパーゼが強固に担持され且つ担体表面に適度に存在しており、この結果、リパーゼの高い触媒活性が有効に発現し、且つリパーゼの脱落が抑制され、長期間にわたって高い触媒活性が持続して発現するものと考えられる。また、このような担体は、エステル交換により副生するグリセリンやアルコール、エステル化により副生する水を吸着保持することができ、グリセリン、アルコールや水によるリパーゼの活性低下を抑制できることも、高い触媒活性を持続して維持できる一因と考えられる。例えば後述する実施例及び比較例に示されているように、担体のＢＥＴ比表面積及び細孔半径が上記範囲外にあるものは、高い触媒活性が発現せず、例えばエステル変換率がかなり低下してしまうし、また高い触媒活性を示したとしても、その活性寿命が短く、短時間で失活してしまい、高い変換効率でエステル交換反応を持続させることができない。 In the present invention, the reason why high catalytic activity and its sustainability can be obtained by using the carrier having the properties as described above has not been precisely clarified, but the present inventors presume as follows. ing. That is, when the BET specific surface area and the pore radius of the support are within the above ranges, a sufficient amount of lipase is firmly supported and appropriately present on the support surface. As a result, the catalytic activity of the lipase is high. It is considered that the lipase is effectively expressed and the lipase omission is suppressed, and high catalytic activity is continuously expressed over a long period of time. In addition, such a carrier can adsorb and retain glycerin and alcohol by-produced by transesterification and water by-produced by esterification, and can suppress a decrease in lipase activity due to glycerin, alcohol and water. This is considered to be one of the reasons that the activity can be maintained continuously. For example, as shown in Examples and Comparative Examples described later, when the BET specific surface area and pore radius of the support are outside the above ranges, high catalytic activity does not appear, and for example, the ester conversion rate is considerably reduced. Even if it shows a high catalytic activity, its activity life is short, it deactivates in a short time, and the transesterification reaction cannot be sustained with high conversion efficiency.
また、導電率は、担体に含まれる可溶性塩類含量を示すパラメータであり、導電率が上記範囲よりも高いものでは、高い触媒活性を発揮することができない。即ち、導電率の高いものは可溶性塩類含量が多く、この可溶性塩類によってリパーゼが失活してしまうのである（後述の比較例２参照）。例えば、シリカは、一般にケイ酸アルカリと鉱酸とを反応することにより製造されるが、不純物として可溶性塩類を含有しているものもある。従って、本発明において、担体としてシリカを用いるためには、洗浄等を繰り返して行い、導電率が上記範囲内となるように可溶性塩類を除去しておく必要がある。 Further, the conductivity is a parameter indicating the content of soluble salts contained in the carrier, and a high catalytic activity cannot be exhibited if the conductivity is higher than the above range. That is, those having high conductivity have a high content of soluble salts, and the lipase is deactivated by these soluble salts (see Comparative Example 2 described later). For example, silica is generally produced by reacting an alkali silicate with a mineral acid, but some contain soluble salts as impurities. Therefore, in order to use silica as a carrier in the present invention, it is necessary to repeat washing and the like to remove soluble salts so that the conductivity is within the above range.
また、本発明においては、１７０℃〜９００℃での温度領域での加熱減量が、１７０℃乾燥品当り３．５重量％未満を用いることが好適である。この加熱減量は、シリカ粒子中のＯＨ基量に相当するものであり、このようなＯＨ基量は、後述する実施例から理解されるように、触媒活性と密接な関係があり、ＯＨ基量が上記範囲内に抑制されているシリカ粒子にリパーゼを担持することにより、極めて高い触媒活性を安定して確保することができる。この理由は、明確ではないが、ＯＨ基量が多いものでは、リパーゼの触媒活性が失活しやすく、また、リパーゼ自体が疎水性であるため、これをシリカ粒子に安定に担持させることが困難になるためと思われる。 In the present invention, it is preferable that the weight loss by heating in the temperature range of 170 ° C. to 900 ° C. is less than 3.5% by weight per 170 ° C. dry product. This loss on heating corresponds to the amount of OH groups in the silica particles, and the amount of such OH groups is closely related to the catalyst activity, as will be understood from the examples described later. By supporting the lipase on silica particles in which is suppressed within the above range, extremely high catalytic activity can be stably secured. The reason for this is not clear, but when the amount of OH groups is large, the catalytic activity of the lipase tends to be deactivated, and since the lipase itself is hydrophobic, it is difficult to stably support it on the silica particles. It seems to be.
本発明においては、さらに、上記のようにＯＨ基量が一定範囲内に抑制されたもののシリカ粒子の中でも、バーミキュライトを酸処理して得られる非晶質シリカ粒子を用いることが、触媒活性が長く、長期にわたって繰り返してエステル合成を行うことができるという点で好ましい。即ち、このような非晶質シリカ粒子は、ＳｉＯ２の薄層が積層されて劈開性の積層体粒子構造を有しており、このような粒子構造に関連して、エステル合成に際して油脂の加水分解により生じたグリセリンが外部に放出されず、シリカ粒子の内部に安定に保持されるため、繰り返しエステル合成を行った場合にも、グリセリンによる反応阻害を回避し、安定してエステル合成を行うことができるものと思われる。 In the present invention, among the silica particles whose OH group amount is suppressed within a certain range as described above, it is possible to use amorphous silica particles obtained by acid-treating vermiculite with a long catalytic activity. It is preferable in that the ester synthesis can be performed repeatedly over a long period of time. That is, such amorphous silica particles have a cleaved laminate particle structure in which a thin layer of SiO 2 is laminated, and in connection with such a particle structure, oil and fat are added during ester synthesis. The glycerin produced by the decomposition is not released to the outside and is stably held inside the silica particles, so even when repeated ester synthesis is performed, reaction inhibition by glycerin is avoided and stable ester synthesis is performed. Seems to be able to.
また、本発明において、上記のエステル合成触媒は、担体として用いるシリカ粒子を、所定濃度のリパーゼ水分散液に混合し、リパーゼの失活温度未満で乾燥することにより製造される。このような方法でリパーゼを担持させることができ、上述した高い触媒活性とその持続性を実現できる。例えば、シリカ粒子とリパーゼとを単に混合したのみでは、リパーゼを担持することができず、たとえ初期の触媒活性が高い場合があったとしても、同じシリカ粒子にリパーゼを担持した触媒と比べると活性の持続は短い（後述の実施例１及び比較例３）。 In the present invention, the above-mentioned ester synthesis catalyst is produced by mixing silica particles used as a carrier with a lipase aqueous dispersion having a predetermined concentration and drying it at a temperature lower than the lipase deactivation temperature. The lipase can be supported by such a method, and the above-described high catalytic activity and its sustainability can be realized. For example, simply mixing silica particles and lipase cannot support lipase, and even if the initial catalytic activity may be high, it is more active than a catalyst that supports lipase on the same silica particles. Is short (Example 1 and Comparative Example 3 described later).
また、リパーゼの失活を最小限に抑えるには担持処理液のｐHを６乃至８の範囲に保持することが重要であり、そのために酸、アルカリまたは塩類を添加することもできるが、それらは担体粒子から溶出した塩類と同様にリパーゼの失活を招く。したがって、担持処理液に溶解している塩類の量が、担体粒子１００重量部に対して０．５重量部以下となるようにしなければならない。 In order to minimize the inactivation of the lipase, it is important to maintain the pH of the supported treatment solution in the range of 6 to 8. For this purpose, an acid, an alkali or a salt can be added. Like the salts eluted from the carrier particles, the lipase is deactivated. Therefore, the amount of salts dissolved in the supporting treatment solution must be 0.5 parts by weight or less with respect to 100 parts by weight of the carrier particles.
上述したように、固定化リパーゼからなる本発明のエステル合成触媒は、高い触媒活性を示し、その持続性にも優れていることから、油脂などを原料としたエステル交換反応によるバイオ燃料の製造に有効に適用される。また、脂肪酸と水とのエステル化反応に対しても高い活性を示すため、脂肪酸を原料としたバイオ燃料の製造にも適用できる。 As described above, the ester synthesis catalyst of the present invention comprising an immobilized lipase exhibits high catalytic activity and is excellent in its sustainability, so that it can be used for the production of biofuels by transesterification using oils and fats as raw materials. Effectively applied. Moreover, since it shows high activity with respect to the esterification reaction between fatty acid and water, it can be applied to the production of biofuel using fatty acid as a raw material.
＜リパーゼ＞
本発明において、リパーゼとしては、油脂を加水分解し、脂肪酸エステルを生成するものであれば、何れをも用いることができ、その由来等は特に限定されず、微生物由来のリパーゼ、植物由来のリパーゼ、動物膵臓由来のリパーゼ等が使用される。
<Lipase>
In the present invention, any lipase can be used as long as it hydrolyzes fats and oils to produce a fatty acid ester, and the origin thereof is not particularly limited. The lipase derived from microorganisms and the lipase derived from plants are used. In addition, lipases derived from animal pancreas are used.
リパーゼの具体的な例として、Candida cylindracea由来のリパーゼOF(名糖産業)、Alcaligenes sp由来のリパーゼQLM(名糖産業)、Candida rugosa由来のリパーゼTypeVII(シグマ)、Rhizopus arrhizus由来のリパーゼType11(シグマ)、Rhizopus oryzae由来のリパーゼF−AP15(天野エンザイム)、Rhizopus japonicus NR400由来のリリパーゼA−10FG(ナガセ)、Aspergillus niger由来のSumizymeNLS(新日本化学)、Phycomyces nitens NRRL 2444由来のリパーゼPN(和光)、Porcine pancreas由来のリパーゼTypeII(シグマ)、Pseudomonas cepacia由来のリパーゼ(シグマ)、Mucor javanicus由来のリパーゼ(シグマ)、アルカリリパーゼ（NOVO）等を挙げることができるが、これらの中でも加水分解活性が２×１０４ＩＵ／ｇ以上のリパーゼ（例えば、リパーゼQLM、リパーゼOF）が高い触媒活性を示し、最も好適に使用される。即ち、本発明においては、このような高活性のリパーゼを使用すれば、その高い触媒活性が有効に発現し、例えば後述する実施例１に示されているように、ナタネ油とメタノールによるエステル交換反応では変換率８０％以上という高い触媒活性を示すだけでなく、反応終了後に遠心分離により触媒を回収して次の反応に供する方法で繰り返し反応を行った場合には高い変換率を保持することができ、総積算変換量が多くなることから、工業的に最も有用である。 Specific examples of lipases include lipase OF derived from Candida cylindracea (name sugar industry), lipase QLM derived from Alcaligenes sp (name sugar industry), lipase type VII derived from Candida rugosa (sigma), lipase type 11 derived from Rhizopus arrhizus (sigma) ), Rhizopus oryzae-derived lipase F-AP15 (Amano Enzyme), Rhizopus japonicus NR400-derived lipase A-10FG (Nagase), Aspergillus niger-derived SumizymeNLS (Nippon Kagaku), Phycomyces nitens NRRL 2444-derived lipase PN (Wako) Porcine pancreas-derived lipase Type II (Sigma), Pseudomonas cepacia-derived lipase (Sigma), Mucor javanicus-derived lipase (Sigma), alkaline lipase (NOVO), etc., among which hydrolytic activity is 2 × 10 4 IU / g or more lipases (e.g., lipase QLM, lipase oF) showed high catalytic activity is most preferably used. That is, in the present invention, when such a highly active lipase is used, its high catalytic activity is effectively expressed. For example, as shown in Example 1 described later, transesterification with rapeseed oil and methanol is performed. The reaction not only shows a high conversion activity of 80% or more, but also retains a high conversion rate when the reaction is repeated by a method in which the catalyst is recovered by centrifugation after completion of the reaction and used for the next reaction. And the total integrated conversion amount increases, and is industrially most useful.
本発明において、上記のリパーゼは、以下に述べる担体粒子１００重量部（１１０℃乾燥物換算）当り１乃至３０重量部、特に５乃至２０重量部の量で担持される。即ち、この量が、上記範囲よりも少ないと、十分な触媒活性を得ることが困難となり、また、上記範囲よりも多量に担持させたとしても、それ以上に触媒活性が向上することはなく、経済的に不利となり、またエステル合成に際して副生するグリセリンの除去機能が低下することもある。 In the present invention, the above lipase is supported in an amount of 1 to 30 parts by weight, particularly 5 to 20 parts by weight, per 100 parts by weight of carrier particles described below (in terms of 110 ° C. dry matter). That is, if this amount is less than the above range, it is difficult to obtain sufficient catalytic activity, and even if it is supported in a larger amount than the above range, the catalytic activity is not further improved. It is economically disadvantageous, and the function of removing glycerin by-produced during ester synthesis may be reduced.
＜担体粒子＞
本発明において、上記のリパーゼを担持する担体粒子としては、シリカ（ＳｉＯ２）を用いるが、このような担体粒子は、ＢＥＴ比表面積が２０乃至３８０ｍ２／ｇ、細孔半径が２５Å以上、及び導電率が２０００μS／ｃｍ以下、好ましくは１８００μS／ｃｍ以下、さらに好ましくは３００μS／ｃｍ以下の範囲にあるものが使用される。即ち、先にも述べたように、ＢＥＴ比表面積、細孔半径及び導電率が上記範囲内にあるシリカ粒子を用いることにより、リパーゼを失活させることなく、且つ適当量のリパーゼが表面に存在し、常に高い触媒活性が長期間にわたって発現するようにリパーゼを担持することが可能となる。シリカ粒子のＢＥＴ比表面積あるいは細孔半径が上記範囲外にある場合は、高い加水分解活性を示すリパーゼを担持したとしても高い触媒活性が発現しない。例えば後述する比較例６に示されているように、初期段階からエステル変換率が低いままである。また、後述する比較例１に示されているように、初期段階において８０％以上の高い触媒活性を示したとしても、その寿命は短く、繰り返し反応においても少ない繰り返し反応回数で失活してしまい、高い変換効率でエステル交換反応を保持することができない。
<Carrier particles>
In the present invention, silica (SiO 2 ) is used as the carrier particles supporting the above lipase. Such carrier particles have a BET specific surface area of 20 to 380 m 2 / g, a pore radius of 25 mm or more, and A material having an electric conductivity of 2000 μS / cm or less, preferably 1800 μS / cm or less, more preferably 300 μS / cm or less is used. That is, as described above, by using silica particles whose BET specific surface area, pore radius and conductivity are within the above ranges, an appropriate amount of lipase is present on the surface without inactivating the lipase. And it becomes possible to carry | support lipase so that always high catalytic activity may be expressed over a long period of time. When the BET specific surface area or pore radius of the silica particles is outside the above range, even if a lipase exhibiting high hydrolysis activity is supported, high catalytic activity is not exhibited. For example, as shown in Comparative Example 6 described later, the ester conversion rate remains low from the initial stage. Further, as shown in Comparative Example 1 to be described later, even if it shows a high catalytic activity of 80% or more in the initial stage, its life is short, and it is deactivated with a small number of repeated reactions even in repeated reactions. The transesterification reaction cannot be maintained with high conversion efficiency.
また、このような担体粒子は、一般に、その中位径が０．５μｍ乃至２mm、特に１乃至７００μｍ程度の範囲にあることが好ましい。この粒径があまり小さいと、担体粒子の凝集が生じ易く、リパーゼを安定に担持させることが困難となり、仮に担持させることができたとしても、触媒活性やその持続性にバラツキが生じ易くなってしまう。また、あまり粒径が大きなものを使用したときにも、担持量にバラツキが生じ易くなり、触媒活性が不均一となり易い。 Such carrier particles generally have a median diameter in the range of about 0.5 μm to 2 mm, particularly about 1 to 700 μm. If the particle size is too small, the carrier particles are likely to aggregate, making it difficult to stably support the lipase, and even if the lipase can be supported, the catalytic activity and its sustainability tend to vary. End up. In addition, even when a particle having a very large particle size is used, variation in the supported amount tends to occur, and catalyst activity tends to be non-uniform.
さらに、本発明においては、上記のようなシリカ粒子の中でも、１７０℃〜９００℃での温度領域での加熱減量が、１７０℃乾燥品当り、３．５重量％未満、特に３．０重量％以下であるものを用いることが好ましい。この加熱減量は、シリカ粒子中のＯＨ基量に相当するものであり、吸着した水分量を除いたＯＨ基量である。図１は、種々の加熱減量を有するシリカ粒子にリパーゼを担持したときのエステル変換率を加熱減量（上記ＯＨ基量）に対してプロットした図を示すものであり、この図によれば、ＯＨ基量が大きいほどエステル変換率が小さくなり、ＯＨ基量が少なくなるほど、エステル変換率が大きくなることが判る。即ち、エステル変換率（触媒活性）とシリカ粒子の加熱減量との間には相関関係があり、本発明では、加熱減量が上記範囲に調整されたシリカ粒子を用いることにより、安定して高いエステル変換率を確保することができるのである。先にも述べたように、加熱減量が上記範囲内となるように小さく調整されたシリカ粒子を用いることにより高いエステル変換率を確保できるのは、この加熱減量（ＯＨ基量）が多いものでは、リパーゼの触媒活性が失活しやすく、また、リパーゼ自体が疎水性であるため、リパーゼのシリカ粒子への担持を有効に行うことが困難になるためと思われる。 Furthermore, in the present invention, among the silica particles as described above, the heat loss in the temperature range of 170 ° C. to 900 ° C. is less than 3.5% by weight, particularly 3.0% by weight, per 170 ° C. dried product. It is preferable to use the following. This loss on heating corresponds to the amount of OH groups in the silica particles, and is the amount of OH groups excluding the amount of adsorbed water. FIG. 1 shows a graph in which the ester conversion rate when lipase is supported on silica particles having various heating losses is plotted against the heating losses (the above OH group amount). It can be seen that the ester conversion rate decreases as the group amount increases, and the ester conversion rate increases as the OH group amount decreases. That is, there is a correlation between the ester conversion rate (catalytic activity) and the heat loss of silica particles. In the present invention, by using silica particles whose heat loss is adjusted to the above range, a stable and high ester is obtained. The conversion rate can be secured. As described above, a high ester conversion rate can be secured by using silica particles that are adjusted to be small so that the heating loss is within the above range. This is probably because the catalytic activity of lipase tends to be deactivated, and since lipase itself is hydrophobic, it is difficult to effectively support lipase on silica particles.
本発明において、シリカ粒子の加熱減量の上記範囲内への抑制は、例えばシリカ粒子を１７０℃以上の温度で焼成することにより容易に行うことができる。例えば、この焼成温度が高いほど、また焼成時間が長いほど、ＯＨ基量を大きく低減させ、加熱減量を上記範囲に調整することができる。 In the present invention, the heating loss of the silica particles can be easily controlled by firing the silica particles at a temperature of 170 ° C. or higher, for example. For example, the higher the firing temperature and the longer the firing time, the greater the amount of OH groups can be reduced, and the heating loss can be adjusted to the above range.
また、本発明においては、上記のようにＯＨ基量が一定範囲内に抑制されたもののシリカ粒子の中でも、バーミキュライトを酸処理して得られる非晶質シリカ粒子を用いることが、触媒活性が長く、長期にわたって繰り返してエステル合成を行うことができるという点で好ましい。 Further, in the present invention, among the silica particles whose OH group amount is suppressed within a certain range as described above, it is possible to use amorphous silica particles obtained by acid-treating vermiculite with a long catalytic activity. It is preferable in that the ester synthesis can be performed repeatedly over a long period of time.
即ち、バーミキュライトを酸処理して得られる非晶質シリカは、ＳｉＯ２の薄層が積層された劈開性積層体粒子からなる葉片状、鱗片状または板状と呼ばれる形状を有しており、多数積層されているシリカの薄層が層として独立した挙動を示しうるという特性即ち劈開性を示す。このようなシリカ粒子（以下、劈開性積層シリカ粒子と呼ぶことがある）は、その劈開性積層粒子構造に関連して、エステル合成に際して油脂の加水分解により生じたグリセリンを速やかに内部に吸収保持し、これを外部に放出しないという性質を有しており、この結果、グリセリンによるエステル交換反応の妨害を回避し、安定してエステル合成を行うことができるものと思われる。例えば、このようなバーミキュライトを酸処理して得られる非晶質シリカを用いた場合には、後述する実施例に示されているように（図２参照）、極めて多数回にわたって繰り返しエステル化反応を行うことができ、他のシリカ粒子に比しても、その積算変換量（総エステル変換量）が著しく高いことが判る。 That is, the amorphous silica obtained by acid treatment of vermiculite has a shape called a leaf shape, a scale shape, or a plate shape composed of cleaved laminate particles in which thin layers of SiO 2 are laminated, It exhibits the property that a thin layer of silica layered in multiple layers can exhibit independent behavior as a layer, that is, a cleavage property. Such silica particles (hereinafter sometimes referred to as “cleavable laminated silica particles”) quickly absorb and retain glycerin produced by hydrolysis of fats and oils during ester synthesis in relation to the structure of the cleaved laminated particles. However, it has the property of not releasing it to the outside, and as a result, it seems that the ester exchange reaction by glycerin can be avoided and the ester synthesis can be carried out stably. For example, when amorphous silica obtained by acid treatment of such vermiculite is used, as shown in an example described later (see FIG. 2), the esterification reaction is repeated extremely many times. It can be seen that the integrated conversion amount (total ester conversion amount) is significantly higher than other silica particles.
＜劈開性積層シリカ粒子の製造＞
このような劈開性シリカ粒子の製造原料として用いるバーミキュライト(vermiculite)は、バーミキュライト群粘土鉱物あるいは雲母群粘土鉱物に分類される加水雲母を主成分とする鉱物であり、蛭石とも呼ばれている。この鉱物を一定温度以上に急熱すると、面指数（００１）の面に垂直な方向（Ｃ軸方向）に著しく延び、蛭に似た形態になるのが名前の由来となっている。このバーミキュライトには、基本的に下記式（１）で表わされる化学構造を有する３八面体型のものと、下記式（２）で表わされる化学構造を有する２八面体型のものとがあり、何れも使用することができる。
<Manufacture of cleaved laminated silica particles>
Vermiculite used as a raw material for producing such cleaved silica particles is a mineral mainly composed of hydromica classified as vermiculite group clay mineral or mica group clay mineral, and is also called meteorite. When this mineral is rapidly heated to a certain temperature or more, the name is derived from the fact that it significantly extends in the direction perpendicular to the plane index (001) (C-axis direction) and has a shape resembling cocoons. The vermiculite basically includes a trioctahedral type having a chemical structure represented by the following formula (1) and a bioctahedral type having a chemical structure represented by the following formula (2). Either can be used.
｛Ｅ０．６〜０．８・４〜５Ｈ２Ｏ｝（Ｍｇ，Ｆｅ３＋，Ｆｅ２＋，Ａｌ）３
・［Ｓｉ，Ａｌ］４Ｏ１０（ＯＨ）２ …（１）
｛Ｅ０．６〜０．８・ｎＨ２Ｏ｝（Ａｌ，Ｆｅ，Ｍｇ）２・［Ｓｉ，Ａｌ］４
・Ｏ１０（ＯＨ）２ …（２）
尚、上記式中、Ｅは層間イオンであり、主としてＫやＭｇからなる。
{E 0.6-0.8 · 4-5H 2 O} (Mg, Fe 3+ , Fe 2+ , Al) 3
[Si, Al] 4 O 10 (OH) 2 (1)
{E 0.6 to 0.8 · nH 2 O} (Al, Fe, Mg) 2. [Si, Al] 4
・ O 10 (OH) 2 (2)
In the above formula, E is an interlayer ion and is mainly composed of K or Mg.
また、バーミキュライトの化学的組成は、産地等によっても相違するが、代表的な組成は以下の通りである。
ＳｉＯ２：３５〜４５重量％
Ａｌ２Ｏ３：１０〜２０重量％
ＭｇＯ：７〜３０重量％
Ｆｅ２Ｏ３：５〜２２重量％
ＣａＯ：０〜３重量％
Ｎａ２Ｏ：０〜１重量％
Ｋ２Ｏ：０〜１０重量％
Ｆｅ以外の重金属含量（Ｐｂ，Ｃｒ，Ｃｄ等）：０.２重量％以下
灼熱減量（１０５０℃）：３〜２５重量％
The chemical composition of vermiculite varies depending on the production area, but typical compositions are as follows.
SiO 2: 35~45 weight%
Al 2 O 3 : 10 to 20% by weight
MgO: 7 to 30% by weight
Fe 2 O 3: 5~22 wt%
CaO: 0 to 3% by weight
Na 2 O: 0 to 1% by weight
K 2 O: 0~10 weight%
Heavy metal content other than Fe (Pb, Cr, Cd, etc.): 0.2 wt% or less Loss on ignition (1050 ° C.): 3-25 wt%
本発明で好適に使用される劈開性積層シリカ粒子は、上記のようなバーミキュライトを酸処理することにより製造される。このような酸処理を行うことにより、結晶構造が破壊され、且つ有色成分が除去され、白色性が向上する。 The cleaved laminated silica particles preferably used in the present invention are produced by acid-treating vermiculite as described above. By performing such an acid treatment, the crystal structure is destroyed, the colored components are removed, and the whiteness is improved.
酸処理に使用される酸としては、硫酸、塩酸、硝酸等の鉱酸が使用され、その使用量は、バーミキュライト中のＦｅ２Ｏ３を含む塩基性成分に対して過剰量である。また、酸濃度は、一般に、１５乃至４０重量％、特に２０乃至３５重量％とするのがよく、酸処理温度は、１０乃至１１０℃の範囲とするのがよい。特に処理温度の高いほうが酸濃度を低くしても処理が短時間で行える。酸処理時間は、酸濃度や酸の使用量、温度等によっても異なり、一概に規定することはできないが、酸処理によって、シリカ（ＳｉＯ２換算）含量が、８２重量％以上、特に８５重量％以上、白色度が８５％以上、特に８８％以上に高められる程度の時間、酸処理を行うのがよく、通常、６乃至４８時間程度である。 As the acid used for the acid treatment, mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid are used, and the amount used is excessive with respect to the basic component containing Fe 2 O 3 in vermiculite. The acid concentration is generally 15 to 40% by weight, particularly 20 to 35% by weight, and the acid treatment temperature is preferably 10 to 110 ° C. In particular, when the treatment temperature is high, the treatment can be performed in a short time even if the acid concentration is lowered. The acid treatment time varies depending on the acid concentration, the amount of acid used, the temperature, etc., and cannot be generally specified. However, the acid treatment results in a silica (SiO 2 equivalent) content of 82% by weight or more, particularly 85% by weight. As described above, the acid treatment is preferably carried out for a time period in which the whiteness is increased to 85% or more, particularly 88% or more, and is usually about 6 to 48 hours.
また、酸処理に先立って、必要により、２００乃至５００℃の温度で加熱処理を行うこともできる。この加熱処理は、膨積処理と呼ばれるものであり、バーミキュライトの層状構造をバラバラにするために行われ、特にアスペクト比の高い粒子を得るために有効である。 In addition, prior to the acid treatment, if necessary, heat treatment can be performed at a temperature of 200 to 500 ° C. This heat treatment is called expansion treatment, and is performed to separate the layered structure of vermiculite, and is particularly effective for obtaining particles having a high aspect ratio.
尚、上記のような酸処理に先立って、必要により、夾雑する脈石の分離を行うのが好ましい。この分離は、水簸、液体サイクロンなどによる湿式分級方法および風簸、サイクロン、ミクロンセパレータなどによる乾式分級方法が一般に適用できる。 Prior to the acid treatment as described above, it is preferable to separate contaminated gangue as necessary. For this separation, a wet classification method using a water tank, a liquid cyclone or the like and a dry classification method using a wind tank, a cyclone, a micron separator or the like can be generally applied.
本発明においては、上記で得られたバーミキュライトの酸処理物からなる劈開性積層シリカ粒子を、そのままリパーゼの担持に使用することもできるが、通常は、これを、さらにｐＨ５．０乃至１０．０での水熱反応に供することが好ましい（以下、このような水熱反応により得られた劈開性積層シリカ粒子を、高活性劈開性積層シリカ粒子と呼ぶ）。即ち、このような水熱反応により、非晶質シリカの各粒子で、小さい粒子のＳｉＯ２成分が溶解し大きい粒子の表面にＯＨ基同士の縮合等を介して再配列して析出することにより、バーミキュライトに由来する特有の層状ケイ酸構造や劈開性を維持したまま、ＯＨ基量（加熱減量）を大きく低減させると同時に、水銀圧入法により測定した０．０２４乃至８．７０μｍの細孔直径での空間容積を２．２ｍｌ／ｇ以上と極めて高くすることが出来る。即ち、粒子間距離が大きく、嵩密度が著しく低減し、少量であってもエステル化反応に際して多量のグリセリンを吸収保持することが可能となり、この結果、触媒寿命が向上し、多数回にわたって繰り返しエステル化反応を行うことができるのである。 In the present invention, the cleaved laminated silica particles comprising the acid-treated product of vermiculite obtained above can be used as it is for supporting lipase, but this is usually further adjusted to pH 5.0 to 10.0. It is preferable to subject to the hydrothermal reaction in (the cleaved laminated silica particles obtained by such a hydrothermal reaction are hereinafter referred to as highly active cleaved laminated silica particles). That is, by such a hydrothermal reaction, small particles of SiO 2 component are dissolved in each particle of amorphous silica, and are rearranged and precipitated on the surface of large particles through condensation of OH groups or the like. While maintaining the peculiar layered silicic acid structure derived from vermiculite, the OH group amount (heat loss) was greatly reduced and at the same time a pore diameter of 0.024 to 8.70 μm measured by mercury porosimetry. The space volume at can be made extremely high at 2.2 ml / g or more. That is, the distance between particles is large, the bulk density is remarkably reduced, and even a small amount can absorb and retain a large amount of glycerin. As a result, the catalyst life is improved and the ester is repeatedly produced many times. The reaction can be carried out.
このようなｐＨ下での水熱反応は、得られたバーミキュライト酸処理物（非晶質シリカ）の水分散液を調製し（水分散液調製工程）、次いで、該水分散液をｐＨ調整する（ｐＨ調整工程）ことにより行われる。 In such a hydrothermal reaction under pH, an aqueous dispersion of the obtained vermiculite-treated product (amorphous silica) is prepared (aqueous dispersion preparation step), and then the pH of the aqueous dispersion is adjusted. (PH adjustment step).
酸処理物の水分散液は、バーミキュライトの酸処理によって得られた酸処理物をろ過し、水洗し、余剰の酸を除去することにより得られた酸処理物のろ過ケーキを、必要により粉砕して再度水に分散することにより調製される。 The aqueous dispersion of the acid-treated product is obtained by filtering the acid-treated product obtained by the acid treatment of vermiculite, washing it with water, and removing the excess acid. And again by dispersing in water.
このようにして調製される酸処理物の水分散液の酸処理物濃度は、通常、１５ 乃至２５重量％の範囲にあることが好適である。この濃度が低いと、生産性が低下してしまうし、また必要以上に高濃度であると、以後の工程で分散液の撹拌が困難となるおそれがある。 The concentration of the acid-treated product in the aqueous dispersion of the acid-treated product thus prepared is usually preferably in the range of 15 to 25% by weight. When this concentration is low, productivity is lowered, and when the concentration is higher than necessary, stirring of the dispersion may be difficult in the subsequent steps.
分散液のｐＨは、ｐＨを５．０乃至１０．０の範囲に調整すれば良い。用いるｐＨ調整に用いるものは、特に制限されないが、ｐＨ調整が容易であることなどの観点から、ＮＨ４ＯＨ水溶液、ケイ酸ソーダ水溶液或いはＭｇ（ＯＨ）２スラリーを用いるのがよい。 The pH of the dispersion may be adjusted in the range of 5.0 to 10.0. It is that used for pH adjustment used is not particularly limited, from the viewpoint of being easy pH adjustment, NH 4 OH aqueous solution, it is preferable to use the aqueous solution of sodium silicate or Mg (OH) 2 slurry.
また、ｐＨを上記範囲とすることは極めて重要であり、ｐＨが上記範囲よりも高いと、酸処理物の多くが溶解してしまい、バーミキュライトに由来する層状ケイ酸構造や劈開性が消失してしまう。また、ｐＨが上記範囲よりも低いと、酸処理物であるシリカ表面に存在するＳｉＯ２の溶解が有効に生ぜず、この結果、前述した空間容積や嵩密度等の物性を得ることができなくなってしまう。 In addition, it is extremely important to set the pH within the above range. If the pH is higher than the above range, most of the acid-treated product is dissolved, and the layered silicic acid structure and cleavage property derived from vermiculite disappear. End up. Further, if the pH is lower than the above range, dissolution of SiO 2 present on the silica surface which is an acid-treated product does not occur effectively, and as a result, the physical properties such as the above-described space volume and bulk density cannot be obtained. End up.
上記のようなアルカリ前処理工程は、ｐＨが上記範囲内で安定し、酸処理物が均一に分散する程度に行えばよく、通常、ｐＨ調整剤との攪拌下の混合を３０乃至６０分程度行えばよい。 The alkali pretreatment step as described above may be carried out to such an extent that the pH is stable within the above range and the acid-treated product is uniformly dispersed. Usually, the mixing with the pH adjuster is performed for about 30 to 60 minutes. Just do it.
かくして得られたｐＨ調整した分散液を、８０℃以上、好ましくは８０乃至１８０℃の温度で水熱処理することにより、リパーゼの担持に好適に使用され、特性の著しく向上した高活性の劈開性積層シリカ粒子を得ることができる。即ち、かかる水熱反応により、ＳｉＯ２の溶解及び再配列が生じ、各種物性の改質が行われるのである。水熱処理温度が、上記範囲よりも低いと、ＳｉＯ２の溶解及び再配列が不十分となり、例えば加熱減量の低減が不十分となり、また、空間容積が小さくなり、また嵩密度も大きくなってしまう。また、水熱処理温度が上記範囲よりも高いと、バーミキュライトに由来する層状ケイ酸構造や劈開性が損なわれてしまう。 The pH-adjusted dispersion thus obtained is hydrothermally treated at a temperature of 80 ° C. or higher, preferably 80 to 180 ° C., so that it can be suitably used for lipase loading and has a highly active cleaving laminate with significantly improved properties. Silica particles can be obtained. That is, such hydrothermal reaction causes dissolution and rearrangement of SiO 2 , and various physical properties are modified. When the hydrothermal treatment temperature is lower than the above range, the dissolution and rearrangement of SiO 2 becomes insufficient, for example, the reduction in heating loss is insufficient, the space volume is reduced, and the bulk density is also increased. . On the other hand, if the hydrothermal treatment temperature is higher than the above range, the layered silicic acid structure derived from vermiculite and the cleavage property are impaired.
また、上記の水熱処理は、オートクレーブにより加圧下で行うことが好ましく、例えば１気圧以上、好ましくは２気圧以上の圧力下で行うことが、ＳｉＯ２の溶解や再配列を促進させ、水熱処理を短時間で行う上で好適である。 The hydrothermal treatment is preferably performed under pressure by an autoclave. For example, the hydrothermal treatment is performed at a pressure of 1 atm or higher, preferably 2 atm or higher, to promote dissolution and rearrangement of SiO 2 and hydrothermal treatment. It is suitable for performing in a short time.
本発明において、上述した水熱処理は、圧力によっても異なるが、一般的には、１乃至１０時間程度行えばよい。水熱処理後は、得られた処理液をろ過し、必要に応じて水洗した後に乾燥し、適度な粒度に粉砕することにより、目的とする高活性劈開性積層シリカ粒子が得られる。 In the present invention, the above-described hydrothermal treatment is generally performed for about 1 to 10 hours, although it varies depending on the pressure. After the hydrothermal treatment, the obtained treatment liquid is filtered, washed with water as necessary, dried, and pulverized to an appropriate particle size to obtain the desired highly active cleaved laminated silica particles.
このようにして得られる高活性劈開性積層シリカ粒子は、原料バーミキュライトに由来して、非晶質シリカ薄層の劈開性積層体粒子構造を有している。図３は、この高活性劈開性積層シリカ粒子の粒子構造を示す電子顕微鏡写真を示す。 The highly active cleaved laminated silica particles thus obtained are derived from raw material vermiculite and have a cleaved laminated particle structure of a thin amorphous silica layer. FIG. 3 shows an electron micrograph showing the particle structure of the highly active cleaved laminated silica particles.
即ち、図３から理解されるように、かかる粒子は、板状粒子形状を有しており、非晶質シリカ薄層が積層した劈開性積層体粒子構造を有している。かかる高活性劈開性積層シリカ粒子は、レーザ回折法で測定して中位径（Ｄ５０）が１乃至２０μｍ、特に１乃至１５μｍの範囲にあり、その面方向最大径／厚みで表されるアスペクト比は、１５乃至４０の範囲にあり、且つその厚みは、０．１５乃至０．５０μｍ程度と極めて薄い。即ち、バーミキュライトを単に酸処理して得られた非晶質シリカは、同様の板状粒子形状を有しているが、加熱減量（ＯＨ基量）が多いばかりか、その厚みも厚い。 That is, as can be understood from FIG. 3, the particles have a plate-like particle shape and have a cleavage laminate particle structure in which thin layers of amorphous silica are laminated. Such highly active cleaved laminated silica particles have a median diameter (D 50 ) in the range of 1 to 20 μm, particularly 1 to 15 μm as measured by a laser diffraction method, and an aspect represented by the maximum diameter / thickness in the plane direction. The ratio is in the range of 15 to 40, and the thickness is as extremely thin as about 0.15 to 0.50 μm. That is, amorphous silica obtained by simply acid-treating vermiculite has a similar plate-like particle shape, but has a large loss on heating (OH group amount) and a large thickness.
このような高活性劈開性積層シリカ粒子は、水銀圧入法により測定した０．０２４乃至８．７０μｍの細孔直径での空間容積が２．２ｍｌ／ｇ以上、特に２．２乃至３．０ｍｌ／ｇの範囲にある。即ち、かかる空間容積は、粒子内の細孔容積ではなく、粒子間空隙の大きさを示すものであり、単にバーミキュライトの酸処理によって得られた非晶質シリカに比して、この空間容積が増大している。従って、かかる非晶質シリカ粒子は、大きな粒子間空隙を有しているため、その嵩密度は、０．１９ｇ／ｍｌ以下、特に０．１０乃至０．１８ｇ／ｍｌの極めて小さな範囲にある。即ち、極めて軽量性に富んでおり、少ない使用量で多量のグリセリンを吸収保持することができる。 Such highly active cleaved laminated silica particles have a spatial volume at a pore diameter of 0.024 to 8.70 μm measured by a mercury intrusion method of 2.2 ml / g or more, particularly 2.2 to 3.0 ml / It is in the range of g. In other words, this spatial volume is not the pore volume in the particles, but the size of the interparticle voids. It is increasing. Therefore, since such amorphous silica particles have large interparticle voids, their bulk density is in the very small range of 0.19 g / ml or less, particularly 0.10 to 0.18 g / ml. That is, it is extremely lightweight and can absorb and retain a large amount of glycerin with a small amount of use.
＜エステル合成触媒の製造＞
上述した担体粒子にリパーゼを担持してなる本発明のエステル合成触媒は、リパーゼの水分散液に担体粒子を混合して攪拌し、得られた混合液を乾燥して水を除去することにより製造される。即ち、担体粒子とリパーゼとを溶媒を介在させずに混合する場合には、リパーゼが担体粒子の細孔に保持されず、エステル合成に際してリパーゼが脱落してしまう結果、高い触媒活性を維持させることができない。
<Manufacture of ester synthesis catalyst>
The ester synthesis catalyst of the present invention formed by supporting lipase on the carrier particles described above is produced by mixing the carrier particles with an aqueous dispersion of lipase and stirring, drying the resulting mixture to remove water. Is done. That is, when the carrier particles and the lipase are mixed without a solvent, the lipase is not retained in the pores of the carrier particles, and the lipase is dropped during ester synthesis, so that high catalytic activity is maintained. I can't.
また、用いるリパーゼの水分散液は、その濃度を０．１乃至１５重量％、好ましくは１乃至１０重量％の範囲とすべきである。即ち、リパーゼの濃度がこの範囲よりも希薄なときには、リパーゼと担体粒子が分離してしまい、均一な担持ができなくなるだけでなく、所定量のリパーゼを担体粒子に担持させるためには、多量の水分散液を使用しなければならず、効率が悪く、乾燥にも長時間を要し、工業的生産には不適当となってしまう。また、リパーゼが上記範囲よりも高濃度の水分散液を使用すると、リパーゼが担体粒子の細孔に有効に浸透せず、その担持が不十分となってしまう。従って、濃度が上記範囲にある水分散液を使用し、これに所定量の担体粒子を混合攪拌することにより、前述した適当量のリパーゼを担体粒子に担持させることができる。 Further, the aqueous dispersion of lipase to be used should have a concentration of 0.1 to 15% by weight, preferably 1 to 10% by weight. That is, when the lipase concentration is less than this range, the lipase and the carrier particles are separated, and not only can not be uniformly supported, but in order to carry a predetermined amount of lipase on the carrier particles, a large amount An aqueous dispersion must be used, is inefficient, takes a long time for drying, and is unsuitable for industrial production. Further, when an aqueous dispersion having a lipase having a concentration higher than the above range is used, the lipase does not effectively penetrate into the pores of the carrier particles, and the loading thereof becomes insufficient. Therefore, the above-mentioned appropriate amount of lipase can be supported on the carrier particles by using an aqueous dispersion having a concentration in the above range and mixing and stirring a predetermined amount of carrier particles therein.
また、担体粒子をリパーゼの水分散液に添加しての混合攪拌に際しては、必要に応じて界面活性剤や分散助剤を用いることもできるが、その種類や使用量は、混合液のｐＨが６乃至８の範囲内となるように選択すべきである。即ち、混合液のｐＨが上記範囲外であると、リパーゼの失活を生じてしまうからである。 In addition, when mixing and stirring the carrier particles by adding them to the aqueous lipase dispersion, a surfactant or a dispersion aid can be used as necessary, but the type and amount used depend on the pH of the mixture. It should be selected to be in the range of 6-8. That is, when the pH of the mixed solution is outside the above range, lipase is deactivated.
混合攪拌は、攪拌の剪断力等にもよるが、一般的には、１乃至６０分程度で十分である。また、混合攪拌後の乾燥は、用いるリパーゼの失活温度未満で加温或いは風乾することにより行われる。因みに、本発明において最も好適に使用されるリパーゼQLMの失活温度は、６５℃以上であり、リパーゼOFの失活温度は、４５℃以上である。 For mixing and stirring, although depending on the shearing force of stirring and the like, generally 1 to 60 minutes is sufficient. Moreover, drying after mixing and stirring is performed by heating or air drying below the deactivation temperature of the lipase used. Incidentally, the deactivation temperature of lipase QLM most preferably used in the present invention is 65 ° C. or higher, and the deactivation temperature of lipase OF is 45 ° C. or higher.
＜バイオ燃料の製造＞
本発明において、上記のようにして得られたエステル合成触媒は、エステル合成によるバイオ燃料の製造に使用される。例えば、低級アルコールと油脂とを、上記エステル合成触媒の存在下でエステル交換反応させることにより、バイオ燃料となる脂肪酸エステルが製造される。
<Manufacture of biofuel>
In the present invention, the ester synthesis catalyst obtained as described above is used for production of biofuel by ester synthesis. For example, the fatty acid ester used as a biofuel is manufactured by transesterifying a lower alcohol and fats and oils in the presence of the ester synthesis catalyst.
低級アルコールは、エステル化剤として使用されるものであり、メタノール、エタノール、プロパノール、ブタノール、ペンタノール等の炭素数５以下のアルコールを挙げることができるが、反応性の点でもコストの点でもメタノールが好ましい。このような低級アルコールは、油脂に対して当量以上の量で用いるのがよい。 The lower alcohol is used as an esterifying agent, and examples thereof include alcohols having 5 or less carbon atoms such as methanol, ethanol, propanol, butanol, and pentanol. Is preferred. Such a lower alcohol is preferably used in an amount equal to or greater than that of the oil.
また、油脂としては、天然界に広く存在する各種の動植物油脂を用いることができるが、一般には、脂肪酸とグリセリンとのエステルを主成分とする植物油、例えばサフラワー油、大豆油、菜種油、パーム油、パーム核油、綿実油、ヤシ油、米糠油、ゴマ油、ヒマシ油、亜麻仁油、オリーブ油、桐油、椿油、落花生油、カポック油、カカオ油、木蝋、ヒマワリ油、コーン油などが好適に使用される。 As the fats and oils, various animal and vegetable fats and oils widely existing in the natural world can be used. In general, vegetable oils mainly composed of esters of fatty acids and glycerin, such as safflower oil, soybean oil, rapeseed oil, palm Oil, palm kernel oil, cottonseed oil, palm oil, rice bran oil, sesame oil, castor oil, linseed oil, olive oil, tung oil, camellia oil, peanut oil, kapok oil, cacao oil, wood wax, sunflower oil, corn oil, etc. are suitably used. The
リパーゼを用いたエステル交換反応は、比較的低温で反応が進行し、エステル交換によって脂肪酸の低級エステルが生成し、同時に遊離脂肪酸やグリセリンも副生する。しかるに、この遊離脂肪酸は、リパーゼによりメチルエステル化されるため、アルカリ触媒を用いてのエステル合成と異なり、石けんが生成しない。従って、ケン化等による精製処理が不必要であるという利点がある。また、本発明のエステル合成触媒を用いた場合には、リパーゼを担持している担体粒子（シリカ）がグリセリン吸着能を有しているため、この担体粒子にグリセリンが捕捉される。このようにエステル交換により副生するグリセリンが捕捉されることも、本発明において、高い触媒効果（高いエステル変換率）が保持され且つこの触媒効果が持続して発揮されることの一因と思われる。 The transesterification reaction using lipase proceeds at a relatively low temperature, and a lower ester of a fatty acid is produced by transesterification, and at the same time, free fatty acid and glycerin are by-produced. However, since this free fatty acid is methyl esterified by lipase, no soap is produced unlike ester synthesis using an alkali catalyst. Therefore, there is an advantage that a purification treatment by saponification or the like is unnecessary. When the ester synthesis catalyst of the present invention is used, since the carrier particles (silica) carrying lipase have glycerin adsorption ability, glycerin is captured by the carrier particles. The trapping of glycerin produced as a by-product by transesterification in this way is also considered to be a factor in the present invention that a high catalytic effect (high ester conversion rate) is maintained and this catalytic effect is sustained. It is.
また、本発明において、油脂の代わりに脂肪酸、例えば不飽和脂肪酸等も使用することができ、その際にはエステル化により副生する水が担体粒子に吸着される。即ち、本発明で用いるエステル合成触媒中のリパーゼは、脂肪酸とアルコールとのエステル化反応に対しても高い触媒効果を示すため、油脂の代わりに脂肪酸を用いた場合にも、バイオ燃料となる脂肪酸エステルを製造することができる。 In the present invention, fatty acids such as unsaturated fatty acids can be used instead of fats and oils, and water produced as a by-product by esterification is adsorbed on the carrier particles. That is, the lipase in the ester synthesis catalyst used in the present invention exhibits a high catalytic effect for the esterification reaction of a fatty acid and an alcohol. Therefore, even when a fatty acid is used instead of an oil or fat, a fatty acid that becomes a biofuel Esters can be produced.
上述した油脂或いは脂肪酸と低級アルコールとの反応は、水分散系及び有機溶媒系の何れでも行うことが可能であるが、本発明では、有機溶媒系で反応を行うことが好ましい。即ち、水分散系で反応を行うと、担体粒子に担持されているリパーゼが担体粒子から脱落してしまい、反応物からのリパーゼの回収などが必要となり、また反応を長時間にわたって継続して行うことも困難となってしまうが、有機溶媒系では、担体粒子に担持されているリパーゼが脱落せず、安定に保持されているため、触媒活性が持続し、長時間にわたって反応を続行させることができ、またリパーゼの回収なども不要となり、極めて効率よく、バイオ燃料を製造することができる。尚、有機溶媒としては、リパーゼを失活させないものであれば特に制限なく使用することができるが、一般には、ヘキサン等の炭化水素系溶媒がコスト等の点から好適に使用される。 The reaction of the above-described oil or fat or fatty acid and the lower alcohol can be carried out in either an aqueous dispersion system or an organic solvent system, but in the present invention, the reaction is preferably carried out in an organic solvent system. That is, when the reaction is carried out in an aqueous dispersion system, the lipase supported on the carrier particles falls off from the carrier particles, and it is necessary to recover the lipase from the reaction product, and the reaction is continued for a long time. However, in the organic solvent system, the lipase supported on the carrier particles does not fall off and is maintained stably, so that the catalytic activity is sustained and the reaction can be continued for a long time. In addition, recovery of lipase is not required, and biofuel can be produced very efficiently. In addition, as an organic solvent, if it does not deactivate lipase, it can be used without a restriction | limiting in particular, However, Generally hydrocarbon type solvents, such as hexane, are used suitably from points, such as cost.
また、反応は、所謂バッチ式で行われるが、触媒を適当な配管等の固定床に充填し、この固定床に油脂或いは脂肪酸や低級アルコール等の反応成分を有機溶媒に分散乃至溶解させて連続的に供給する連続式で反応を行うことも可能となる。 The reaction is carried out in a so-called batch system, and the catalyst is filled in a fixed bed such as an appropriate pipe, and reaction components such as fats and oils, fatty acids and lower alcohols are dispersed or dissolved in an organic solvent continuously in this fixed bed. It is also possible to carry out the reaction in a continuous manner.
尚、反応は、リパーゼが活性を保つ温度（即ち、失活温度未満）に加温して行うのがよい。 The reaction is preferably performed by heating to a temperature at which the lipase maintains activity (that is, below the deactivation temperature).
油脂と低級アルコールとの反応により得られた脂肪酸エステルは、モノグリセリド、ジグリセリド、トリグリセリド或いはグリセリンや低級アルコールを含み、脂肪酸と低級アルコールとの反応により得られた脂肪酸エステルは、脂肪酸あるいは水や低級アルコールを含むが、蒸留、抽出、油水分離等のそれ自体公知の手段で分離回収することができる。 Fatty acid esters obtained by the reaction of fats and oils with lower alcohols include monoglycerides, diglycerides, triglycerides, glycerin and lower alcohols, and fatty acid esters obtained by the reaction of fatty acids with lower alcohols include fatty acids, water and lower alcohols. Including, it can be separated and recovered by means known per se such as distillation, extraction, oil-water separation.
本発明の優れた効果を、次の実施例及び比較例により説明する。なお、測定は以下の方法で行った。 The excellent effects of the present invention will be described with reference to the following examples and comparative examples. The measurement was performed by the following method.
（１）標準メチルエステル調製方法
ナタネ油１ｇにメタノール０．３ｇ、水酸化ナトリウム０．０１５ｇ添加して、振とう器を用いて１５０ｒｐｍで撹拌しながら９０℃で１時間加熱した。加熱後、水５０ｍｌ、ヘキサン５０ｍｌ加えて撹拌し、液をコニカルチューブに移して８０００ｒｐｍで遠心分離した。遠心分離後、一番上の透明な液層をガラス管に移し、７０℃に加熱してヘキサンを除去し、標準メチルエステルとした。
(1) Standard methyl ester preparation method 0.3 g of methanol and 0.015 g of sodium hydroxide were added to 1 g of rapeseed oil and heated at 90 ° C. for 1 hour while stirring at 150 rpm using a shaker. After heating, 50 ml of water and 50 ml of hexane were added and stirred, and the liquid was transferred to a conical tube and centrifuged at 8000 rpm. After centrifugation, the uppermost transparent liquid layer was transferred to a glass tube and heated to 70 ° C. to remove hexane to obtain a standard methyl ester.
（２）エステル変換率測定方法
試料２．５μｇを測り取り、クロロホルム１．５ｇと混合して試料液とした。ガスクロマトグラフＧＣ−１４Ａ（島津製作所製）を用いて、検出器：ＦＩＤ、ガラスカラム：内径３．２ｍｍ長さ２．１ｍ、カラム充填剤：Ａｄｖａｎｃｅ−ＤＳ Ｃｈｒｏｍｏｓｏｒｂ Ｗ ８０／１００ｍｅｓｈｅｓ（島津製作所製）、キャリアーガス：Ｎ２、キャリアーガス流量：４０ｍｌ／分、カラム温度：１９０℃、注入口温度：２４０℃、検出器温度：２４０℃の条件に設定した。マイクロシリンジで試料液２μlを取り、注入口から注入して測定し、得られたチャートから試料のピーク面積を得た。同様にして標準メチルエステルのピーク面積を得て、標準メチルエステルのピーク面積を１００％として試料のピーク面積の比率を求め、エステル変換率を算出した。
(2) Ester conversion rate measuring method 2.5 μg of a sample was measured and mixed with 1.5 g of chloroform to obtain a sample solution. Using gas chromatograph GC-14A (manufactured by Shimadzu Corporation), detector: FID, glass column: inner diameter 3.2 mm, length 2.1 m, column filler: Advance-
（３）総積算変換量測定方法
繰り返し反応で得られた反応１回毎のエステル変換率から、次の式により反応１回毎の変換量を求め、得られた変換量の総和を総積算変換量とした。
反応１回毎の変換量（ｇ）＝１．４ｘ８４６/８４２ｘエステル変換率/１００
１．４：反応に使用したナタネ油重量（ｇ）
８４２：ナタネ油分子量
８４６：ナタネ油が完全にメチルエステルに変換した場合のメチルエステル分子量
(3) Total integrated conversion amount measurement method From the ester conversion rate for each reaction obtained in the repetitive reaction, the conversion amount for each reaction is obtained by the following formula, and the total of the obtained conversion amounts is converted into the total integrated conversion. The amount.
Conversion amount per reaction (g) = 1.4 × 846/842 × ester conversion / 100
1.4: Weight of rapeseed oil used in the reaction (g)
842: Rapeseed oil molecular weight 846: Methyl ester molecular weight when rapeseed oil is completely converted to methyl ester
（４）粒径（中位径）測定
Malvern社製Mastersizer２０００を使用して、レーザ回折散乱法で測定した。
(4) Particle size (median diameter) measurement
Measurement was performed by laser diffraction scattering using a Mastersizer 2000 manufactured by Malvern.
（５）比表面積および細孔半径測定
Micromeritics社製TriStar３０００を使用し、窒素吸着等温線を測定した。比表面積S（ｍ２／ｇ）は比圧が０．０５から０．３５以下の吸着枝側窒素吸着等温線からＢＥＴ法で求めた。比圧０．９６において吸着した窒素の容積を細孔容積V（ｃｍ３／ｇ）とし、細孔半径ｒ（Å）は、以下の式を用いて求めた。
ｒ＝２（V／S）×１０４
(5) Specific surface area and pore radius measurement
Nitrogen adsorption isotherm was measured using TriStar 3000 manufactured by Micromeritics. The specific surface area S (m 2 / g) was determined by the BET method from an adsorption branch side nitrogen adsorption isotherm having a specific pressure of 0.05 to 0.35 or less. The volume of nitrogen adsorbed at a specific pressure of 0.96 was defined as the pore volume V (cm 3 / g), and the pore radius r (Å) was determined using the following equation.
r = 2 (V / S) × 10 4
（６）導電率
１１０℃で２時間乾燥したシリカ５ｇを９５ｇの脱イオン水に分散し、５分煮沸後２５℃に調整し、カスタニーLAB導電率計DS-14（堀場製作所製）を用い、電極＃３５５１−１０Dを使用して測定した。
(6) Conductivity 5 g of silica dried at 110 ° C. for 2 hours is dispersed in 95 g of deionized water, boiled for 5 minutes, adjusted to 25 ° C., and using a castany LAB conductivity meter DS-14 (manufactured by Horiba Seisakusho) Measurements were made using electrode # 3551-10D.
（７）加熱減量（ＯＨ基量）
セイコーインスツルメンツ（株）製ＴＧ／ＤＴＡ６３００を用いて、熱重量分析を行った。標準物質α−Ａｌ２Ｏ３ 、昇温速度１０℃／min、空気雰囲気で測定し、１７０乃至９００℃迄の範囲での試料の加熱減量（ＯＨ基量）を求めた。
(7) Heat loss (OH group amount)
Thermogravimetric analysis was performed using TG / DTA6300 manufactured by Seiko Instruments Inc. Measurement was performed in a standard substance α-Al 2 O 3 , a heating rate of 10 ° C./min, in an air atmosphere, and the loss on heating (OH group amount) of the sample in the range of 170 to 900 ° C. was determined.
（８）空間容積
Micromeritics社製Auto Pore ＩＶを用い、水銀圧入法により細孔容積を測定し、０．０２４乃至８．７０μｍの細孔直径での細孔容積より空間容積を求めた。
(8) Space volume
Using Auto Pore IV manufactured by Micromeritics, the pore volume was measured by mercury porosimetry, and the space volume was determined from the pore volume at a pore diameter of 0.024 to 8.70 μm.
（９）嵩密度
ＪＩＳ Ｋ ６２２０−１ ７．７：２００１に準拠して測定した。
(9) Bulk density Measured according to JIS K 6220-1 7.7: 2001.
（実施例１）
Alcaligenes sp.由来のリパーゼQLM（名糖産業製）（加水分解活性２．６８×１０４ＩＵ／ｇ）３．５ｇを蒸留水３１．５ｇに３０分間撹拌しながら分散して、１１０℃で２時間乾燥した表１に示す物性のシリカ粒子（水澤化学工業製ミズカシルＰ−８０３）２５ｇおよび蒸留水４３ｇを混合し（混合液のｐＨは７．１）、５０℃で１２時間乾燥して、ミズカシルＰ−８０３を担体としてリパーゼ１４重量部を担持させたエステル合成触媒２８．５ｇを得た。
Example 1
Lipase QLM derived from Alcaligenes sp. (Manufactured by Meito Sangyo Co., Ltd.) (hydrolysis activity 2.68 × 10 4 IU / g) 3.5 g was dispersed in 31.5 g of distilled water with stirring for 30 minutes. 25 g of silica particles having physical properties shown in Table 1 (Mizusawa Chemical Industries Mizukasil P-803) and 43 g of distilled water were mixed (pH of the mixed solution was 7.1) and dried at 50 ° C. for 12 hours. 28.5 g of an ester synthesis catalyst carrying 14 parts by weight of lipase using P-803 as a carrier was obtained.
３０mlのガラス製遠心沈降管に、上記で得られたエステル合成触媒４ｇ、ヘキサン１２ｇ、ナタネ油１．４ｇ、メタノール０．１８ｇ添加して蓋をかけ、シェーカーを用いて３７℃、１００rpmで撹拌し４時間エステル交換反応を行った。エステル交換反応終了後３０００ｒｐｍで１０分間遠心分離して上澄み液を回収し、７０℃に加熱してヘキサンを除去し、エステル変換率を求めた。 Add 4 g of the ester synthesis catalyst obtained above, 12 g of hexane, 1.4 g of rapeseed oil, and 0.18 g of methanol to a 30 ml glass centrifugal settling tube, cover it, and stir at 37 ° C. and 100 rpm using a shaker. The transesterification reaction was performed for 4 hours. After completion of the transesterification reaction, the mixture was centrifuged at 3000 rpm for 10 minutes to recover the supernatant, heated to 70 ° C. to remove hexane, and the ester conversion rate was determined.
また、遠心分離により得られた固形分に、ヘキサン１．６ｇ、ナタネ油１．４ｇ、メタノール０．１８ｇ添加して蓋をかけ、シェーカーを用いて３７℃、１００ｒｐｍで撹拌し６時間反応させた後、１回目の反応と同様の操作でエステル変換率を求めた。また、エステル変換率が１０％未満となるまで遠心分離以降の操作を反復して、繰り返し反応を行い、総積算変換量を求めた。
エステル変換率及び総積算量、及びリパーゼの担持に用いたシリカ粒子の物性を表１に示した。
In addition, 1.6 g of hexane, 1.4 g of rapeseed oil, and 0.18 g of methanol were added to the solid content obtained by centrifugation, the lid was put on, and the mixture was stirred at 37 ° C. and 100 rpm for 6 hours with a shaker. Thereafter, the ester conversion rate was determined in the same manner as in the first reaction. Further, the operation after centrifugation was repeated until the ester conversion rate became less than 10%, and the reaction was repeated to obtain the total integrated conversion amount.
Table 1 shows the ester conversion rate, the total integrated amount, and the physical properties of the silica particles used for supporting the lipase.
エステル変換率については、その加熱減量（ＯＨ基量）に対してプロットして図１に示し、繰り返し反応の各回における積算変換量を図２に示した。 The ester conversion rate was plotted with respect to the loss on heating (OH group amount) and shown in FIG. 1, and the integrated conversion amount in each iteration of the reaction was shown in FIG.
（実施例２）
実施例１のシリカ粒子を、表１に示す物性のシリカ粒子（ミズカシルＰ−７０７；水澤化学工業製）に置き換え、それ以外は実施例１と同様にして行い（混合液のｐＨは６．９）、ミズカシルＰ−７０７を担体としてリパーゼ１４重量部を担持させたエステル合成触媒２８．５ｇを得た。
(Example 2)
The silica particles of Example 1 were replaced with silica particles having physical properties shown in Table 1 (Mizukasil P-707; manufactured by Mizusawa Chemical Co., Ltd.), and the others were carried out in the same manner as in Example 1 (the pH of the mixed solution was 6.9). ), 28.5 g of an ester synthesis catalyst carrying 14 parts by weight of lipase using Mizukacil P-707 as a carrier was obtained.
このエステル合成触媒について、実施例１と同様に、エステル変換率及び総積算量を測定し、その結果を表１に示した。また、エステル変換率については、その加熱減量（ＯＨ基量）に対してプロットして図１に示した。 For this ester synthesis catalyst, the ester conversion rate and the total integrated amount were measured in the same manner as in Example 1. The results are shown in Table 1. Further, the ester conversion rate is plotted against the loss on heating (OH group amount) and shown in FIG.
（実施例３）
実施例１のシリカ粒子を、表１に示す物性のシリカ粒子（ミズカシルＰ−７３；水澤化学工業製）に置き換え、それ以外は実施例１と同様にして行い（混合液のｐＨは７．２）、ミズカシルＰ−７３を担体としてリパーゼ１４重量部を担持させたエステル合成触媒２８．５ｇを得た。
(Example 3)
The silica particles of Example 1 were replaced with silica particles having physical properties shown in Table 1 (Mizukasil P-73; manufactured by Mizusawa Chemical Industry Co., Ltd.), and the others were carried out in the same manner as in Example 1 (the pH of the mixed solution was 7.2). ), 28.5 g of an ester synthesis catalyst carrying 14 parts by weight of lipase using Mizukasil P-73 as a carrier.
このエステル合成触媒について、実施例１と同様に、エステル変換率及び総積算量を測定し、その結果を表１に示した。また、エステル変換率については、その加熱減量（ＯＨ基量）に対してプロットして図１に示した。 For this ester synthesis catalyst, the ester conversion rate and the total integrated amount were measured in the same manner as in Example 1. The results are shown in Table 1. Further, the ester conversion rate is plotted against the loss on heating (OH group amount) and shown in FIG.
（比較例１）
実施例１のシリカを、表１に示す物性の合成シリカＡ（水澤化学工業製）に置き換え、それ以外は実施例１と同様にして行い、合成シリカＡを担体としてリパーゼ１４重量部を担持させたエステル合成触媒２８．５ｇを得た。
(Comparative Example 1)
The silica of Example 1 was replaced with synthetic silica A (manufactured by Mizusawa Chemical Co., Ltd.) having the physical properties shown in Table 1, and the others were carried out in the same manner as in Example 1, with 14 parts by weight of lipase supported using synthetic silica A as a carrier 28.5 g of an ester synthesis catalyst was obtained.
このエステル合成触媒について、実施例１と同様に、エステル変換率及び総積算量を測定し、その結果を表１に示した。また、エステル変換率については、その加熱減量（ＯＨ基量）に対してプロットして図１に示し、繰り返し反応の各回における積算変換量を図２に示した。 For this ester synthesis catalyst, the ester conversion rate and the total integrated amount were measured in the same manner as in Example 1. The results are shown in Table 1. Further, the ester conversion rate was plotted with respect to the loss on heating (OH group amount) and shown in FIG. 1, and the integrated conversion amount in each round of the repeated reaction is shown in FIG.
（比較例２）
実施例１のシリカを、表１に示す物性の合成シリカＢ（水澤化学工業製）に置き換え、それ以外は実施例１と同様にして行い、合成シリカＢを担体としてリパーゼ１４重量部を担持させたエステル合成触媒２８．５ｇを得た。
(Comparative Example 2)
The silica of Example 1 was replaced with synthetic silica B (manufactured by Mizusawa Chemical Co., Ltd.) having the physical properties shown in Table 1, and the others were carried out in the same manner as in Example 1, with 14 parts by weight of lipase being supported on synthetic silica B 28.5 g of an ester synthesis catalyst was obtained.
このエステル合成触媒について、実施例１と同様に、エステル変換率及び総積算量を測定し、その結果を表１に示した。また、エステル変換率については、その加熱減量（ＯＨ基量）に対してプロットして図１に示した。 For this ester synthesis catalyst, the ester conversion rate and the total integrated amount were measured in the same manner as in Example 1. The results are shown in Table 1. Further, the ester conversion rate is plotted against the loss on heating (OH group amount) and shown in FIG.
（比較例３）
Alcaligenes sp.由来のリパーゼQLM（名糖産業製）３．５ｇと、実施例１で用いたシリカ粒子（ミズカシルＰ−８０３；水澤化学工業製）２５ｇを混合し、ミズカシルＰ−８０３を１００重量部とリパーゼ１４重量部の混合物２８．５ｇを得た。
(Comparative Example 3)
Alcaligenes sp.-derived lipase QLM (manufactured by Meisei Sangyo) 3.5 g and silica particles (Mizukasil P-803; Mizusawa Chemical Industry) 25 g used in Example 1 were mixed, and 100 parts by weight of Mizukacil P-803 was mixed. And 28.5 g of a mixture of 14 parts by weight of lipase.
この混合物（エステル合成触媒）について、実施例１と同様に、エステル変換率及び総積算量を測定し、その結果を表１に示した。また、エステル変換率については、その加熱減量（ＯＨ基量）に対してプロットして図１に示した。 For this mixture (ester synthesis catalyst), the ester conversion rate and the total integrated amount were measured in the same manner as in Example 1, and the results are shown in Table 1. Further, the ester conversion rate is plotted against the loss on heating (OH group amount) and shown in FIG.
（実施例４）
高活性劈開性積層シリカ粒子の製造：
南アフリカ産バーミキュライト原石１．０ｋｇに水５．２ｋｇと９８％硫酸２．３ｋｇを加え、９５℃で２０時間加熱した。ろ過、水洗を行い、水洗後のケーキ５００ｇを水５００ｇに分散、撹拌しバーミキュライト酸処理物の水分散液を調製した。次に前記水分散液に、６ｍｏｌ／Ｌに調整したＮＨ４ＯＨ水溶液を滴下、良く撹拌し分散液を調製した。分散液のｐＨは８．５７／２３．７℃であった。pＨ調整した分散液をオートクレーブに移し、３００ｒｐｍ攪拌下１６０℃で６ｈｒ水熱処理を行った。処理後の液をろ過、乾燥、粉砕、分級を行い、高活性劈開性積層シリカ粒子を得た。
Example 4
Production of highly active cleaved laminated silica particles:
5.2 kg of water and 2.3 kg of 98% sulfuric acid were added to 1.0 kg of South African vermiculite ore and heated at 95 ° C. for 20 hours. Filtration and water washing were performed, and 500 g of the cake after water washing was dispersed in 500 g of water and stirred to prepare an aqueous dispersion of a vermiculite-treated product. Next, an aqueous NH 4 OH solution adjusted to 6 mol / L was dropped into the aqueous dispersion and stirred well to prepare a dispersion. The pH of the dispersion was 8.57 / 23.7 ° C. The dispersion adjusted to pH was transferred to an autoclave and subjected to hydrothermal treatment for 6 hours at 160 ° C. with stirring at 300 rpm. The treated liquid was filtered, dried, pulverized, and classified to obtain highly active cleaved laminated silica particles.
上記で得られた高活性劈開性積層シリカ粒子は、中位径が５．６μm、ＢＥＴ比表面積が４８ｍ２／ｇ、細孔半径が１２２Å、導電率が４６μＳ／ｃｍ、加熱減量が２．１重量％、空間容積が２．８８ｍｌ／ｇ、嵩密度が０．１３ｇ／ｍｌであった。また、このシリカ粒子の電子顕微鏡写真を図３に示した（倍率１０００倍）。 The highly active cleaved laminated silica particles obtained above have a median diameter of 5.6 μm, a BET specific surface area of 48 m 2 / g, a pore radius of 122 kg, a conductivity of 46 μS / cm, and a heat loss of 2.1. The weight percentage, the space volume was 2.88 ml / g, and the bulk density was 0.13 g / ml. Moreover, the electron micrograph of this silica particle was shown in FIG. 3 (magnification 1000 times).
実施例１のシリカを、上記で得られた高活性劈開性積層シリカ粒子に代えた以外は実施例１と同様にして行い（混合液のｐＨは７．０）、該シリカ粒子を担体としてリパーゼ１４重量部を担持させたエステル合成触媒２８．５ｇを得た。 The same procedure as in Example 1 was conducted except that the silica of Example 1 was replaced with the highly active cleaved laminated silica particles obtained above (the pH of the mixed solution was 7.0). 28.5 g of an ester synthesis catalyst carrying 14 parts by weight was obtained.
このエステル合成触媒について、実施例１と同様に、エステル変換率及び総積算量を測定したところ、エステル変換率は、１００％であり、総積算量は８０ｇであった。また、エステル変換率については、その加熱減量（ＯＨ基量）に対してプロットして図１に示した。また、繰り返し反応の各回における積算変換量を図２に示した。 With respect to this ester synthesis catalyst, the ester conversion rate and the total integrated amount were measured in the same manner as in Example 1. The ester conversion rate was 100%, and the total integrated amount was 80 g. Further, the ester conversion rate is plotted against the loss on heating (OH group amount) and shown in FIG. Further, FIG. 2 shows the integrated conversion amount at each time of the repetitive reaction.
（実施例５）
分散液のｐＨ調整を８．５３／２３．７℃にし、水熱処理を１４０℃で３ｈｒに代えた以外は、実施例４と同様にして高活性劈開性積層シリカ粒子を得た。このシリカ粒子は、中位径が５．５μm、ＢＥＴ比表面積が７０ｍ２／ｇ、細孔半径が５２Å、加熱減量が２．５重量％、空間容積が２．６７ｍｌ／ｇ、嵩密度が０．１５ｇ／ｍｌであった。
(Example 5)
Highly active cleaved laminated silica particles were obtained in the same manner as in Example 4 except that the pH of the dispersion was adjusted to 8.53 / 23.7 ° C and the hydrothermal treatment was changed to 140 ° C for 3 hours. This silica particle has a median diameter of 5.5 μm, a BET specific surface area of 70 m 2 / g, a pore radius of 52 mm, a loss on heating of 2.5% by weight, a space volume of 2.67 ml / g, and a bulk density of 0. .15 g / ml.
実施例１のシリカを、上記で得られた高活性劈開性積層シリカ粒子に代えた以外は実施例１と同様にして行い、該シリカ粒子を担体としてリパーゼ１４重量部を担持させたエステル合成触媒２８．５ｇを得た。 An ester synthesis catalyst in which the silica of Example 1 was replaced with the highly active cleaved laminated silica particles obtained above in the same manner as in Example 1, and supported by 14 parts by weight of lipase using the silica particles as a carrier. 28.5 g was obtained.
このエステル合成触媒について、実施例１と同様に、エステル変換率及び総積算量を測定したところ、エステル変換率は、９０％であった。また、エステル変換率については、その加熱減量（ＯＨ基量）に対してプロットして図１に示した。 With respect to this ester synthesis catalyst, the ester conversion rate and the total integrated amount were measured in the same manner as in Example 1. As a result, the ester conversion rate was 90%. Further, the ester conversion rate is plotted against the loss on heating (OH group amount) and shown in FIG.
（実施例６）
分散液のｐＨ調整を８．４５／２０．７℃にし、水熱処理を１２０℃で３ｈｒに代えた以外は、実施例４と同様にして高活性劈開性積層シリカ粒子を得た。このシリカ粒子は、中位径が５．６μm、ＢＥＴ比表面積が８４ｍ２／ｇ、細孔半径が５０Å、加熱減量が２．６重量％、空間容積が２．７７ｍｌ／ｇ、嵩密度が０．１４ｇ／ｍｌであった。
(Example 6)
Highly active cleaved laminated silica particles were obtained in the same manner as in Example 4 except that the pH of the dispersion was adjusted to 8.45 / 20.7 ° C and the hydrothermal treatment was changed to 120 ° C for 3 hours. The silica particles have a median diameter of 5.6 μm, a BET specific surface area of 84 m 2 / g, a pore radius of 50 mm, a loss on heating of 2.6 wt%, a space volume of 2.77 ml / g, and a bulk density of 0. .14 g / ml.
実施例１のシリカを、上記で得られた高活性劈開性積層シリカ粒子に代えた以外は実施例１と同様にして行い、該シリカ粒子を担体としてリパーゼ１４重量部を担持させたエステル合成触媒２８．５ｇを得た。 An ester synthesis catalyst in which the silica of Example 1 was replaced with the highly active cleaved laminated silica particles obtained above in the same manner as in Example 1, and supported by 14 parts by weight of lipase using the silica particles as a carrier. 28.5 g was obtained.
このエステル合成触媒について、実施例１と同様に、エステル変換率及び総積算量を測定したところ、エステル変換率は、９０％であった。また、エステル変換率については、その加熱減量（ＯＨ基量）に対してプロットして図１に示した。 With respect to this ester synthesis catalyst, the ester conversion rate and the total integrated amount were measured in the same manner as in Example 1. As a result, the ester conversion rate was 90%. Further, the ester conversion rate is plotted against the loss on heating (OH group amount) and shown in FIG.
（比較例４）
実施例４と同様のバーミキュライトの酸処理によって得られ、ｐＨ調整下での水熱反応を行わなかった劈開性積層シリカ粒子を担体として使用し、実施例４と同様にしてリパーゼ１４重量部を担持させたエステル合成触媒２８．５ｇを得た。
(Comparative Example 4)
Cleaved laminated silica particles obtained by acid treatment of vermiculite as in Example 4 and not subjected to hydrothermal reaction under pH adjustment were used as a carrier, and 14 parts by weight of lipase was supported in the same manner as in Example 4. 28.5 g of the ester synthesis catalyst was obtained.
上記のシリカ粒子は、中位径が５．４μｍ、ＢＥＴ比表面積が３７４ｍ２／ｇ、細孔半径が２０Å、導電率が７７μＳ／ｃｍ 、加熱減量が３．７重量％、空間容積が２．０５ｍｌ／ｇ、嵩密度が０．２１ｇ／ｍｌであった。 The silica particles have a median diameter of 5.4 μm, a BET specific surface area of 374 m 2 / g, a pore radius of 20 mm, an electrical conductivity of 77 μS / cm 2, a loss on heating of 3.7% by weight, and a space volume of 2. It was 05 ml / g and the bulk density was 0.21 g / ml.
このエステル合成触媒について、実施例１と同様に、エステル変換率及び総積算量を測定したところ、エステル変換率は、５４％であった。また、エステル変換率については、その加熱減量（ＯＨ基量）に対してプロットして図１に示した。 About this ester synthesis catalyst, when the ester conversion rate and the total integrated amount were measured similarly to Example 1, the ester conversion rate was 54%. Further, the ester conversion rate is plotted against the loss on heating (OH group amount) and shown in FIG.
（実施例７〜９、比較例５〜７）
表２に示す物性を有する市販のシリカ粒子を使用し、実施例４と同様にしてリパーゼ１４重量部を担持させたエステル合成触媒２８．５ｇを得た。
(Examples 7-9, Comparative Examples 5-7)
Using commercially available silica particles having the physical properties shown in Table 2, 28.5 g of an ester synthesis catalyst carrying 14 parts by weight of lipase was obtained in the same manner as in Example 4.
このエステル合成触媒について、実施例１と同様に、エステル変換率及び総積算量を測定し、その結果を表２に併せて示した。また、エステル変換率については、その加熱減量（ＯＨ基量）に対してプロットして図１に示した。 For this ester synthesis catalyst, the ester conversion rate and the total integrated amount were measured in the same manner as in Example 1, and the results are also shown in Table 2. Further, the ester conversion rate is plotted against the loss on heating (OH group amount) and shown in FIG.
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