JP2014018101A - Fat extraction method from algae - Google Patents
Fat extraction method from algae Download PDFInfo
- Publication number
- JP2014018101A JP2014018101A JP2012157347A JP2012157347A JP2014018101A JP 2014018101 A JP2014018101 A JP 2014018101A JP 2012157347 A JP2012157347 A JP 2012157347A JP 2012157347 A JP2012157347 A JP 2012157347A JP 2014018101 A JP2014018101 A JP 2014018101A
- Authority
- JP
- Japan
- Prior art keywords
- algae
- oils
- cell
- barrel
- fats
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 241000195493 Cryptophyta Species 0.000 title claims abstract description 97
- 238000000605 extraction Methods 0.000 title abstract description 10
- 210000004027 cell Anatomy 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000012530 fluid Substances 0.000 claims abstract description 29
- 230000006378 damage Effects 0.000 claims abstract description 25
- 210000002421 cell wall Anatomy 0.000 claims abstract description 15
- 239000003925 fat Substances 0.000 claims description 32
- 238000000227 grinding Methods 0.000 claims description 32
- 239000003921 oil Substances 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 27
- 150000001768 cations Chemical class 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 8
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000001963 growth medium Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 22
- 239000002609 medium Substances 0.000 description 18
- 239000007788 liquid Substances 0.000 description 10
- 239000006228 supernatant Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 238000010298 pulverizing process Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 238000004062 sedimentation Methods 0.000 description 6
- 230000004931 aggregating effect Effects 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 239000008394 flocculating agent Substances 0.000 description 5
- 235000014593 oils and fats Nutrition 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 239000002551 biofuel Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- -1 methacrylate ester Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 230000029553 photosynthesis Effects 0.000 description 2
- 238000010672 photosynthesis Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- 241000227166 Harrimanella hypnoides Species 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 241000592344 Spermatophyta Species 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
Description
本発明は藻類が生産する油脂類を低コスト・低環境負荷で効率よく抽出する方法に関するものである。さらに詳しくは、培養されて油脂類を細胞内に蓄えた藻類から、有機溶媒などで該油脂類を抽出されるまでの中間工程に関するものである。 The present invention relates to a method for efficiently extracting oils and fats produced by algae at low cost and low environmental load. More specifically, the present invention relates to an intermediate process until the fats and oils are extracted from the algae cultured and stored in the cells with an organic solvent or the like.
現在、化石資源の利用は、地球温暖化や環境汚染に象徴されるような深刻な問題の要因となっている。さらに、グローバルな産業の拡大によって、化石資源の枯渇という問題が懸念されている。このような中、植物などの生物資源を原料として製造される、バイオ燃料への関心が高まっている。しかし、従来のバイオ燃料は食料を原料としているなどの問題があった。そこで、新たなバイオ燃料の原料として、食料と競合せず、光合成を行うことで油脂類を蓄える藻類が注目されており、この油脂類を蓄えた藻類から効率良く油脂類を抽出するプロセスの開発が行われてきた。 Currently, the use of fossil resources is a cause of serious problems as symbolized by global warming and environmental pollution. Furthermore, due to the expansion of global industries, there is a concern about the problem of fossil resource depletion. Under such circumstances, there is an increasing interest in biofuels produced using biological resources such as plants as raw materials. However, conventional biofuels have problems such as using food as a raw material. Therefore, as a new raw material for biofuel, algae that store oils and fats by photosynthesis without attracting attention to food are attracting attention, and development of a process for efficiently extracting oils and fats from algae that store these oils and fats Has been done.
藻類から油脂類を抽出させる方法はいくつか報告されているが、最適な条件・工程ごとの組み合わせについては報告されていない。下記に工程ごとの内容を示す。 Several methods for extracting oils and fats from algae have been reported, but no optimal conditions / process combinations have been reported. The contents of each process are shown below.
藻類から油脂類を抽出するには、まず、培養した藻類を回収する必要がある。その方法として遠心分離による方法と、特許文献１に開示されるような凝集による方法とがある。 In order to extract fats and oils from algae, it is first necessary to collect the cultured algae. There are a method by centrifugation and a method by aggregation as disclosed in Patent Document 1.
次に、藻類が蓄えた油脂類は硬い細胞壁に囲まれているため、細胞の破壊などの油脂類の抽出効率化を目的とした処理を行う必要がある。機械的な方法としては、ホモジナイザー・ビーズミル・ボールミルなどを用いた細胞破壊方法（特許文献２〜５）が報告されている。 Next, since the fats and oils stored by algae are surrounded by hard cell walls, it is necessary to perform a treatment aimed at improving the extraction efficiency of the fats and oils such as cell destruction. As a mechanical method, a cell disruption method using a homogenizer, a bead mill, a ball mill or the like (Patent Documents 2 to 5) has been reported.
しかしながら、培養された培養液にある藻類を回収・濃縮を行うために遠心分離操作のみを用いる方法は、対象となる藻類の細胞径が５〜１０μｍと小さく、また、比重も軽いため、分離効率が悪い。そこで、分離効率を上げるために遠心分離操作を行う前処理として凝集剤を用いることが行われるが、特許文献１に開示されている凝集の方法は、無機凝集剤を併用しているため、培養液に金属類が混入してしまい、上澄み液である培養液を再利用するのに弊害が生じる。 However, the method using only the centrifugation operation for collecting and concentrating the algae in the cultured broth has a small cell diameter of 5 to 10 μm and a low specific gravity, so that the separation efficiency is low. Is bad. Therefore, in order to increase the separation efficiency, a flocculant is used as a pretreatment for performing a centrifugal separation operation. However, since the flocculant method disclosed in Patent Document 1 uses an inorganic flocculant in combination, Metals are mixed in the liquid, which causes a harmful effect on reusing the culture medium that is the supernatant.
ホモジナイザーは、ラボレベルの少量処理に適しており、藻類をエネルギーとして生産する大量処理に適用することは難しい。ホモジナイザーの粉砕原理は、固定外刃と回転内刃からなっているジェネレータ（シャフトの先端部分）の内刃の高速回転による遠心力により、液体が対流し、内刃と外刃の間で粉砕される。大量処理をするためには、膨大なシャフトが必要であり、また、多くのエネルギーが必要となるため、現実的ではない。さらに、藻類は自然な状態でもフロックを形成するため、フロック状態の粗大な藻類の塊はジェネレータの内刃と外刃の間を通ることができないため、ある程度時間をかけて内刃のみの粗砕を行わなければならず、粉砕効率が良くない。 The homogenizer is suitable for small-scale processing at a laboratory level, and it is difficult to apply it to large-scale processing for producing algae as energy. The pulverization principle of the homogenizer is that the liquid is convected by the centrifugal force generated by the high speed rotation of the inner blade of the generator (shaft tip) consisting of a fixed outer blade and a rotating inner blade, and is crushed between the inner blade and the outer blade. The In order to perform a large amount of processing, a huge shaft is required and a lot of energy is required, which is not realistic. In addition, since algae form flocs even in the natural state, coarse flocs of flocs cannot pass between the inner and outer blades of the generator. Must be carried out, and the grinding efficiency is not good.
ビーズミルは、粉砕効率は高いが、設備コスト・運転コストの点で実用化を行うにあたり、現実的ではない。 The bead mill has high crushing efficiency, but is not practical for practical use in terms of equipment cost and operation cost.
ボールミルは、運転コスト・設備コストの安価な方法であるが、粉砕効率が低い。ボールミルの粉砕原理は、円筒容器内に粉砕媒体であるボールを一定量投入して、水平軸を中心に回転させたときの、ボールと内壁・ボールとボール間の摩砕力およびボールが転がり落ちるときの衝撃力によるものである。細胞壁に覆われている藻類を粉砕するには、粉砕媒体が小径のボールの場合では上記の力が弱いため、粉砕効率が低い。また、ボール径が大きいものを使用した場合では、衝突回数が減少するため細胞径が５〜１０μｍほどの藻類を粉砕するには適した方法とは言えない。 The ball mill is an inexpensive method of operating cost and equipment cost, but the grinding efficiency is low. The grinding principle of the ball mill is that when a certain amount of balls, which are grinding media, are put into a cylindrical container and rotated around a horizontal axis, the grinding force between the balls and the inner wall, the balls and the balls, and the balls roll down. This is due to the impact force. In order to pulverize the algae covered with the cell wall, when the pulverizing medium is a small-diameter ball, the above-described force is weak, so the pulverizing efficiency is low. In addition, when a ball having a large ball diameter is used, the number of collisions is reduced, so that it is not a suitable method for pulverizing algae having a cell diameter of about 5 to 10 μm.
藻類から油脂類を抽出するために重要なことは、ただ単に細胞を微細に粉砕すれば良いのではなく、実用化を踏まえてコストとのバランスを考えた効率的な細胞破壊方法を選定することである。
しかしながら、上述した文献には、コストとのバランスを考えた効率的な細胞破壊方法についての具体的な最適条件の検討はされておらず、そのような記載もない。
What is important for extracting fats and oils from algae is not just to finely pulverize the cells, but to select an efficient cell destruction method that balances cost with practical application. It is.
However, the above-mentioned document does not examine specific optimum conditions for an efficient cell destruction method considering the balance with cost, and there is no such description.
そこで、本発明は、叙上の事情に鑑み、藻類が生産する油脂類を、低コスト・低環境負荷で効率よく抽出する方法を提供することを目的とする。 In view of the above circumstances, an object of the present invention is to provide a method for efficiently extracting fats and oils produced by algae at low cost and low environmental load.
本発明では、上記目的を実現するために、請求項１に記載の藻類からの油脂抽出方法は、藻類が培養された培養液にある藻類を回収し濃縮するための回収・濃縮工程と、前記回収・濃縮された藻類の細胞壁を破壊する細胞破壊工程と、を含み、前記細胞破壊工程が、流動バレル装置によって行われることを特徴としている。 In the present invention, in order to achieve the above object, the method for extracting fats and oils from algae according to claim 1 includes a recovery / concentration step for recovering and concentrating algae in a culture solution in which algae are cultured, A cell destruction step of destroying the cell wall of the collected and concentrated algae, wherein the cell destruction step is performed by a fluid barrel device.
請求項１に記載の発明によれば、藻類が培養された培養液にある藻類を回収・濃縮し、回収・濃縮された藻類の細胞壁を破壊する工程において、流動バレル装置を用いて行っている。これにより、従来の藻類からの油脂の抽出方法に比べ、低エネルギーかつ効率的に藻類から油脂を抽出することができる。 According to the first aspect of the present invention, in the step of recovering and concentrating the algae in the culture solution in which the algae are cultured, and destroying the cell walls of the recovered and concentrated algae, the fluid barrel apparatus is used. . Thereby, compared with the extraction method of the fats and oils from the conventional algae, fats and oils can be extracted from algae efficiently with low energy.
請求項２に記載の発明では、請求項１に記載の藻類からの油脂抽出方法において、前記回収・濃縮工程が、強カチオン・高重合の高分子凝集剤を用いることを特徴としている。 The invention according to claim 2 is characterized in that in the method for extracting fats and oils from algae according to claim 1, the recovery / concentration step uses a polymer flocculating agent of strong cation / high polymerization.
請求項２に記載の発明によれば、培養液にある藻類を回収・濃縮させるために用いる凝集剤として、強カチオン・高重合の高分子凝集剤を使用することによって、少量の凝集剤で藻類を回収し濃縮することが可能である。 According to the invention described in claim 2, by using a high cation high polymerization polymer flocculant as the flocculant used for collecting and concentrating the algae in the culture solution, the algae can be obtained with a small amount of flocculant. Can be recovered and concentrated.
請求項４に記載の発明では、請求項３に記載の藻類からの油脂抽出方法において、前記高分子凝集剤が、前記培養液中の藻類の乾燥重量に対して０．１〜０．５重量％であることを特徴としている。 In invention of Claim 4, in the oil-fat extraction method from algae of Claim 3, the said polymer flocculent is 0.1-0.5 weight with respect to the dry weight of the algae in the said culture solution. %.
請求項４に記載の発明によれば、培養液中の藻類の乾燥重量に対して、０．１〜０．５重量％という少量の高分子凝集剤の利用であるため、低コストで効率的に凝集でき、さらに、培養液の上澄み液を再利用できる。 According to invention of Claim 4, since it is utilization of a small amount of polymer flocculants of 0.1 to 0.5 weight% with respect to the dry weight of the algae in a culture solution, it is low-cost and efficient. In addition, the supernatant of the culture solution can be reused.
請求項３に記載の発明では、請求項１に記載の藻類からの油脂抽出方法において、前記培養液が、ｐＨ７．０〜９．１であることを特徴としている。 The invention according to claim 3 is characterized in that, in the method for extracting fats and oils from algae according to claim 1, the culture solution has a pH of 7.0 to 9.1.
請求項５に記載の発明では、請求項１に記載の藻類からの油脂抽出方法において、前記細胞破壊工程が、該流動バレル装置内に固定されたバレル槽の壁面に対して、該バレル槽の底部に設けられたバレル槽底部回転盤を回転させることによって流動状態を作り出し、該流動状態の遠心力と、粉砕媒体の荷重によって行われることを特徴としている。 In the invention according to claim 5, in the method for extracting fats and oils from algae according to claim 1, the cell destruction step is performed on the wall surface of the barrel tank fixed in the fluid barrel apparatus. A fluidized state is created by rotating a barrel tank bottom rotating disk provided at the bottom, and this is performed by the centrifugal force in the fluidized state and the load of the grinding medium.
請求項５に記載の発明によれば、藻類の細胞壁の破壊が、流動バレル装置内に固定されたバレル槽の壁面に対して、該バレル槽の底部に設けられたバレル槽底部回転盤を回転させることによって流動状態を作り出し、該流動状態の遠心力と粉砕媒体の荷重によって行われる。これにより、藻類の細胞壁の破壊が、低エネルギーかつ効率的に行うことができる。 According to invention of Claim 5, destruction of the cell wall of algae rotates the barrel tank bottom part rotary disk provided in the bottom part of this barrel tank with respect to the wall surface of the barrel tank fixed in the fluid barrel apparatus. To create a fluidized state, and is performed by the centrifugal force of the fluidized state and the load of the grinding media. Thereby, destruction of the cell wall of algae can be performed efficiently with low energy.
請求項６に記載の発明では、請求項５に記載の藻類からの油脂抽出方法において、前記粉砕媒体の直径が、３〜１０ｍｍであることを特徴としている。 The invention according to claim 6 is characterized in that, in the method for extracting fats and oils from algae according to claim 5, the grinding medium has a diameter of 3 to 10 mm.
請求項７に記載の発明では、請求項５に記載の藻類からの油脂抽出方法において、前記バレル槽底部回転盤の回転条件は、２００〜２５０ｒｐｍ、５〜６０ｍｉｎであることを特徴としている The invention according to claim 7 is characterized in that, in the method for extracting fats and oils from algae according to claim 5, the rotation conditions of the barrel tank bottom rotating disk are 200 to 250 rpm and 5 to 60 min.
本発明によれば、藻類が培養された培養液にある藻類を回収し濃縮するための回収・濃縮工程と、前記凝集された藻類の細胞壁を破壊する細胞破壊工程と、を含む藻類から油脂を抽出する方法であって、前記細胞破壊工程が、流動バレル装置によって行われることにより、藻類が生産する油脂を低コスト・低環境負荷で効率よく抽出することができる。 According to the present invention, fats and oils are obtained from algae, including a collection / concentration step for collecting and concentrating algae in a culture solution in which algae are cultured, and a cell destruction step for destroying the cell walls of the agglomerated algae. In the extraction method, the cell destruction step is performed by a fluid barrel apparatus, whereby the fats and oils produced by the algae can be efficiently extracted at low cost and low environmental load.
図１に示すのは本発明にかかわる、藻類からの油脂抽出方法を示すフロー図である。図１に示されるように、本発明は、藻類が培養された培養液から、藻類を回収・濃縮する工程と、藻類の細胞壁を破壊する細胞破壊工程に関するものである。 FIG. 1 is a flowchart showing a method for extracting fats and oils from algae according to the present invention. As shown in FIG. 1, the present invention relates to a step of collecting and concentrating algae from a culture solution in which algae are cultured, and a cell destruction step of destroying the cell walls of algae.
以下、添付図面に基づいて本発明の藻類からの油脂抽出方法を説明する。
本発明において「藻類」とは、光合成により酸素を発生する生物の中で、主に陸上植物であるコケ植物やシダ植物、種子植物を除いたものを指す。すなわち、淡水や海水などの水圏に棲む、一般的に藻類と呼称されるものを指す。
Hereinafter, the method for extracting fats and oils from algae according to the present invention will be described with reference to the accompanying drawings.
In the present invention, “algae” refers to organisms that generate oxygen by photosynthesis, excluding moss plants, fern plants, and seed plants, which are mainly land plants. In other words, it refers to what is generally called algae that lives in hydrospheres such as freshwater and seawater.
（回収・濃縮工程）
本発明の方法では、まず藻類が培養された培養液中に、強カチオン・高重合の高分子凝集剤を添加し、藻類を凝集させることで沈降させる。
本発明に限らず、有機物の凝集で用いられる高分子凝集剤としては、表面電荷の違いによるカチオン・アニオン・ノニオンなどのイオン性と重合度が異なる種々の高分子凝集剤が挙げられる。
本発明者らは、藻類を凝集させるための凝集剤を検討した結果、強カチオン・高重合の高分子凝集剤がもっとも良い結果（沈降具合、凝集）を見せた。
なお、アニオンの高分子凝集剤では、藻類の沈降（凝集）が見られなかった。また、強カチオン・低重合の高分子凝集剤では藻類の沈降は見られたが、強カチオン・高重合の高分子凝集剤（メタクリル酸エステル系）と比較すると、沈降具合は良くなかった。
また、藻類が培養された培養液のｐＨを測定してみると、およそｐＨ７．０〜９．１を示していた。このことから、藻類の培養液が負の電荷を帯びているため、カチオンの高分子凝集剤が良い結果をもたらしたのではないかと考察し、様々な検討を行ったところ、強カチオン・高重合の高分子凝集剤が好適であることを見出しました。
本発明で用いることができる強カチオン・高重合の高分子凝集剤としては、特に、強カチオン・高重合のメタクリル酸エステル系および、アクリル酸エステル系の高分子凝集剤が好適である。
また、本発明において、藻類が培養された培養液は、ｐＨ７．０〜９．１が好適である。
(Recovery / concentration process)
In the method of the present invention, first, a strong cation and highly polymerized polymer flocculant is added to the culture solution in which algae are cultured, and the algae are aggregated to cause sedimentation.
Examples of the polymer flocculant used for the aggregation of organic substances are not limited to the present invention, and various polymer flocculants having different degrees of polymerization and ionic properties such as cations, anions, and nonions due to the difference in surface charge.
As a result of examining the aggregating agent for aggregating the algae, the present inventors showed the best result (sedimentation condition, agglomeration) with the polymer flocculating agent of strong cation and high polymerization.
In the anionic polymer flocculant, no algae sedimentation (aggregation) was observed. Algae sedimentation was observed with the high cation / low polymerization polymer flocculant, but the sedimentation condition was not good compared with the strong cation / high polymerization polymer flocculant (methacrylic acid ester type).
Moreover, when the pH of the culture solution in which the algae was cultured was measured, it was about pH 7.0 to 9.1. From this, we considered that the polymer flocculant of the cation had a good result because the culture liquid of algae was negatively charged. We have found that the polymer flocculants are suitable.
As the strong cation / highly polymerized polymer flocculant that can be used in the present invention, a strong cation / highly polymerized methacrylic ester-based and acrylic acid ester-based polymer flocculant are particularly suitable.
In the present invention, the culture solution in which the algae is cultured preferably has a pH of 7.0 to 9.1.
なお、高分子凝集剤の添加量は任意に決定することができる。ただし、高分子凝集剤の使用量は多くても回収率はほとんど変わらないので、コストの観点より、本発明における高分子凝集剤の添加量は、培養液中の藻類の乾燥重量に対して０．１〜０．５重量％が適量である。 In addition, the addition amount of a polymer flocculent can be determined arbitrarily. However, even if the amount of the polymer flocculant used is large, the recovery rate hardly changes. From the viewpoint of cost, the amount of the polymer flocculant added in the present invention is 0 with respect to the dry weight of the algae in the culture solution. .1 to 0.5% by weight is an appropriate amount.
表１に強カチオン・高重合のメタクリル酸エステル系の高分子凝集剤を用いた凝集試験の結果を示す。
ここで、凝集剤添加量は、培養液中の藻類の乾燥重量に対する数値である。また、原液（攪拌直後）のＳＳは、１．０１８［ｇ／Ｌ］、原液（攪拌直後）のＣＯＤＭｎは、３２０［ｍｇ／Ｌ］であった。また、回収率は、下記の式で算出した。
回収率［％］＝（（原液ＳＳ−３０ｍｉｎ静置後の上澄み液ＳＳ）／原液ＳＳ）×１００
また、ＳＳとは、水質指標の一つで、水中に浮遊する粒径２ｍｍ以下の不溶解性物質の総称であり、浮遊物質（Ｓｕｓｐｅｎｄｅｄ ｓｏｌｉｄｓ）または懸濁物質（ｓｕｓｐｅｎｄｅｄ ｓｕｂｓｔａｎｃｅ）と呼ばれるものである。
比較のために行った遠心分離装置による回収・濃縮は、遠心力２０００Ｇ、時間１０ｍｉｎの条件にて行った。
Table 1 shows the results of an agglutination test using a strong cationic and highly polymerized methacrylate ester polymer flocculant.
Here, the addition amount of the flocculant is a numerical value with respect to the dry weight of the algae in the culture solution. The SS of the stock solution (immediately after stirring) was 1.018 [g / L], and the COD Mn of the stock solution (immediately after stirring) was 320 [mg / L]. The recovery rate was calculated by the following formula.
Recovery rate [%] = ((Superior solution SS after standing for 30 min) / Undiluted solution SS) × 100
SS is one of the water quality indicators and is a general term for insoluble substances having a particle diameter of 2 mm or less suspended in water, and is called suspended solids or suspended substances. .
The collection / concentration by the centrifuge performed for comparison was performed under the conditions of a centrifugal force of 2000 G and a time of 10 min.
ＳＶ３０を見ると分かるように、凝集剤を入れることで、３０分静置後の見掛け体積は、どれも良好な結果になっている。さらに、ＣＯＤＭｎおよび電気伝導度が、強カチオン・高重合のメタクリル酸エステル系の高分子凝集剤の添加量を多くしても大きく変化しないことから、高分子凝集剤の培養液への影響が少なく、上澄み液の再利用が可能であると考えられ、検証を行った。その検証は後述する。また、沈降速度は、凝集剤添加量０．１〜０．５重量％のものが高い数値を示している。
表１から強カチオン・高重合のメタクリル酸エステル系の高分子凝集剤を適量添加することで遠心分離と同等回収率で藻類を回収できることがわかる。さらに、培養液中の藻類の乾燥重量に対して０．１〜０．５重量％が適量であることがわかる。
As can be seen from SV30, by adding a flocculant, the apparent volume after standing for 30 minutes is good. Furthermore, since COD Mn and electrical conductivity do not change greatly even if the addition amount of a strong cationic / highly polymerized methacrylate ester polymer flocculant is increased, the influence of the polymer flocculant on the culture medium is not affected. It was considered that the supernatant liquid could be reused, and verification was performed. The verification will be described later. Moreover, the sedimentation rate shows a high numerical value when the addition amount of the flocculant is 0.1 to 0.5% by weight.
It can be seen from Table 1 that algae can be recovered at the same recovery rate as that of centrifugation by adding an appropriate amount of a strong cationic and highly polymerized methacrylate ester polymer flocculant. Furthermore, it turns out that 0.1 to 0.5 weight% is a suitable quantity with respect to the dry weight of the algae in a culture solution.
（細胞破壊工程）
次に、沈降させて濃縮した藻類のスラリーに対して、流動バレル装置で細胞（細胞壁）破壊処理を行う。
本発明で用いられた流動バレル装置を図２に示す。この流動バレル装置Ａは、新東工業株式会社製の流動バレル研磨機（ＥＶＦ−０４型）である。バレル槽１の容量は４０［Ｌ］、藻類のスラリーおよび粉砕媒体の投入容量は１５［Ｌ］である。なお、前記バレル槽１には、その底部に排水用ボールバルブ２が設けられ、さらにバレル槽反転用レバー３が設けられている。前記バレル槽１内の内壁の材質はポリウレタンである。前記バレル槽１内部には、ジャマ板４が設けられている（図４参照）。
藻類のスラリーと粉砕媒体は、直接バレル槽１内に投入する。また、細胞壁を破壊された藻類の回収は、前記排水用ボールバルブ２から排出し、粉砕媒体の回収は、バレル槽反転用レバー３を倒してバレル槽１を反転させて行う。
(Cell destruction process)
Next, the cell (cell wall) destruction process is performed with the fluid barrel apparatus with respect to the algal slurry settled and concentrated.
The flow barrel apparatus used in the present invention is shown in FIG. This fluid barrel apparatus A is a fluid barrel polisher (EVF-04 type) manufactured by Shinto Kogyo Co., Ltd. The capacity of the barrel tank 1 is 40 [L], and the input capacity of the algal slurry and the grinding medium is 15 [L]. The barrel tank 1 is provided with a drain ball valve 2 at the bottom and a barrel tank reversing lever 3. The material of the inner wall in the barrel tank 1 is polyurethane. A jammer plate 4 is provided inside the barrel tank 1 (see FIG. 4).
The algae slurry and the grinding medium are put directly into the barrel tank 1. In addition, the algae whose cell walls have been destroyed are collected from the drainage ball valve 2 and the grinding media are collected by turning the barrel tank reversing lever 3 and inverting the barrel tank 1.
表２に、ボールミルと流動バレルとの処理条件を示す。凝集剤（メタクリル酸エステル系高分子凝集剤）によって凝集・回収された藻類を、ボールミルおよび流動バレルによって細胞破壊処理を行ったときのそれぞれの処理条件を示したものである。なお、ここでは検体である藻類のスラリーと粉砕媒体の割合は、体積あたりで１：１とした。回転数は複数回の検討した中での最適条件である。 Table 2 shows the processing conditions of the ball mill and the fluid barrel. The processing conditions when the algae aggregated and collected by the aggregating agent (methacrylic acid ester polymer aggregating agent) are subjected to cell disruption treatment by a ball mill and a fluid barrel are shown. Here, the ratio of the algal slurry, which is the specimen, to the grinding medium was 1: 1 per volume. The number of revolutions is the optimum condition in the examination several times.
表２から分るように、ボールミルでは１回あたりの処理量が少ないことが分かる。細胞破壊処理を行ったあとに油脂を抽出するには、まとまった量が必要となるが、ボールミルでは流動バレルに比べより多くの回数を必要とするので、効率が良くない。流動バレルとボールミルではボールミルの方が、コスト面では優位ではあるが、コストと効率を考慮すると、流動バレルの方が良い。
また、使用したボールミルの容器は低容量であるが、大容量の容器を使用した場合、流動バレルと比べて回数は変わらなくなるが細胞破壊の効率が悪いと考えられる。
As can be seen from Table 2, the ball mill has a small amount of treatment per one time. Extraction of fats and oils after cell destruction treatment requires a large amount, but the ball mill requires a larger number of times than a fluid barrel, so it is not efficient. In the fluid barrel and ball mill, the ball mill is superior in cost, but the fluid barrel is better in consideration of cost and efficiency.
Although the used ball mill container has a low capacity, the use of a large capacity container does not change the number of times compared to the flow barrel, but is considered to be inefficient in cell destruction.
コストの点では、流動バレルとビーズミルとを比較すると、ビーズミルは、流動バレルと比べて、設備コストでおよそ５倍、運転コストでおよそ３．５倍、それらをあわせた細胞破壊処理コストではおよそ４．５倍となった。よってビーズミルで処理するより、流動バレルで処理した方がコスト面でも有利である。 In terms of cost, when comparing the flow barrel and the bead mill, the bead mill is about 5 times the equipment cost, about 3.5 times the operation cost, and about 4 times the cell destruction treatment cost when they are combined, compared to the flow barrel. It became 5 times. Therefore, it is more advantageous in terms of cost to process with a fluidized barrel than with a bead mill.
図３に、細胞画像を示す。図３（ａ）が未処理の細胞であり、図３（ｂ）が流動バレルによって、破壊処理した細胞である。図３に示されるように、細胞破壊処理したもののほうが、細かい粒子や、透明な細胞が多数確認できる。これは、細胞から押し出された葉緑素成分や破壊された細胞である。 FIG. 3 shows a cell image. FIG. 3 (a) shows an untreated cell, and FIG. 3 (b) shows a cell that has been destroyed by a flow barrel. As shown in FIG. 3, a larger number of fine particles and transparent cells can be confirmed in the case of cell destruction treatment. This is a chlorophyll component extruded from the cell or a broken cell.
図４に、流動バレルによって細胞を破壊処理している槽内の状態の模式図を示す。図５に流動バレルで処理している様子の画像を示す。流動バレル装置Ａは、バレル槽底部回転盤５が回転することにより、バレル槽内に投入された藻類のスラリーと粉砕媒体とが固定されたバレル槽１の壁面６に、流動状態を作り出す。この時に、該流動状態の遠心力と粉砕媒体の加重によって、細胞（細胞壁）が破壊される。渦を巻くような流動状態Ｂが、様々な方向に力を作用させている。また、図５からも、バレル槽内部の前記ジャマ板４によって流動状態が、他方向に力を発生させていることがわかる。 FIG. 4 shows a schematic diagram of the state in the tank in which the cells are destroyed by the flow barrel. FIG. 5 shows an image of processing with a fluid barrel. The fluid barrel apparatus A creates a fluid state on the wall surface 6 of the barrel tank 1 to which the algae slurry and the grinding medium charged in the barrel tank are fixed by rotating the barrel tank bottom turntable 5. At this time, the cells (cell walls) are destroyed by the centrifugal force in the fluidized state and the weight of the grinding medium. A flow state B that winds in a vortex applies forces in various directions. Further, FIG. 5 also shows that the flow state generates a force in the other direction by the jammer plate 4 inside the barrel tank.
表４に、細胞破壊における油脂類抽出物量の比較を示す。図６に使用粉砕媒体の画像を示す。
ここで、凝集剤は、表２で示した処理条件で行ったものと同じものを使用した。粉砕媒体のＶ−３は直径３ｍｍの球形、Ｖ−１０は直径１０ｍｍの球形、Ｖ−３−Ｔ６×５は一辺が３ｍｍ、高さが５ｍｍの三角柱であり、材質は全てアルミナである。
Table 4 shows a comparison of the amount of oil and fat extract in cell destruction. FIG. 6 shows an image of the grinding media used.
Here, the same flocculant as that used under the processing conditions shown in Table 2 was used. The grinding media V-3 is a sphere with a diameter of 3 mm, V-10 is a sphere with a diameter of 10 mm, V-3-T6 × 5 is a triangular prism with a side of 3 mm and a height of 5 mm, and the material is all alumina.
表３に示すように、流動バレルを用いて細胞の破壊処理を行うと、ボールミルを用いて行った場合より、油脂類抽出物量が約３倍高くなった。
また、小径の粉砕媒体を用いた方が、油脂類抽出物量が高くなることがわかる。すなわち、粉砕媒体の直径が３〜１０ｍｍの間のとき抽出量が多く、特に、粉砕媒体の直径を３〜５ｍｍとするとより抽出量が増加している。
また、種々の条件で処理を行った結果、流動バレルの粉砕時間は、５〜６０ｍｉｎで、回転数が２００〜２５０ｒｐｍが最適であった。
As shown in Table 3, when the cell destruction treatment was performed using a fluid barrel, the amount of the oil and fat extract was about three times higher than that when using a ball mill.
Moreover, it turns out that the direction which uses the grinding medium of a small diameter becomes high in fats and oils extract amount. That is, the amount of extraction is large when the diameter of the grinding medium is between 3 and 10 mm. In particular, the amount of extraction is increased when the diameter of the grinding medium is 3 to 5 mm.
Moreover, as a result of performing the treatment under various conditions, the pulverization time of the fluid barrel was 5 to 60 min, and the rotation speed was 200 to 250 rpm.
流動バレルは、槽内が流動状態になり強い遠心力が起こり、粉砕媒体と内壁や粉砕媒体間の摩砕力が高くなるため、検体と粉砕媒体の衝突回数が多い高効率の細胞破壊が行われる。一方、ボールミルで強い遠心力を生み出そうとすると、臨界回転数を越えてしまい、粉砕媒体が内壁を滑るだけになり、粉砕が起きなくなる。 The flow barrel is in a fluid state and a strong centrifugal force is generated, and the grinding force between the grinding media and the inner wall or grinding media increases, so that high-efficiency cell destruction is performed with a large number of collisions between the specimen and the grinding media. Is called. On the other hand, if a strong centrifugal force is generated by the ball mill, the critical rotational speed is exceeded, and the grinding medium only slides on the inner wall, so that grinding does not occur.
また、ボールミルは、粉砕媒体の転がり落ちる衝撃力でも粉砕を行うが、藻類のスラリーの場合では、ほとんどが水分であるため細胞との接触が少なく、粉砕効率が低くなったと考えられる（比較例５に示すように、４８０ｍｉｎ処理しても抽出物量が高くなっていないことからもわかる）。さらに、流動バレルでも大径の粉砕媒体を用いた場合でも、大径の粉砕媒体と小さい細胞では接触が少なく、効率が低くなったと考えられる。よって、小径の粉砕媒体を用いた流動バレル処理が細胞破壊工程に適した方法であると言える。 In addition, the ball mill pulverizes even with the impact force of rolling of the pulverizing medium. However, in the case of algae slurry, it is considered that the pulverization efficiency is low because most of the algae slurry is in water and there is little contact with cells (Comparative Example 5). (As can be seen from the fact that the amount of extract does not increase even after 480 min treatment). Furthermore, even when a large-diameter grinding medium is used in the fluid barrel, it is considered that the large-diameter grinding medium and small cells have little contact and the efficiency is low. Therefore, it can be said that fluid barrel treatment using a small-diameter grinding medium is a suitable method for the cell disruption step.
なお、本発明で使用した流動バレルは、ボールミルと比較して連続処理が行える点や、バレル槽内の反転による粉砕媒体の取出しなど作業性にも優れている。 In addition, the fluid barrel used in the present invention is excellent in workability such as the ability to perform continuous processing as compared with a ball mill and the removal of a grinding medium by inversion in a barrel tank.
上述した高分子凝集剤の培養液への影響を検証するために、以下に、凝集工程で藻類を凝集したあとの上澄み液の再利用についての試験を示す。
表５に、本発明にかかわる、１種類の強カチオン・高重合の高分子凝集剤によって凝集し残った上澄み液によって培養した藻類と、一般的な培養液によって培養した藻類との乾燥重量による比較を示す。
また、図７に、本発明にかかわる上澄み液を用いた藻類の培養における溶存酸素の経日変化を示す。
In order to verify the influence of the above-described polymer flocculant on the culture solution, a test for reusing the supernatant after aggregating algae in the aggregation step is shown below.
Table 5 shows a comparison of dry weight between algae cultured with a supernatant liquid agglomerated by one kind of strong cation and high polymerization polymer flocculant and algae cultured with a general culture liquid according to the present invention. Indicates.
Moreover, FIG. 7 shows the daily change of dissolved oxygen in the culture of algae using the supernatant liquid according to the present invention.
表４では、本発明にかかわる上澄み液を用いて培養され得られた藻類と、一般的な培養液を用いて培養され得られた藻類とは同等の値を示していることがわかる。また、図７では、本発明にかかわる上澄み液でも一般的な培養液と比べても遜色のない溶存酸素が含まれていることがわかる。 In Table 4, it can be seen that the algae cultivated using the supernatant solution according to the present invention and the algae cultivated using a general culture solution show equivalent values. Moreover, in FIG. 7, it turns out that the dissolved oxygen which is inferior compared with the supernatant liquid concerning this invention compared with a general culture solution is contained.
これらのことから、本発明にかかわる１種類の強カチオン・高重合の高分子凝集剤による凝集後の上澄み液は、藻類の培養に再利用が可能である。よって、藻類を培養する際の水や培養液のコスト削減が可能である。さらに、培養液を余分に使用しなくて済み、環境への負荷を低減できる。 From these facts, the supernatant liquid after flocculation by one type of strong cation and high polymerization polymer flocculant according to the present invention can be reused for algae culture. Therefore, it is possible to reduce the cost of water and culture solution when culturing algae. Furthermore, it is not necessary to use an extra culture solution, and the burden on the environment can be reduced.
１ バレル槽
２ 排水用ボールバルブ
３ バレル槽反転用レバー
４ ジャマ板
５ バレル槽底部回転盤
６ 壁面
Ａ 流動バレル装置
Ｂ 流動状態
DESCRIPTION OF SYMBOLS 1 Barrel tank 2 Drain ball valve 3 Barrel tank reversing lever 4 Jama plate 5 Barrel tank bottom turntable 6 Wall surface A Fluid barrel device B Flow state
Claims (7)
前記凝集された藻類の細胞壁を破壊する細胞破壊工程と、
を含む藻類から油脂を抽出する方法であって、
前記細胞破壊工程が、流動バレル装置によって行われることを特徴とする藻類からの油脂抽出方法。
A collection / concentration step for collecting and concentrating the algae in the culture solution in which the algae are cultured;
A cell disruption step of disrupting the cell walls of the agglomerated algae;
A method for extracting fats and oils from algae containing
The method for extracting fats and oils from algae, wherein the cell destruction step is performed by a fluid barrel apparatus.
強カチオン・高重合の高分子凝集剤を用いることを特徴とする請求項１記載の藻類からの油脂抽出方法。
The recovery / concentration step
2. The method for extracting fats and oils from algae according to claim 1, wherein a strong cation / polymerized polymer flocculant is used.
The method for extracting fats and oils from algae according to claim 2, wherein the polymer flocculant is 0.1 to 0.5% by weight based on the dry weight of the algae in the culture solution.
The method for extracting fats and oils from algae according to claim 2, wherein the culture solution has a pH of 7.0 to 9.1.
The cell disruption step creates a fluid state by rotating a barrel tank bottom rotating disk provided at the bottom of the barrel tank with respect to the wall surface of the barrel tank fixed in the fluid barrel apparatus, and the fluid state The method for extracting fats and oils from algae according to claim 1, wherein the method is performed by the centrifugal force of the above and the load of the grinding medium.
6. The method for extracting fats and oils from algae according to claim 5, wherein the grinding medium has a diameter of 3 to 10 mm.
6. The method for extracting fats and oils from algae according to claim 5, wherein the rotation condition of the barrel tank bottom rotating disk is 200 to 250 rpm and 5 to 60 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012157347A JP2014018101A (en) | 2012-07-13 | 2012-07-13 | Fat extraction method from algae |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012157347A JP2014018101A (en) | 2012-07-13 | 2012-07-13 | Fat extraction method from algae |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2014018101A true JP2014018101A (en) | 2014-02-03 |
Family
ID=50193707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012157347A Pending JP2014018101A (en) | 2012-07-13 | 2012-07-13 | Fat extraction method from algae |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2014018101A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011068741A (en) * | 2009-09-25 | 2011-04-07 | Nippon Shokubai Co Ltd | Method for extracting oil-and-fat from scenedesmus algae, and application of oil-and-fat and degreaded residue |
| JP2011068738A (en) * | 2009-09-25 | 2011-04-07 | Nippon Shokubai Co Ltd | Method for extracting oil-and-fat from scenedesmus, and application of oil-and-fat and degreased residue |
| WO2011059074A1 (en) * | 2009-11-13 | 2011-05-19 | 森六ケミカルズ株式会社 | Fine powder manufacturing method and fine powder manufactured using same |
| JP2011212624A (en) * | 2010-04-01 | 2011-10-27 | Toyota Motor Corp | Method for flocculation separation of algae |
| JP2012024752A (en) * | 2010-06-22 | 2012-02-09 | Denso Corp | Adsorbing agent for noble metal and method for recovering the noble metal |
-
2012
- 2012-07-13 JP JP2012157347A patent/JP2014018101A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011068741A (en) * | 2009-09-25 | 2011-04-07 | Nippon Shokubai Co Ltd | Method for extracting oil-and-fat from scenedesmus algae, and application of oil-and-fat and degreaded residue |
| JP2011068738A (en) * | 2009-09-25 | 2011-04-07 | Nippon Shokubai Co Ltd | Method for extracting oil-and-fat from scenedesmus, and application of oil-and-fat and degreased residue |
| WO2011059074A1 (en) * | 2009-11-13 | 2011-05-19 | 森六ケミカルズ株式会社 | Fine powder manufacturing method and fine powder manufactured using same |
| JP2011212624A (en) * | 2010-04-01 | 2011-10-27 | Toyota Motor Corp | Method for flocculation separation of algae |
| JP2012024752A (en) * | 2010-06-22 | 2012-02-09 | Denso Corp | Adsorbing agent for noble metal and method for recovering the noble metal |
Non-Patent Citations (1)
| Title |
|---|
| JPN6016017268; 株式会社シンマルエンタープライゼス: '"ビーズミルとは"' ［ｏｎｌｉｎｅ］， ２０１１年１２月３０日， ［２０１６年４月２８日検索］， インターネット＜ｈｔｔｐｓ：／／ｗｅｂ．ａｒｃｈｉｖｅ．ｏｒｇ／ｗｅｂ／２０１１１２３００５ * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | Microalgae Chlorella vulgaris biomass harvesting by natural flocculant: effects on biomass sedimentation, spent medium recycling and lipid extraction | |
| Pahl et al. | Harvesting, thickening and dewatering microalgae biomass | |
| Ananthi et al. | A critical review on different harvesting techniques for algal based biodiesel production | |
| Fayad et al. | Harvesting of microalgae Chlorella vulgaris using electro-coagulation-flocculation in the batch mode | |
| Liu et al. | Freshwater microalgae harvested via flocculation induced by pH decrease | |
| Sadia et al. | Microplastics pollution from wastewater treatment plants: A critical review on challenges, detection, sustainable removal techniques and circular economy | |
| Agbakpe et al. | Algae harvesting for biofuel production: influences of UV irradiation and polyethylenimine (PEI) coating on bacterial biocoagulation | |
| Zhao et al. | Harvesting Chlorella vulgaris by magnetic flocculation using Fe3O4 coating with polyaluminium chloride and polyacrylamide | |
| Gupta et al. | Wastewater to biofuels: comprehensive evaluation of various flocculants on biochemical composition and yield of microalgae | |
| Liu et al. | Effective flocculation of target microalgae with self-flocculating microalgae induced by pH decrease | |
| Gutiérrez et al. | Settling velocity distribution of microalgal biomass from urban wastewater treatment high rate algal ponds | |
| Bharte et al. | Techniques for harvesting, cell disruption and lipid extraction of microalgae for biofuel production | |
| Hu et al. | A magnetic separator for efficient microalgae harvesting | |
| Mohamed Noor et al. | Assessing the effectiveness of magnetic nanoparticles coagulation/flocculation in water treatment: a systematic literature review | |
| Liang et al. | Optimum conditions to treat high-concentration microparticle slime water with bioflocculants | |
| Zhao et al. | The comparison between vibration and aeration on the membrane performance in algae harvesting | |
| Henderson et al. | Polymers as bubble surface modifiers in the flotation of algae | |
| Surendhiran et al. | Study on flocculation efficiency for harvesting Nannochloropsis oculata for biodiesel production | |
| Goswami et al. | A low-cost and scalable process for harvesting microalgae using commercial-grade flocculant | |
| Chatsungnoen et al. | Continuous flocculation-sedimentation for harvesting Nannochloropsis salina biomass | |
| Muylaert et al. | Harvesting of microalgae by means of flocculation | |
| Wang et al. | Optimization of cyanobacterial harvesting and extracellular organic matter removal utilizing magnetic nanoparticles and response surface methodology: A comparative study | |
| Yang et al. | A novel low cost microalgal harvesting technique with coagulant recovery and recycling | |
| Salama et al. | Harvesting of freshwater microalgae Scenedesmus obliquus and Chlorella vulgaris using acid mine drainage as a cost effective flocculant for biofuel production | |
| Boli et al. | Magnetic harvesting of marine algae Nannochloropsis oceanica |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150625 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160513 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20161118 |