JP2012180481A - Method of manufacturing high density coal/water slurry - Google Patents
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本発明は、微細藻を育成培地ごと添加する、高濃度石炭−水スラリーの製造方法に関する。 The present invention relates to a method for producing a high-concentration coal-water slurry in which microalgae are added together with a growth medium.
石炭は固体であるため、液体に比べハンドリングが複雑なこと、粉塵に対する環境対策が必要なこと、貯炭場等の広い用地を要する等の問題があり、石炭をクリーンで重油並に利用する手段として、石炭スラリーが開発された。中でも、石炭と水を混合した石炭−水スラリーは、自然発火や粉塵飛散の問題もなく、ハンドリングし易い流体として取扱うことができる利点を持っている。高濃度石炭−水スラリーは、石炭の粒度分布や分散剤等の添加剤の開発によって、加える水を少なくしても流動性と安定性が保たれ、脱水することなく直接燃焼することが可能であり、ごく少量の添加剤を加えることによって、特定の粒度分布を有する石炭粒子が、約７０％の重量濃度で均一に分散することが知られている。 Because coal is solid, handling is more complicated than liquid, environmental measures against dust are necessary, and there is a problem of requiring a large site such as a coal yard. As a means to use coal as clean and heavy oil as possible Coal slurry was developed. Among them, the coal-water slurry in which coal and water are mixed has an advantage that it can be handled as a fluid that is easy to handle without problems of spontaneous ignition and dust scattering. High-concentration coal-water slurry maintains fluidity and stability even if less water is added due to the development of coal particle size distribution and additives such as dispersants, and can be directly burned without dehydration. It is known that by adding a very small amount of additive, coal particles having a specific particle size distribution are uniformly dispersed at a weight concentration of about 70%.
一般的傾向として、炭化度が高く、固有水分が低く、酸素含有量の少ない石炭が高濃度石炭−水スラリーを作るのに適している。高濃度石炭−水スラリーの製造は、石炭をスラリーに適した粒度分布に粉砕し、適正な添加剤を選定し、石炭と水と添加剤を適切に混合することにより、高濃度かつ低粘性で安定性に優れる高濃度石炭−水スラリーを製造することが可能となる。 As a general trend, coal with a high degree of carbonization, low intrinsic moisture and low oxygen content is suitable for making a high concentration coal-water slurry. The production of high-concentration coal-water slurry is achieved by high-concentration and low-viscosity by pulverizing coal into a particle size distribution suitable for the slurry, selecting appropriate additives, and appropriately mixing coal, water and additives. It becomes possible to produce a high-concentration coal-water slurry having excellent stability.
石炭−水スラリーの製造プロセスには、原料石炭を予め１０ｍｍ以下程度に粗砕した石炭を、乾式粉砕して所望の粒度分布となるように調製した後、粉砕した石炭と水と添加剤を混合することにより石炭−水スラリーを製造する方法（乾式法）と、予め粗砕した石炭と水と添加剤を湿式ミルに投入し、石炭の粉砕と水、添加剤との混合を一つの粉砕機で行う方法（湿式法）とがある。 In the manufacturing process of the coal-water slurry, the coal obtained by coarsely crushing raw material coal to about 10 mm or less is prepared by dry pulverization so as to obtain a desired particle size distribution, and then the pulverized coal, water and additives are mixed. A coal-water slurry manufacturing method (dry method), and pre-crushed coal, water, and additives are put into a wet mill, and coal pulverization and mixing of water and additives are performed in one pulverizer. (Wet method).
石炭−水スラリーの高濃度化・安定化を図るには、粉砕された石炭粒子の粒子径分布はシャープな分布よりも幅の広い分布の方が好ましく、通常、最大粒子径１５０〜５００μｍ、平均粒子径１０〜２０μｍ、７４μｍ以下の粒子が８０％以上、数μｍ以下の微粒子が１０％程度である。粒子径７４μｍ以下の石炭粒子の間に入り込んだ、粒子径数μｍ以下の微粒子が、石炭粒子を動かすコロの役割となることで、流動性及び高濃度化が図られている。石炭−水スラリーの流動特性は、炭種、石炭濃度、添加剤及び流動状態（レオロジー特性）等によっても変化するが、見掛け粘度は概略１０００ｍＰａ・ｓ（室温、剪断速度＝１００／ｓ）である。 In order to increase the concentration and stabilization of the coal-water slurry, the particle size distribution of the pulverized coal particles is preferably wider than the sharp distribution, and usually has a maximum particle size of 150 to 500 μm, an average The particle diameter is 10 to 20 μm, particles of 74 μm or less are 80% or more, and fine particles of several μm or less are about 10%. Fluidity and high concentration are achieved by the fine particles having a particle diameter of several μm or less that have entered between coal particles having a particle diameter of 74 μm or less serving as a roller that moves the coal particles. The flow characteristics of the coal-water slurry vary depending on the coal type, coal concentration, additives, flow conditions (rheological characteristics), etc., but the apparent viscosity is approximately 1000 mPa · s (room temperature, shear rate = 100 / s). .
高濃度石炭−水スラリーは、燃料供給が容易であるため、火力発電所等のボイラ燃料として使用実績があり、その他に石炭ガス化炉の燃料としても利用されている。ガス化は、石炭を部分燃焼させて一酸化炭素と水素に変換させる方法であり、石炭ガス化燃料には、炭化度が低く酸素含有量の多い石炭が適している。しかしながら、炭化度が低く酸素含有量の多い石炭の場合、添加剤が石炭表面に吸着しにくいため、安定な高濃度石炭−水スラリーを作り難い。しかも、スラリー中の石炭濃度が５０％程度と低いため、ガス化炉内で大量の水を蒸発することになり、ガス化効率が低くなるという問題がある。さらに、スラリーの安定性を向上させるために、安定剤として、モンモリロナイト等の粘土鉱物やキサンタンガム等の多糖類をごく少量添加するが、これらを添加することによってスラリー粘性が高くなり、石炭濃度を高くすることができないという問題がある。 Since high-concentration coal-water slurry is easy to supply fuel, it has been used as boiler fuel for thermal power plants and the like, and is also used as fuel for coal gasifiers. Gasification is a method of partially burning coal to convert it into carbon monoxide and hydrogen, and coal having a low carbonization and a high oxygen content is suitable for coal gasification fuel. However, in the case of coal with a low degree of carbonization and a high oxygen content, it is difficult to make a stable high-concentration coal-water slurry because the additive is difficult to adsorb on the coal surface. And since the coal density | concentration in a slurry is as low as about 50%, a large amount of water will be evaporated in a gasification furnace, and there exists a problem that gasification efficiency becomes low. Furthermore, in order to improve the stability of the slurry, clay minerals such as montmorillonite and polysaccharides such as xanthan gum are added as stabilizers, but adding these increases the slurry viscosity and increases the coal concentration. There is a problem that you can not.
混焼用のバイオマス燃料としてユーカリやオリーブ等の固体バイオマスの添加が考えられる。しかし、石炭の湿式粉砕時に石炭よりも柔らかい固体バイオマスを添加しても、固体バイオマスを石炭微粒子の粒子径まで粉砕するのは容易ではなく、固体バイオマスを微粒子まで粉砕しようとすると、石炭粒子の粒度分布が狭くなりすぎてしまうことでスラリー粘度が高くなる。また、固体バイオマスと石炭の混合粉砕では、固体バイオマスが石炭よりも柔らかいため、固体バイオマスが衝撃を吸収することで石炭に対する粉砕動力が低減し、微細粒子径が減少するため、スラリー流動性が低下する要因ともなる。 Addition of solid biomass such as eucalyptus and olive as biomass fuel for co-firing can be considered. However, even if solid biomass softer than coal is added during coal wet pulverization, it is not easy to pulverize the solid biomass to the particle size of the coal fine particles. If the distribution becomes too narrow, the slurry viscosity increases. Also, in the mixed pulverization of solid biomass and coal, the solid biomass is softer than coal, so the solid biomass absorbs the impact, so the pulverization power for coal is reduced and the fine particle diameter is reduced, so the slurry fluidity is reduced. It becomes a factor to do.
特許文献１には、炭酸ガス含有廃ガスを発生する火力発電所等の工場に、微細藻類池を併設し、当該廃ガスから分離した炭酸ガスを、光合成を利用して微細藻類に固定し、得られる微細藻類を乾燥・粉砕したものを、別途調製した石炭−水スラリーに添加している。第２図では、微細藻類を脱水機で水分約３０％に調整した湿潤微細藻類に界面活性剤を加えミルで十分混合したものを、別途調製した石炭−水スラリーに添加・混合し、燃料として使用することを開示している。 In Patent Document 1, a microalgae pond is installed in a factory such as a thermal power plant that generates carbon dioxide-containing waste gas, and carbon dioxide separated from the waste gas is fixed to microalgae using photosynthesis, What dried and grind | pulverized the micro algae obtained is added to the coal-water slurry prepared separately. In Fig. 2, a microalgae that has been adjusted to a moisture content of about 30% with a dehydrator and added with a surfactant and thoroughly mixed with a mill is added to and mixed with a separately prepared coal-water slurry as fuel. The use is disclosed.
しかしながら、微細藻培養槽における微細藻の濃度は、微細藻が光合成するために、極めて低濃度に設定されている。従って、特許文献１に開示された方法においては、微細藻乾燥粉末を得るための脱水・乾燥工程で動力・熱が必要となり、多大なエネルギーロスが生じることになるばかりか、微細藻類を取り出した後に残る培養液等を排水する場合に、今後の規制状況によっては、残細胞の処理及び水処理が必要となる問題がある。また、別途調製された石炭−水スラリーに添加・混合するためには、スラリー濃度に影響を及ぼさないよう、水分量の少ない湿潤微細藻類を添加する必要があり、かかる微細藻類の調製工程が煩雑となるばかりか、脱水後の水処理の問題も生じる。 However, the concentration of the microalgae in the microalgae culture tank is set to a very low concentration in order for the microalgae to photosynthesis. Therefore, in the method disclosed in Patent Document 1, power and heat are required in the dehydration / drying process for obtaining a dry microalgae powder, which results in a significant energy loss, and the microalgae is removed. When draining the remaining culture solution or the like later, there is a problem that treatment of residual cells and water treatment are required depending on future regulations. In addition, in order to add and mix into a separately prepared coal-water slurry, it is necessary to add wet microalgae with a low water content so as not to affect the slurry concentration, and the preparation process of such microalgae is complicated. In addition, there is a problem of water treatment after dehydration.
また、培養槽で培養された微細藻を処理する方法として、微細藻をスラリー化したバイオスラリー燃料として燃焼させることも提案されている（例えば、特許文献２参照）。しかしながら、微細藻３０％に対して７０％の水を加えた組成のスラリーを燃焼させる方法であるため、安定燃焼が難しく、エネルギー利用効率も低い。 In addition, as a method for treating microalgae cultured in a culture tank, it is also proposed to burn the microalgae as a slurry of bioslurry (see, for example, Patent Document 2). However, since it is a method of burning a slurry having a composition in which 70% of water is added to 30% of microalgae, stable combustion is difficult and energy utilization efficiency is low.
本発明はこのような事情の下になされたものであり、残細胞の処理及び水処理が不要で微細藻を培地ごと利用することができ、しかもエネルギーロスの少ない、高濃度石炭−水スラリーの製造方法を提供することを目的とする。 The present invention has been made under such circumstances, and treatment of residual cells and water treatment are unnecessary, microalgae can be used together with the medium, and there is little energy loss. An object is to provide a manufacturing method.
上記課題を解決するため、本発明者等は鋭意検討した結果、湿式ミルを用いて高濃度石炭−水スラリーを製造する方法において、スラリー製造時の水を微細藻培養槽の培地で代替することにより、残細胞の処理及び培養液等の水処理が不要となり、しかも、微細藻類には細胞形状が球形に近く、石炭微粒子と同程度の大きさの微細藻類も存在するため、これらの微細藻がスラリー中で石炭微粒子と同様の働きをすることに着目し、本発明に到達した。 In order to solve the above-mentioned problems, the present inventors diligently studied. As a result, in the method for producing a high-concentration coal-water slurry using a wet mill, the water during slurry production is replaced with the medium of the microalgae culture tank. As a result, the treatment of residual cells and the water treatment of the culture solution are not necessary, and the microalgae are close to spherical cells, and there are microalgae of the same size as fine coal particles. The present invention has been achieved by paying attention to the same function as fine coal particles in the slurry.
すなわち、本発明は、以下の通りである。
（１）湿式ミルを用いて、高濃度石炭−水スラリーを製造する方法において、
湿式ミル内に、石炭と、微細藻培養槽の内容物をそのまま投入するとともに、必要量の水を投入して石炭を粉砕することを特徴とする、高濃度石炭−水スラリーの製造方法。
（２）湿式ミルを用いて、高濃度石炭−水スラリーを製造する方法において、
湿式ミル内に、石炭と、微細藻培養槽の内容物を濃縮処理して得られる微細藻濃縮液を投入するとともに、前記濃縮処理で得られる水を含む必要量の水を投入して石炭を粉砕することを特徴とする、高濃度石炭−水スラリーの製造方法。
（３）前記水が、用水及び／又は微細藻培養槽の内容物の濃縮処理で得られる水であることを特徴とする、前記（１）又は（２）に記載の高濃度石炭水スラリーの製造方法。
（４）前記微細藻が球形細胞を有する微細藻であることを特徴とする、前記（１）又は（２）に記載の高濃度石炭−水スラリーの製造方法。
（５）前記微細藻が、炭酸ガス含有廃ガスを発生する施設に微細藻培養槽を併設し、当該炭酸ガスを、光合成を利用して微細藻に固定して得られる微細藻であることを特徴とする、前記（１）〜（４）いずれかに記載の高濃度石炭−水スラリーの製造方法。
（６）前記（１）又は（２）に記載の方法で製造した高濃度石炭−水スラリーに、微細藻培養槽の内容物をそのまま或いはこれを濃縮処理して得られる微細藻濃縮液を混合添加することを特徴とする、高濃度石炭−水スラリーの製造方法。
（７）前記高濃度石炭−水スラリーがガス化燃料或いはボイラ燃料であることを特徴とする、前記（１）〜（６）いずれかに記載の高濃度石炭−水スラリーの製造方法。
That is, the present invention is as follows.
(1) In a method for producing a high-concentration coal-water slurry using a wet mill,
A method for producing a high-concentration coal-water slurry, wherein coal and the contents of a microalgae culture tank are charged as they are into a wet mill, and a required amount of water is added to pulverize the coal.
(2) In a method for producing a high-concentration coal-water slurry using a wet mill,
Into the wet mill, coal and the microalgae concentrate obtained by concentrating the contents of the microalgae culture tank are added, and the required amount of water including the water obtained by the concentration process is added to the coal. A method for producing a high-concentration coal-water slurry, characterized by pulverizing.
(3) The high-concentration coal water slurry according to (1) or (2), wherein the water is water obtained by concentrating the water and / or the contents of the microalgae culture tank. Production method.
(4) The method for producing a high-concentration coal-water slurry according to (1) or (2), wherein the microalga is a microalga having spherical cells.
(5) The microalgae is a microalgae obtained by attaching a microalgae culture tank to a facility that generates carbon dioxide-containing waste gas and fixing the carbon dioxide gas to microalgae using photosynthesis. The method for producing a high-concentration coal-water slurry according to any one of (1) to (4), wherein
(6) The high concentration coal-water slurry produced by the method described in (1) or (2) above is mixed with the microalgae concentrate obtained as it is or by concentrating the contents of the microalgae culture tank. A method for producing a high-concentration coal-water slurry, which is characterized by being added.
(7) The method for producing a high-concentration coal-water slurry according to any one of (1) to (6), wherein the high-concentration coal-water slurry is gasification fuel or boiler fuel.
本発明の高濃度石炭−水スラリーの製造方法によれば、微細藻を育成培地ごと用いるため、ガス化燃料やボイラ燃料への微細藻の利用が容易になるとともに、石炭微粒子に加えて微細藻（１〜１０μｍ）が流動性に寄与するため、得られるスラリーの流動性が向上する。それにより、スラリーの高濃度が可能となり、スラリー中の水分が減少し蒸発潜熱が低減することで、ガス化熱効率や燃焼効率が向上する。 According to the method for producing a high-concentration coal-water slurry of the present invention, since microalgae are used for each growth medium, the use of microalgae for gasification fuel and boiler fuel is facilitated, and in addition to coal microparticles, microalgae are used. Since (1 to 10 μm) contributes to fluidity, the fluidity of the resulting slurry is improved. Thereby, a high concentration of the slurry becomes possible, and moisture in the slurry is reduced and latent heat of vaporization is reduced, thereby improving gasification heat efficiency and combustion efficiency.
さらに石炭のみで必要となる微粒子の量を製造調整するには、その分粉砕機の動力が必要となるが、本発明の方法では微細藻がこの石炭微粒子量を補うため、粉砕機動力を減らす効果が生まれる。 Furthermore, in order to adjust the production of the amount of fine particles required only by coal, the power of the pulverizer is required correspondingly. However, in the method of the present invention, the microalgae supplements the amount of fine coal particles, so the pulverizer power is reduced. An effect is born.
また、石炭−水スラリー製造用の水を、培地を含む微細藻で代替することにより、微細藻の脱水・乾燥工程が不要となるため、微細藻の後処理という観点から見て、エネルギー利用効率が格段に向上する。添加された微細藻は、ガス化炉内で燃焼し、水分はガス化剤（Ｃ＋Ｈ２Ｏ→ＣＯ＋Ｈ２）として消費され、余剰水分は水蒸気となり、一方、細胞分泌物質及び栄養塩は還元性微量成分ガス（Ｎ→ＮＨ３、Ｓ→Ｈ２Ｓ）となりガス精製過程で処理されるため、残細胞の処理（培地の殺菌）及び水処理といった問題も解決される。 In addition, since the water for producing coal-water slurry is replaced with microalgae containing a medium, dehydration and drying processes of microalgae are not required, so that energy utilization efficiency is seen from the viewpoint of post-treatment of microalgae. Is significantly improved. The added microalgae burns in the gasification furnace, the water is consumed as a gasifying agent (C + H 2 O → CO + H 2 ), the surplus water becomes water vapor, while the cellular secretions and nutrients are reducing trace amounts. Since component gases (N → NH 3 , S → H 2 S) are processed in the gas purification process, problems such as residual cell processing (medium sterilization) and water treatment are also solved.
微細藻は、細胞を保護するため高粘性物質を生産する種類が存在しており、当該物質が石炭表面に吸着し、石炭粒子の親水性が向上することにより、石炭粒子の分散状態を維持するために添加していた添加剤が不要となる。 There are types of microalgae that produce highly viscous substances to protect cells, and these substances are adsorbed on the surface of coal and maintain the dispersed state of coal particles by improving the hydrophilicity of coal particles. Therefore, the additive that has been added becomes unnecessary.
微細藻培養槽を、炭酸ガス含有廃ガスを発生する火力発電所等の施設に併設し、当該廃ガス中の炭酸ガスを微細藻に固定し、得られる微細藻を含む培養槽内容物をそのまま添加することもできる。 A microalgae culture tank is attached to a facility such as a thermal power plant that generates carbon dioxide-containing waste gas, the carbon dioxide in the waste gas is fixed to the microalgae, and the contents of the culture tank containing the resulting microalgae are left as they are. It can also be added.
本発明の実施の形態を以下に説明するが、本発明はこれらの実施の形態に限定されるものではない。 Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.
（実施の形態１）
図１及び図２は、本発明の実施の形態である高濃度石炭−水スラリーの製造方法を示す説明図である。本実施の形態に係る高濃度石炭−水スラリーの製造方法では、原料炭を予め１０ｍｍ以下程度に粗砕した石炭１、スラリー濃度調整用の水２、微細藻培養槽３の内容物をポンプＰ１により、ボールミル、ロッドミル等の湿式ミル４に投入した後、湿式粉砕して高濃度石炭−水スラリー５を得る。
(Embodiment 1)
FIG.1 and FIG.2 is explanatory drawing which shows the manufacturing method of the high concentration coal-water slurry which is embodiment of this invention. In the method for producing a high-concentration coal-water slurry according to the present embodiment, the content of the coal 1 obtained by previously crushing raw coal to about 10 mm or less, water 2 for adjusting the slurry concentration, and the microalgae culture tank 3 is pumped P1. Then, after putting into wet mill 4 such as a ball mill or a rod mill, wet pulverization is performed to obtain high-concentration coal-water slurry 5.
原料炭としては、瀝青炭、亜瀝青炭が好適である。石炭の灰分が多い場合は、浮選法、水中造粒法等で脱灰したものを用いることもできる。 As the raw coal, bituminous coal and subbituminous coal are suitable. When there is much ash content of coal, what was deashed by the flotation method, the underwater granulation method, etc. can also be used.
湿式ミル４内に投入する粗砕炭１の量は、石炭の炭種、石炭濃度及び流動状態等によって変化するため、所望の粘度が得られるような石炭濃度を予め設定しておき、設定した濃度になるように、粗砕炭１、微細藻培養槽３の内容物をそのまま、及び必要量の水を投入する。微細藻培養槽３の内容物中の水分で、石炭−水スラリーの媒体となる水の量を賄うことができる場合は、微細藻培養槽３の内容物をそのまま湿式ミル内に投入するだけでも良い。湿式ミル内には、必要に応じて、ナフタレンスルホン酸、それらの塩またはこれらの脂肪族アルデヒド付加縮合物、ポリスチレンスルホン酸塩等の分散剤や、粘土鉱物、カルボキシメチルセルロース、キサンタンガム等の安定剤等の添加剤を添加することもできる。 The amount of the coarsely pulverized coal 1 put into the wet mill 4 varies depending on the coal type, coal concentration, flow state, and the like of the coal. Therefore, the coal concentration is set so as to obtain a desired viscosity. The contents of the coarsely pulverized coal 1 and the microalgae culture tank 3 are added as they are and the required amount of water is added so as to obtain a concentration. When the water in the contents of the microalgae culture tank 3 can cover the amount of water used as a medium for the coal-water slurry, the contents of the microalgae culture tank 3 can be simply put into the wet mill. good. In the wet mill, if necessary, dispersants such as naphthalene sulfonic acid, salts thereof or aliphatic aldehyde addition condensates, polystyrene sulfonates, stabilizers such as clay minerals, carboxymethyl cellulose, xanthan gum, etc. These additives can also be added.
所望の湿式ミル運転条件に従い、石炭を所定時間湿式粉砕することにより、石炭濃度約５０〜７０％で、見掛け粘度約１０００ｍＰａ・ｓ（室温、剪断速度＝１００／ｓ）以下の高濃度石炭−水スラリーを製造する。そして、得られる石炭−水スラリー５を、スラリー貯槽６に貯留し、ポンプＰ２によりガス化炉７またはボイラ８に投入する。これにより、投入した培養液中の水分は、前述のようにガス化剤として消費される。余剰水分はガス化炉７またはボイラ８内での燃焼で水蒸気として排出されるため、燃焼に悪影響を及ぼす恐れがない。また、スルホン酸基を含む分散剤や安定剤の添加量が減少することにより排ガス中のＳＯｘを減らす効果も期待できる。 High-concentration coal-water having an apparent viscosity of about 1000 mPa · s (room temperature, shear rate = 100 / s) or less at a coal concentration of about 50 to 70% by wet-pulverizing coal for a predetermined time according to desired wet mill operation conditions A slurry is produced. And the obtained coal-water slurry 5 is stored in the slurry storage tank 6, and is thrown into the gasification furnace 7 or the boiler 8 with the pump P2. Thereby, the water | moisture content in the culture solution supplied is consumed as a gasifying agent as mentioned above. Excess water is discharged as water vapor by combustion in the gasification furnace 7 or the boiler 8, so there is no fear of adversely affecting the combustion. In addition, an effect of reducing SOx in the exhaust gas can be expected by reducing the amount of dispersant or stabilizer containing a sulfonic acid group.
微細藻培養槽３の中は、水、微量の栄養塩（窒素、リン酸、カリウム分等）、極く低濃度の微細藻、微量の細胞分泌物質が存在する。本発明では、これらを全て石炭−水スラリー製造用の湿式ミル内に添加し、培養液中の水分をスラリー媒体として利用し、微細藻を石炭微粒子と同様に扱うので、排水処理や残細胞の処理が不要になると共に、微細藻を混燃用バイオマス燃料として扱う場合よりも微細藻の特性を有効利用し、かつ、エネルギーロスを少なくすることができる。 In the microalgae culture tank 3, there are water, trace amounts of nutrients (nitrogen, phosphoric acid, potassium, etc.), extremely low concentrations of microalgae, and trace amounts of cell-secreted substances. In the present invention, all of these are added into a wet mill for producing a coal-water slurry, the water in the culture medium is used as a slurry medium, and microalgae are treated in the same manner as fine coal particles. The treatment is not necessary, and the characteristics of the microalgae can be effectively used and the energy loss can be reduced as compared with the case where the microalgae are treated as a mixed fuel for biomass fuel.
本発明で用いる微細藻類としては、石炭微粒子と同程度の大きさ（１〜１０μｍ）のものが好ましく、特に球形細胞を有するものが好ましい。かかる微細藻類としては、ナンノクロロプシス、クロロコックム、アファノカプサ、クラミドモナス、クロレラ、シネココッカス、ミクロキスティス等を挙げることができる。これらの微細藻は、淡水で生育する微細藻であるため、培地（淡水）ごと湿式ミル内に添加した場合でも、石炭−水スラリーの分散安定性を損ねる恐れがない。図５に、淡水性微細藻類であるクロロコックムの電子顕微鏡写真を示す。 As the microalgae used in the present invention, those having the same size (1 to 10 μm) as coal fine particles are preferable, and those having spherical cells are particularly preferable. Examples of such microalgae include Nannochloropsis, Chlorococcum, Afanocapsa, Chlamydomonas, Chlorella, Synecococcus, Microcystis and the like. Since these microalgae are microalgae that grow in fresh water, there is no risk of impairing the dispersion stability of the coal-water slurry even when the medium (freshwater) is added to the wet mill. FIG. 5 shows an electron micrograph of chlorococcum, which is a freshwater microalgae.
上記した微細藻類のうち、アファノカプサ、クラミドモナス等は、高粘性物質（多糖類）を生産する微細藻である。これらの微細藻を用いることにより、石炭−水スラリーを安定させるための添加剤、特に安定剤を減少させ、或いは、無くすことができる。 Among the above-mentioned microalgae, afanocapsa, Chlamydomonas, etc. are microalgae that produce highly viscous substances (polysaccharides). By using these microalgae, additives for stabilizing the coal-water slurry, particularly stabilizers can be reduced or eliminated.
図６は、本発明の高濃度石炭−水スラリーの製造方法で得られるスラリーの説明図である。スラリーは、水（培地からの水が主体）、石炭粒子、石炭微粒子及び微細藻等を含む組成物であり、石炭粒子（７４μｍ以下）の間に、石炭微粒子（１〜１０μｍ）及び微細藻（１〜１０μｍ）が入り込んで、石炭粒子を動かすコロの役割を果たすことによって、スラリーの安定性が向上する。 FIG. 6 is an explanatory diagram of a slurry obtained by the method for producing a high concentration coal-water slurry of the present invention. The slurry is a composition containing water (mainly water from the culture medium), coal particles, coal fine particles, microalgae, and the like, and between the coal particles (74 μm or less), coal fine particles (1-10 μm) and microalgae ( 1-10 μm) enters and acts as a roller that moves the coal particles, thereby improving the stability of the slurry.
（実施の形態２）
図３及び図４は、本発明の別の実施の形態を示した図である。本実施の形態に係る高濃度石炭−水スラリーの製造方法では、原料炭を予め１０ｍｍ以下程度に粗砕した石炭１、微細藻培養槽３の内容物を濃縮処理して得られる微細藻濃縮液３１、前記濃縮処理で得られる水３２、スラリー濃度調整用の水２を、湿式ミル４内に投入した後、実施の形態１と同様、湿式粉砕して高濃度石炭−水スラリー５を得る。濃縮処理で得られる水３２及びスラリー濃度調整用の水２を投入し、微細藻濃縮液３１中の水分のみでは賄い切れない石炭−水スラリーの媒体となる必要量の水を賄う。この場合、濃縮処理で得られる水３２を含む必要量の水を湿式ミル内に投入して石炭を粉砕するので、微細藻の濃縮処理で発生する水の排水処理が不要となる。
(Embodiment 2)
3 and 4 are diagrams showing another embodiment of the present invention. In the method for producing a high-concentration coal-water slurry according to the present embodiment, a microalga concentrate obtained by concentrating the contents of coal 1 and microalgae culture tank 3 obtained by preliminarily crushing raw coal to about 10 mm or less. 31. After the water 32 obtained by the concentration process and the water 2 for adjusting the slurry concentration are put into the wet mill 4, as in the first embodiment, wet pulverization is performed to obtain a high-concentration coal-water slurry 5. The water 32 obtained by the concentration treatment and the water 2 for adjusting the slurry concentration are added, and a necessary amount of water serving as a coal-water slurry medium that cannot be covered only with the water in the microalgae concentrate 31 is provided. In this case, since the required amount of water including the water 32 obtained by the concentration treatment is put into the wet mill and the coal is pulverized, the drainage treatment of the water generated by the concentration treatment of the microalgae becomes unnecessary.
本実施の形態でも、湿式ミル内には、必要に応じて、分散剤、安定剤等の添加剤を添加することができる。本実施の形態では、石炭の粉砕時に投入する微細藻量を調節するのが容易であり、しかも培地ごと投入するのに比べて多量の微細藻を投入できる利点がある。 Also in this embodiment, additives such as a dispersant and a stabilizer can be added to the wet mill as necessary. In the present embodiment, it is easy to adjust the amount of microalgae to be input at the time of coal pulverization, and there is an advantage that a large amount of microalgae can be input as compared with the case where the whole medium is input.
微細藻培養槽の内容物の濃縮処理方法としては、公知の濃縮方法を採用することができる。濃縮液３１における微細藻濃度は、石炭−水スラリー濃度（石炭濃度約５０〜７０％）及び添加剤量を考慮すると、水分量を極端に減らす必要はなく、培養液中の微細藻濃度は低濃度（例えば０．２〜１％程度）であっても良い。 As a concentration treatment method for the contents of the microalgae culture tank, a known concentration method can be employed. The concentration of microalgae in the concentrate 31 does not need to be extremely reduced when considering the coal-water slurry concentration (coal concentration of about 50 to 70%) and the amount of additives, and the concentration of microalgae in the culture solution is low. It may be a concentration (for example, about 0.2 to 1%).
そして、得られる石炭−水スラリー５を、スラリー貯槽６に貯留し、ポンプＰ２によりガス化炉７またはボイラ８に投入する。 And the obtained coal-water slurry 5 is stored in the slurry storage tank 6, and is thrown into the gasification furnace 7 or the boiler 8 with the pump P2.
上記の実施の形態１、２で説明した、湿式ミルを用いて高濃度石炭−水スラリーを製造する方法においては、高濃度石炭−水スラリーを製造した後、得られるスラリーに、微細藻培養槽の内容物をそのまま或いはこれを濃縮処理して得られる微細藻濃縮液を、混合添加することもできる。こうすることで、湿式ミル内で製造した高濃度石炭−水スラリーにさらに微細藻を添加するので、より安定性の高い高濃度石炭−水スラリーを製造することができる。添加した微細藻は、ガス化炉或いはボイラ内で容易に燃焼可能である。 In the method for producing a high-concentration coal-water slurry using the wet mill described in the first and second embodiments, after producing the high-concentration coal-water slurry, the resulting slurry is subjected to a microalgae culture tank. It is also possible to mix and add the microalga concentrate obtained as it is or by concentrating it. By carrying out like this, since a micro algae is further added to the high concentration coal-water slurry manufactured in the wet mill, a highly stable high concentration coal-water slurry can be manufactured. The added microalgae can be easily burned in a gasification furnace or a boiler.
以下、本発明の高濃度石炭−水スラリーの製造方法の一実施例を説明する。 Hereinafter, an embodiment of the method for producing a high concentration coal-water slurry of the present invention will be described.
（実施例１）
瀝青炭の粗砕炭１０００部、微細藻培養槽の内容物（微細藻濃度：約０．１％）１０００部、及び分散剤５部を、湿式ミル内に投入し、７４μｍ以下の石炭粒子が８０％程度になるように粉砕する。得られる石炭−水スラリーをスラリー貯槽に貯留し、ボイラ又は石炭ガス化炉に供給し燃料として利用する。
Example 1
1000 parts of coarsely crushed coal of bituminous coal, 1000 parts of the contents of a microalgae culture tank (microalgae concentration: about 0.1%) and 5 parts of a dispersing agent are put into a wet mill, and coal particles of 74 μm or less are 80 Grind to about%. The obtained coal-water slurry is stored in a slurry storage tank, supplied to a boiler or a coal gasifier, and used as fuel.
（実施例２）
亜瀝青炭の粗砕炭１０００部、微細藻培養槽の内容物を、濃縮処理して得た微細藻濃縮液（微細藻濃度：約０．２％）１０００部、及び分散剤５部を湿式ミル内に投入し、実施例１と同様にして、石炭−水スラリーを得る。かかる濃縮処理法としては加圧ろ過、遠心分離、真空加熱などの方式による。得られる石炭−水スラリーを、スラリー貯槽に貯留し、ボイラ又は石炭ガス化炉に供給し燃料として利用する。
(Example 2)
Wet mill 1000 parts of coarsely crushed coal of sub-bituminous coal, 1000 parts of fine algae concentrate (fine algae concentration: about 0.2%) obtained by concentrating the contents of the microalgae culture tank, and 5 parts of dispersant The coal-water slurry is obtained in the same manner as in Example 1. Such a concentration treatment method may be a method such as pressure filtration, centrifugation, or vacuum heating. The obtained coal-water slurry is stored in a slurry storage tank, supplied to a boiler or a coal gasifier, and used as fuel.
（実施例３）
亜瀝青炭の粗砕炭１０００部、実施例２と同様の方法で得られる微細藻濃縮液（微細藻濃度：約１％）２００部、調整用の水７００部、及び分散剤５部を湿式ミル内に投入し、実施例１と同様にして、石炭−水スラリーを得る。得られる石炭−水スラリーを、スラリー貯槽に貯留し、ボイラ又は石炭ガス化炉に供給し燃料として利用する。
(Example 3)
Wet mill 1000 parts of sub-bituminous coal, 200 parts of microalga concentrate (microalga concentration: about 1%) obtained by the same method as in Example 2, 700 parts of water for adjustment, and 5 parts of dispersant The coal-water slurry is obtained in the same manner as in Example 1. The obtained coal-water slurry is stored in a slurry storage tank, supplied to a boiler or a coal gasifier, and used as fuel.
（実施例４）
実施例１で得られる石炭水スラリー１９００部を、湿式ミルからスラリー貯槽へ移送する際の配管中に、実施例３で得られる微細藻濃縮液（微細藻濃度：約１％）１００部を添加混合した後、この石炭−水スラリーをスラリー貯槽に貯留する。ボイラ又は石炭ガス化炉に供給し燃料として利用する。
Example 4
100 parts of the microalga concentrate (microalgae concentration: about 1%) obtained in Example 3 is added to the pipe for transferring 1900 parts of the coal water slurry obtained in Example 1 from the wet mill to the slurry storage tank. After mixing, the coal-water slurry is stored in a slurry storage tank. Supply to boiler or coal gasifier and use as fuel.
本発明によれば、微細藻を培地のまま用いるため、湿式燃料供給のガス化炉に対してバイオマス利用が容易になるとともに、製造される石炭−水スラリーを各種燃料に好適に利用することができる。微細藻培養槽の内容物の処理法として、極めて有用な方法である。 According to the present invention, since the microalga is used as it is in the culture medium, it is easy to use biomass for the gasification furnace supplied with wet fuel, and the produced coal-water slurry can be suitably used for various fuels. it can. This is an extremely useful method for treating the contents of the microalgae culture tank.
１ 粗砕炭
２ 水
３ 培養槽
４ 湿式ミル
５ 石炭−水スラリー
６ スラリー貯槽
７ ガス化炉
８ ボイラ
３１ 微細藻濃縮液
３２ 水
DESCRIPTION OF SYMBOLS 1 Crushed coal 2 Water 3 Culture tank 4 Wet mill 5 Coal-water slurry 6 Slurry storage tank 7 Gasifier 8 Boiler 31 Microalgae concentrate 32 Water
Claims (7)
湿式ミル内に、石炭と、微細藻培養槽の内容物をそのまま投入するとともに、必要量の水を投入して石炭を粉砕することを特徴とする、高濃度石炭−水スラリーの製造方法。 In a method for producing a high concentration coal-water slurry using a wet mill,
A method for producing a high-concentration coal-water slurry, wherein coal and the contents of a microalgae culture tank are charged as they are into a wet mill, and a required amount of water is added to pulverize the coal.
湿式ミル内に、石炭と、微細藻培養槽の内容物を濃縮処理して得られる微細藻濃縮液を投入するとともに、前記濃縮処理で得られる水を含む必要量の水を投入して石炭を粉砕することを特徴とする、高濃度石炭−水スラリーの製造方法。 In a method for producing a high concentration coal-water slurry using a wet mill,
Into the wet mill, coal and the microalgae concentrate obtained by concentrating the contents of the microalgae culture tank are added, and the required amount of water including the water obtained by the concentration process is added to the coal. A method for producing a high-concentration coal-water slurry, characterized by pulverizing.
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| CN106085524A (en) * | 2016-05-31 | 2016-11-09 | 神华集团有限责任公司 | The preparation method of gasification water-coal-slurry |
| EP2999772A4 (en) * | 2013-05-21 | 2016-11-16 | Nelson Mandela Metropolitan University | Upgrading coal fines using microalgae |
| KR20170030140A (en) | 2015-09-08 | 2017-03-17 | 부산대학교 산학협력단 | enhancement of gasification by LCO2 throttling process |
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| EP2999772A4 (en) * | 2013-05-21 | 2016-11-16 | Nelson Mandela Metropolitan University | Upgrading coal fines using microalgae |
| US10538715B2 (en) | 2013-05-21 | 2020-01-21 | Nelson Mandela Metropolitan University | Upgrading coal fines using microalgae |
| KR20170030140A (en) | 2015-09-08 | 2017-03-17 | 부산대학교 산학협력단 | enhancement of gasification by LCO2 throttling process |
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