JP2010248459A - Method of manufacturing liquid oil making biomass as raw material - Google Patents

Method of manufacturing liquid oil making biomass as raw material Download PDF

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JP2010248459A
JP2010248459A JP2009133495A JP2009133495A JP2010248459A JP 2010248459 A JP2010248459 A JP 2010248459A JP 2009133495 A JP2009133495 A JP 2009133495A JP 2009133495 A JP2009133495 A JP 2009133495A JP 2010248459 A JP2010248459 A JP 2010248459A
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Kazuteru Shinohara
一照 篠原
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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
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method in which a biomass raw material of vegetable origins of grass, tree, coal or the like is thermally decomposed, CO and H<SB>2</SB>are selectively separated from the gas component, the gases of the optimal flow rate are supplied to the polymerization reaction (FT synthesis) by a catalyst, thereby the reaction rate of a catalytic reactor is raised, and the yield of a liquid oil is raised. <P>SOLUTION: The biomass is made to be a raw material, a pyrolysis gas is formed from the raw material by a thermal decomposition furnace 4, CO and H<SB>2</SB>are respectively separated from the gas component, each of the gases is separately stored in a H<SB>2</SB>storage tank 11 and a CO storage tank 14. The method is characterized by including: a H<SB>2</SB>gas flow control valve 12; a CO gas flow control valve 15; a H<SB>2</SB>gas flow rate transmitter 13; a CO gas flow rate transmitter 16; and a ratio controller 17 for keeping constant the mutual flow ratio of each of gases, so as to supply the gases by the optimal flow ratio to the polymerization reaction in a catalytic reactor 18. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

発明の詳細な説明Detailed Description of the Invention

本発明は植物由来のバイオマス原料から液状油を製造する方法に関する。  The present invention relates to a method for producing liquid oil from a plant-derived biomass raw material.

近年、カーボンニュートラルの意識の高まりから、バイオマス原料からの有害物を含まない液体燃料の提供が望まれている。  In recent years, with the increasing awareness of carbon neutrality, it has been desired to provide liquid fuels that do not contain harmful substances from biomass raw materials.

バイオマスを原料として液体燃料を得る手段としては、発酵によりエタノール、又はメタノールを得る方法と、原料を熱分解したのち、その生成ガス中のＨ２及びＣＯガスを触媒を用いて重合反応により、液状油を合成する方法が挙げられるが、本発明は後者に属する。
As a means of obtaining liquid fuel from biomass as a raw material, a method of obtaining ethanol or methanol by fermentation, and after pyrolyzing the raw material, H 2 and CO gas in the product gas are polymerized using a catalyst to form a liquid Although the method of synthesizing oil is mentioned, this invention belongs to the latter.

従来の方法では熱分解炉で生成したＨ２、及びＣＯを主成分とし、他にＣＯ２、Ｎ２、ＣＨ４、Ｏ２、ＣｍＨｎ、Ｈ２Ｏと微小なＨｃｌ、ＳＯ２等を含む熱分解ガスから、ＣＯ２、Ｏ２、Ｎ２、Ｈ２Ｏ、及びＨｃｌ、ＳＯ２を除去し、Ｈ２、及びＣＯが主体の混合ガス体として取り出し、触媒反応器に送り重合反応させるが、この混合ガスには、Ｈ２、ＣＯ以外に微小ながら、他のガスが残留することが避け難く、触媒の活性が低下する難点があった。In the conventional method, heat containing H 2 and CO generated in a pyrolysis furnace as main components, and additionally containing CO 2 , N 2 , CH 4 , O 2 , CmHn, H 2 O, minute Hcl, SO 2 and the like. From the cracked gas, CO 2 , O 2 , N 2 , H 2 O, and Hcl, SO 2 are removed and taken out as a mixed gas body mainly composed of H 2 and CO, and sent to the catalyst reactor for polymerization reaction. Although this mixed gas is minute in addition to H 2 and CO, it is difficult to avoid the remaining of other gases, and the activity of the catalyst is reduced.

従来の方法では、触媒反応器に送り込む熱分解ガスは、Ｈ２とＣＯの混合ガス体であり、Ｈ２とＣＯとの流量比率を調整することは不可能であり、そのため触媒反応器に送り込む熱分解ガスのＨ２とＣＯの流量比を常に最良の比に保つことが不可能なため、触媒の反応率が低下し、液状油の生成量が低下する難点があった。In the conventional method, the pyrolysis gas sent to the catalytic reactor is a mixed gas body of H 2 and CO, and it is impossible to adjust the flow rate ratio of H 2 and CO. Therefore, the heat sent to the catalytic reactor Since it is impossible to always keep the flow rate ratio of H 2 and CO of the cracked gas at the best ratio, the reaction rate of the catalyst is lowered, and the production amount of liquid oil is reduced.

本発明は、バイオマス原料を熱分解した熱分解ガスより、反応基材のＨ２、及びＣＯのみを選択的に分離し、そのＨ２とＣＯを最適流量比で触媒反応器に導き、重合反応率を上げることにより、液状油の生成量を増加させる方法を提供する。The present invention selectively separates only H 2 and CO of the reaction base material from the pyrolysis gas obtained by pyrolyzing the biomass raw material, guides the H 2 and CO to the catalytic reactor at the optimum flow rate ratio, and the polymerization reaction rate A method for increasing the amount of liquid oil produced by increasing

本発明は以下の発明を含む。
（１）熱分解炉において、生成した熱分解ガスから、Ｈ２とＣＯのみを選択的に分離し、この各々のガスを一旦各々の貯留タンクに貯留したのち、触媒反応に必要なＨ２とＣＯ量を制御し、触媒反応器に供給することを特徴とする、バイオマス原料を熱分解後、触媒反応によるＦＴ合成により液状油を製造する方法。
（２）熱分解炉は、酸化材としてＯ２ガスを吹き込むため、大気よりＯ２を分離し、熱分解炉へ供給し、残りの分離されたＮ２は貯蔵するＯ２分離器とＮ２貯蔵タンクを有する。
（３）熱分解中に含まれるＨ２Ｏ、及びタール分を除去するため、熱分解ガスと水を直接接触させることにより、冷却と洗浄を行う洗浄器を有する
（４）この洗浄後の熱分解ガスから、Ｈ２、及びＣＯを各々別個に分別分離するガス分離器を有する。
（５）分離されたＨ２、及びＣＯを別個に貯蔵する貯蔵タンクを有する。
（６）貯蔵タンクに貯蔵されたＨ２及びＣＯを各々最適の流量比で触媒反応器に供給できるよう、各ガスの流量検出器とＨ２とＣＯの流量比を一定値に担保する比率調節計と各ガスの流量調節弁を有する。
（７）ガス分離器により、Ｈ２とＣＯを分離した残ガス中のＣＯ２を分離するＣＯ２分離器と、このＣＯ２を貯蔵する貯蔵タンクを有する。The present invention includes the following inventions.
(1) In the pyrolysis furnace, only H 2 and CO are selectively separated from the generated pyrolysis gas, and each gas is temporarily stored in each storage tank, and then H 2 required for the catalytic reaction A method for producing liquid oil by FT synthesis by catalytic reaction after pyrolyzing a biomass raw material, characterized in that the amount of CO is controlled and supplied to a catalytic reactor.
(2) Since the pyrolysis furnace injects O 2 gas as an oxidant, O 2 is separated from the atmosphere, supplied to the pyrolysis furnace, and the remaining separated N 2 is stored as an O 2 separator and N 2 Has a storage tank.
(3) In order to remove H 2 O and tar content contained in the thermal decomposition, the thermal decomposition gas and the water are brought into direct contact with each other to have a cleaning device for cooling and cleaning. (4) Heat after this cleaning It has a gas separator that separates H 2 and CO separately from the cracked gas.
(5) It has a storage tank for storing separated H 2 and CO separately.
(6) Adjusting the ratio of each gas flow rate detector and the flow rate ratio of H 2 and CO to a constant value so that H 2 and CO stored in the storage tank can be supplied to the catalytic reactor at an optimum flow rate ratio. It has a meter and a flow control valve for each gas.
(7) It has a CO 2 separator that separates CO 2 in the residual gas from which H 2 and CO have been separated by a gas separator, and a storage tank that stores this CO 2 .

本発明によれば、触媒反応器に導くＨ２とＣＯの純度が高く他のガスを含まないため、触媒の活性を損なうことがない。According to the present invention, the purity of H 2 and CO led to the catalyst reactor is high and does not contain other gases, so that the activity of the catalyst is not impaired.

又本発明によれば、触媒反応において最も重要なＨ２とＣＯの流量比を、正確に、且つ安定して供給することができる。Further, according to the present invention, the flow rate ratio of H 2 and CO, which is the most important in the catalytic reaction, can be supplied accurately and stably.

又本発明によれば、熱分解時に避けられないＣＯ２を大気中に放散することが無く、有用化がはかれる。一例として、Ｃａ（ＯＨ）２と反応させて、ＣａＣＯ３とし、セメント原料にすることが考えられる。Further, according to the present invention, CO 2 unavoidable during thermal decomposition is not diffused into the atmosphere, and it is useful. As an example, it is conceivable to react with Ca (OH) 2 to make CaCO 3 to be a cement raw material.

以下に、本発明の実施の形態について、図面を参照して説明する。  Embodiments of the present invention will be described below with reference to the drawings.

図１は本実施形態のフローシート図である。バイオマス原料は、細粒化され定量的に熱分解炉４に投入し、同時に酸素分離器２により分離されたＯ２を、燃焼に必要な化学量論比の１０％〜３５％と、過熱水蒸気を吹き込み、熱分解炉４内の温度を１０００℃〜１２００℃に維持することにより、バイオマスを熱分解し、熱分解ガスを生成する。FIG. 1 is a flow sheet diagram of the present embodiment. The biomass raw material is finely granulated and quantitatively charged into the pyrolysis furnace 4, and at the same time, O 2 separated by the oxygen separator 2 is superheated steam with a stoichiometric ratio of 10% to 35% necessary for combustion. And the temperature in the pyrolysis furnace 4 is maintained at 1000 ° C. to 1200 ° C., whereby the biomass is pyrolyzed to generate pyrolysis gas.

熱分解したガスは、先ず蒸気過熱器５を通過し、熱分解炉４に吹き込む水蒸気を６５０℃〜８００℃の過熱水蒸気とし、同ガス自身は減温される。続いて同熱分解ガスは、分解ガス冷却器６を通過し、この時蒸気ドラム７に貯留された蒸気の温度を維持する加熱源となり、自身ガスは減温される。  The pyrolyzed gas first passes through the steam superheater 5 and the steam blown into the pyrolysis furnace 4 is converted to superheated steam at 650 ° C. to 800 ° C., and the gas itself is reduced in temperature. Subsequently, the pyrolysis gas passes through the cracking gas cooler 6 and becomes a heating source for maintaining the temperature of the steam stored in the steam drum 7 at this time, and the temperature of the gas itself is reduced.

次に分解ガス冷却器６を通過した熱分解ガスは、洗浄器８に導き、冷水と接触させることにより、熱分解ガス中のダスト分とタール分を凝縮させ、熱分解ガスを、ダストとタールを含まない清浄ガスとする、と同時に減温する。  Next, the pyrolysis gas that has passed through the cracking gas cooler 6 is guided to the scrubber 8 and brought into contact with cold water to condense the dust and tar components in the pyrolysis gas, thereby converting the pyrolysis gas into dust and tar. The temperature is reduced at the same time as a clean gas that does not contain gas.

清浄化された熱分解ガスは、次にガス分離器１０に導き、ここでＨ２とＣＯに各々分離し、Ｈ２はＨ２貯蔵タンク１１に、ＣＯはＣＯ貯蔵タンク１４に、コンプレッサ９により５ｋｇ／ｃｍ２・Ｇ〜３０ｋｇ／ｃｍ２・Ｇの圧力を維持できるように圧入する。The cleaned pyrolysis gas is then directed to a gas separator 10 where it is separated into H 2 and CO, respectively, H 2 into the H 2 storage tank 11, CO into the CO storage tank 14 and by the compressor 9. press-fitted so as to maintain a pressure of 5kg / cm 2 · G~30kg / cm 2 · G.

一方、ガス分離器１０で分離されなかった、Ｈ２、及びＣＯ以外のガスは、ＣＯ２分離器２８に送られ、ＣＯ２のみを選択分離して、ＣＯ２貯蔵タンク２９に圧送する。On the other hand, gases other than H 2 and CO that have not been separated by the gas separator 10 are sent to the CO 2 separator 28, and only CO 2 is selectively separated and sent to the CO 2 storage tank 29 by pressure.

Ｈ２貯蔵タンク１１、ＣＯ貯蔵タンク１４の各貯蔵タンクに貯蔵されたＨ２及びＣＯは触媒反応器１８に送り込まれ重合反応により、液状炭化水素を合成するが、この合成反応には、最適なＨ２量とＣＯ量の比が存在する。そこで本発明では、Ｈ２流量を計測するＨ２ガス流量発信器１３と、Ｈ２ガス流量調節弁１２を設け、一方同様にＣＯガス流量発信器１６とＣＯガス流量調節弁１５を設け、且つ両ガスの流量比を一定に保てるよう比率調節計１７を設けることにより、常に最適な流量比で安定して触媒反応器１８にＨ２及びＣＯガスを供給することが可能となる。The H 2 H 2 and CO which is stored in the storage tanks of the storage tank 11, CO storage tank 14 is fed to the catalytic reactor 18 the polymerization reaction, to synthesize a liquid hydrocarbon, in the synthesis reaction, optimal the ratio of H 2 amount and CO amount is present. Therefore, in the present invention, the H 2 gas flow rate transmitter 13 which measures the flow rate of H 2, H 2 gas flow rate control valve 12 is provided, whereas similarly provided CO gas flow transmitter 16 and the CO gas flow rate control valve 15, and By providing the ratio controller 17 so that the flow ratio of both gases can be kept constant, it becomes possible to stably supply H 2 and CO gas to the catalytic reactor 18 at an optimum flow ratio at all times.

表１は、バイオマス原料の組成を示し、表２は、それを水分３３％の状態で熱分解炉４の温度を１１００℃に保持した場合の熱分解ガスの組成である。Table 1 shows the composition of the biomass raw material, and Table 2 shows the composition of the pyrolysis gas when the temperature of the pyrolysis furnace 4 is maintained at 1100 ° C. in a state where the moisture content is 33%.

本発明のバイオマスを原料とした液状油の製造方法は、木片、草、間伐材、及びメタンガス等の有機物を、貯蔵及び輸送の容易な液体燃料として提供することが出来る。表３に製造した液状油の一例を示す。  The method for producing liquid oil using biomass of the present invention as a raw material can provide wood chips, grass, thinned wood, and organic substances such as methane gas as liquid fuel that is easy to store and transport. Table 3 shows an example of the liquid oil produced.

本発明の実施形態に係るフローシート図である。It is a flow sheet figure concerning the embodiment of the present invention.

１・・・コンプレッサー
２・・・酸素分離器
３・・・Ｎ２貯蔵タンク
４・・・熱分解炉
５・・・蒸気加熱器
６・・・分解ガス冷却器
７・・・蒸気タンク
８・・・洗浄器
９・・・コンプレッサー
１０・・・ガス分離器
１１・・・Ｈ２貯蔵タンク
１２・・・Ｈ２ガス流量調節弁
１３・・・Ｈ２ガス流量発信器
１４・・・ＣＯ貯蔵タンク
１５・・・ＣＯガス流量調節弁
１６・・・ＣＯガス流量発信器
１７・・・比率調節計
１８・・・触媒反応器
１９・・・分離タンク
２０・・・重／軽質油分離タンク
２１・・・冷却器
２２・・・冷却器
２３・・・ガス／軽質油分離タンク
２４・・・冷却器
２５・・・油／水分離タンク
２６・・・重質油貯蔵タンク
２７・・・軽質油貯蔵タンク
２８・・・ＣＯ２分離器
２９・・・ＣＯ２貯蔵タンク
３０・・・空気加熱器
３１・・・ポンプ
３２・・・送風機1 ... Compressor 2 ... oxygen separator 3 ... N 2 storage tanks 4 ... pyrolysis furnace 5 ... steam heater 6 ... cracked gas cooler 7 ... vapor tank 8, ..Washer 9 ... Compressor 10 ... Gas separator 11 ... H 2 storage tank 12 ... H 2 gas flow rate control valve 13 ... H 2 gas flow rate transmitter 14 ... CO storage Tank 15 ... CO gas flow rate control valve 16 ... CO gas flow rate transmitter 17 ... Ratio controller 18 ... Catalyst reactor 19 ... Separation tank 20 ... Heavy / light oil separation tank 21 ... Cooler 22 ... Cooler 23 ... Gas / light oil separation tank 24 ... Cooler 25 ... Oil / water separation tank 26 ... Heavy oil storage tank 27 ... Light oil storage tank 28 · · · CO 2 separator 29 · · · CO 2 storage tank 30 .. Air heater 31 ... pump 32 ... blower

Claims (6)

熱分解ガスから、Ｈ２ガスとＣＯガスを別個に選択分離するガス分離器と、そのＨ２ガスとＣＯガスを各々別個に貯蔵する貯蔵タンクと、各ガスを一定の流量比に保つ弁及び調節装置と、このガスを重合反応させる触媒反応器を有する液状炭化水素を合成する液状油製造装置。A gas separator that selectively separates H 2 gas and CO gas from pyrolysis gas, a storage tank that separately stores the H 2 gas and CO gas, a valve that maintains each gas at a constant flow rate ratio, and A liquid oil production apparatus for synthesizing liquid hydrocarbons having a regulator and a catalytic reactor for polymerizing the gas. 酸素分離器により、９５％から９９％の純度のＯ２ガスを分離し、これを部分燃焼の酸化剤として用いる熱分解炉を含むことを特徴とする請求項１に記載の方法。The method according to claim 1, further comprising a pyrolysis furnace using an oxygen separator to separate 95% to 99% pure O 2 gas and using this as an oxidizing agent for partial combustion. 酸素分離器により分離したＮ２ガスをＮ２貯蔵タンクに貯蔵回収することを特徴とする請求項１に記載の方法。The method according to claim 1, wherein the N 2 gas separated by the oxygen separator is stored and recovered in an N 2 storage tank. 熱分解炉から発生した８００℃〜１２００℃の熱分解ガスにより、同炉に吹き込む水蒸気を６５０℃〜８００℃に加熱する蒸気加熱器と蒸気タンクの低部より凝縮水を加熱すると同時に熱分解ガスを３５０℃まで冷却する分解ガス冷却器を有することを特徴とする請求項１に記載の方法。  The pyrolysis gas generated from the pyrolysis furnace at 800 ° C to 1200 ° C heats the condensed water from the lower part of the steam heater and the steam tank that heats the steam blown into the furnace to 650 ° C to 800 ° C, and at the same time, the pyrolysis gas The method according to claim 1, further comprising a cracked gas cooler that cools the liquid to 350 ° C. 熱分解ガス冷却器を通過した熱分解ガスに含まれるタール分を除去し、含有水分量を減らすため水洗浄を行う洗浄器を有することを特徴とする請求項１に記載の方法。  The method according to claim 1, further comprising a washer that performs water washing to remove a tar content contained in the pyrolysis gas that has passed through the pyrolysis gas cooler and to reduce a moisture content. ガス分離器によりＨ２、及びＣＯを分離された残ガス中には、ＣＯ２ガスが最大分圧を占めるため、ＣＯ２を選択的に分離するＣＯ２分離器と分離したＣＯ２を貯蔵するＣＯ２貯蔵タンクを有することを特徴とする請求項１に記載の方法。H 2, and the residual gas is separated CO by gas separator, CO 2 gas to occupy the maximum partial pressure, for storing the CO 2 separated from the CO 2 separator for selectively separating CO 2 The method according to claim 1, comprising a CO 2 storage tank.
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JP6552030B1 (en) * 2018-09-14 2019-07-31 株式会社 ユーリカ エンジニアリング Syngas production system for low carbon FT synthetic oil production
WO2020054088A1 (en) * 2018-09-14 2020-03-19 株式会社 ユーリカ エンジニアリング Synthetic gas production system for low-carbon ft synthetic oil production
WO2020054063A1 (en) * 2018-09-14 2020-03-19 株式会社 ユーリカ エンジニアリング Synthetic gas production system for low-carbon ft synthetic oil production
WO2023286730A1 (en) * 2021-07-12 2023-01-19 東洋エンジニアリング株式会社 Synthetic fuel production method
WO2023286731A1 (en) * 2021-07-12 2023-01-19 東洋エンジニアリング株式会社 Synthetic fuel production method

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