JP5846160B2 - Alcohol production wastewater treatment device and treatment method - Google Patents
Alcohol production wastewater treatment device and treatment method Download PDFInfo
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 55
- 238000011282 treatment Methods 0.000 title claims description 51
- 238000000034 method Methods 0.000 title claims description 30
- 238000004065 wastewater treatment Methods 0.000 title claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 130
- 239000002351 wastewater Substances 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 150000007524 organic acids Chemical class 0.000 claims description 20
- 238000004821 distillation Methods 0.000 claims description 13
- 244000005700 microbiome Species 0.000 claims description 10
- 230000005484 gravity Effects 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 238000003672 processing method Methods 0.000 claims description 2
- 239000010802 sludge Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000008187 granular material Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000000855 fermentation Methods 0.000 description 5
- 230000004151 fermentation Effects 0.000 description 5
- 238000010979 pH adjustment Methods 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000003337 fertilizer Substances 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 235000019645 odor Nutrition 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2833—Anaerobic digestion processes using fluidized bed reactors
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/40—Liquid flow rate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/02—Odour removal or prevention of malodour
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- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Description
本発明は、サトウキビ、トウモロコシ、小麦などを原料としてバイオエタノール、蒸留酒などのアルコールを製造する際に発生する排水の処理装置及び処理方法に関するものであり、特にアルコール製造排水を蒸留処理して得られる凝縮水を嫌気性処理する装置及び方法に関する。 The present invention relates to a treatment apparatus and a treatment method for wastewater generated when sugar alcohol, corn, wheat and the like are used as raw materials for producing alcohol such as bioethanol and distilled liquor. The present invention relates to an apparatus and method for anaerobically treating condensed water produced.
バイオエタノールや蒸留酒は、サトウキビ、トウモロコシ、小麦などの穀物原料に対して、酸処理、アルカリ処理、生物学的処理、物理的処理等の前処理及び糖化処理を施して炭素源とし、得られた炭素源を酵母により発酵させることにより低濃度のエタノール含有発酵液を得、この発酵液を濃縮、蒸留し、必要に応じて更に精製することにより製造されている（例えば特許文献１）。 Bioethanol and distilled liquor are obtained by subjecting cereal raw materials such as sugarcane, corn, and wheat to acid treatment, alkali treatment, biological treatment, physical treatment, and other pretreatments and saccharification treatments as carbon sources. It is produced by fermenting the carbon source with yeast to obtain a low-concentration ethanol-containing fermented liquid, concentrating and distilling the fermented liquid, and further purifying it as necessary (for example, Patent Document 1).
アルコールの製造プロセスでは、発酵液の蒸留工程において、１０万ｍｇ／Ｌ以上の非常に高濃度のＣＯＤ含有排水が排出される。このアルコール製造排水は、穀物残渣や廃酵母、糖類のほか、発酵工程で生成される有機酸を主体とするものであり、従来、次のような方法で処理されている。
（１）広大な土地を有する工場においては、アルコール製造排水を直接嫌気ラグーンで処理して処理水を得る。この嫌気ラグーンの残留汚泥は、発酵液中の窒素、リン、カリウムなどの成分が濃縮されたものであるため、肥料等に有効利用される。
（２）バイオマスボイラー等を保有し、大量の蒸気を確保し得る工場では、アルコール製造排水を更に蒸留して蒸留塔の缶出液（濃縮残渣）を液体肥料として再利用し、一方、蒸留によりＣＯＤ濃度が数千ｍｇ／Ｌ程度に低減された、塔頂留出ガスの凝縮水を嫌気ラグーンで処理する。
In the process for producing alcohol, wastewater containing COD containing a very high concentration of 100,000 mg / L or more is discharged in the fermentation liquid distillation step. This alcohol production wastewater mainly contains organic acids produced in the fermentation process, in addition to grain residues, waste yeast, and sugars, and has been conventionally treated by the following method.
(1) In a factory having vast land, treated water is obtained by directly treating alcohol production wastewater with an anaerobic lagoon. The residual sludge of the anaerobic lagoon is effectively used for fertilizers and the like because components such as nitrogen, phosphorus, and potassium in the fermentation liquid are concentrated.
(2) In factories that have biomass boilers and can secure a large amount of steam, the alcohol production wastewater is further distilled to recycle the bottoms of the distillation tower (concentrated residue) as liquid fertilizer, while by distillation The condensed water of the tower top distillate gas whose COD concentration is reduced to about several thousand mg / L is treated with an anaerobic lagoon.
従来、ビール、飲料、食品工場などから排出される高濃度有機性排水の処理方法として、高密度で沈降性の大きいグラニュール汚泥を用いて高負荷高速処理を行うＵＡＳＢ（Upflow Anaerobic Sludge Blanket：上向流嫌気性スラッジブランケット）法が知られている。ＵＡＳＢ法では、グラニュール汚泥で形成したスラッジブランケットを保持する反応槽内に有機性排水を導入し上向流通液することで、スラッジブランケットと接触させる。また、ＵＡＳＢ法よりも高負荷高速処理を可能とする処理法として、高さの高い反応槽内に有機性排水をさらに高流速で通液し、スラッジブランケットを高展開率で展開させるＥＧＳＢ法（Expanded Granule Sludge Blanket）も知られている。 Conventionally, UASB (Upflow Anaerobic Sludge Blanket), which performs high-load high-speed treatment using granular sludge with high density and large sedimentation as a treatment method for high-concentration organic wastewater discharged from beer, beverages, food factories, etc. The counter-current anaerobic sludge blanket method is known. In the UASB method, organic wastewater is introduced into a reaction tank that holds a sludge blanket formed of granular sludge, and is allowed to contact the sludge blanket by flowing upward. In addition, as a treatment method that enables high-load and high-speed treatment compared to the UASB method, an organic wastewater is passed through the reaction vessel with a high height at a higher flow rate, and the sludge blanket is developed at a high deployment rate ( Expanded Granule Sludge Blanket) is also known.
これらＵＡＳＢ法、ＥＧＳＢ法では、嫌気性微生物が粒状化したグラニュール汚泥を用いており、嫌気性微生物を含む汚泥をグラニュール（粒）状に維持、増殖させる。グラニュール汚泥を用いる生物処理法は、担体に微生物を保持させる固定床や流動床と比較して高い汚泥保持濃度が得られるため高負荷運転が可能である。このようなグラニュール汚泥を用いるＵＡＳＢ法等、ＥＧＳＢ法において、有機性排水を安定的かつ良好に処理する最大のポイントは、グラニュール汚泥を安定的に形成、維持させることである。反応槽内に、グラニュール汚泥を形成、維持させることができないと、処理性能は徐々に低下し、やがて処理不能に陥ることもある。このため、反応槽内のグラニュール汚泥を安定的に形成、維持させるための検討がなされている（例えば特許文献２）。 In these UASB method and EGSB method, granular sludge in which anaerobic microorganisms are granulated is used, and sludge containing anaerobic microorganisms is maintained and propagated in the form of granules (grains). The biological treatment method using granular sludge can be operated at a high load because a high sludge retention concentration can be obtained as compared with a fixed bed or fluidized bed in which microorganisms are held on a carrier. In the EGSB method such as the UASB method using granule sludge, the greatest point for stably and satisfactorily treating organic wastewater is to stably form and maintain granule sludge. If granule sludge cannot be formed and maintained in the reaction tank, the treatment performance gradually decreases and may eventually become untreatable. For this reason, studies have been made to stably form and maintain granular sludge in the reaction tank (for example, Patent Document 2).
従来のアルコール製造排水の処理方法のうち、直接嫌気ラグーンで処理する方法は、臭気、及びメタンのような温室効果ガスを環境中に排出してしまう問題がある。また、ＨＲＴ１００日以上の広大なスペースが必要となり、土地の有効利用の観点でも問題がある。 Of the conventional methods for treating alcohol production wastewater, the method of treating directly with an anaerobic lagoon has a problem of exhausting odors and greenhouse gases such as methane into the environment. Moreover, a vast space of 100 days or more for HRT is required, and there is a problem in terms of effective use of land.
アルコール製造排水を蒸留して得られた凝縮水を嫌気ラグーンで処理する方法では、アルコール製造排水中の窒素、リン、カリウムなどの肥料成分を濃縮（水量として１／３〜１／４程度）して肥料として回収、有効利用することができると共に、嫌気ラグーンに供する凝縮水のＣＯＤ濃度は蒸留前のアルコール製造排水よりも大幅に低減されているため、排水処理の有機物負荷が低減され、アルコール製造排水をそのまま直接嫌気ラグーン処理する場合よりも処理設備が小型化され、また良好な水質の処理水が得られるが、嫌気ラグーンを利用するかぎりにおいて、やはり、臭気、その他の排出ガス、必要スペースの問題が残る。 In the method of treating the condensed water obtained by distilling alcohol production wastewater with an anaerobic lagoon, fertilizer components such as nitrogen, phosphorus and potassium in the alcohol production wastewater are concentrated (about 1/3 to 1/4 of the amount of water). Can be recovered and used effectively as fertilizer, and the COD concentration of the condensed water used in the anaerobic lagoon is significantly lower than the alcohol production wastewater before distillation, reducing the organic load of wastewater treatment and producing alcohol. The treatment equipment is downsized compared to the case where wastewater is directly treated with anaerobic lagoon, and treated water with good water quality can be obtained. However, as long as the anaerobic lagoon is used, odor, other exhaust gas, and necessary space The problem remains.
そこで、アルコール製造排水の蒸留凝縮水の処理に、ＵＡＳＢ法やＥＧＳＢ法のような高負荷処理を適用しようとすると、この凝縮水は有機酸を主体とし、グラニュールを形成させるのに必要とされる糖などを含まないため、グラニュールを安定して形成、維持することができない上に、有機酸を中和するために多量のアルカリ剤が必要になるという問題がある。 Therefore, when applying high load treatment such as UASB method or EGSB method to the treatment of distilled condensate from alcohol production wastewater, this condensate is mainly composed of organic acids and is required to form granules. Therefore, there is a problem that a granule cannot be stably formed and maintained and a large amount of an alkaline agent is required to neutralize an organic acid.
本発明は上記従来の問題点を解決し、アルコール製造排水の蒸留凝縮水の嫌気処理において、アルカリ剤の消費量を抑えると共に、高負荷かつ安定した処理を行うことを可能とするアルコール製造排水の処理装置及び処理方法を提供することを課題とする。 The present invention solves the above-mentioned conventional problems, and in the anaerobic treatment of distilled condensed water of alcohol production wastewater, while reducing the consumption of alkaline agent, the alcohol production wastewater that makes it possible to perform high load and stable treatment It is an object to provide a processing apparatus and a processing method.
本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、アルコール製造排水の蒸留凝縮水の嫌気性処理に、処理水の一部を循環させながら、担体の表面に付着した嫌気性微生物により処理を行う上向流式流動床型嫌気反応槽を適用することにより、グラニュールを形成させる必要がなく、良好な処理を行うことができること、また、原水（凝縮水）に対する処理水の循環量を大きくすることで、処理水のアルカリ度を原水中の有機酸の中和に利用することができ、アルカリ剤の必要量を大幅に削減することができることを見出した。
なお、処理水の循環は、グラニュールを用いるＵＡＳＢ法、ＥＧＳＢ法でも行われるが、循環量を大きくすると嫌気性反応槽内の上向流速（ＬＶ）が上がり、グラニュールが流出しやすくなるため、ＬＶ２〜４ｍ／ｈｒ程度にまでしか循環量を高められないが、担体を用いた処理では、担体の沈降速度が２００〜５００ｍ／ｈｒと、グラニュールの沈降速度５０〜８０ｍ／ｈｒよりも著しく大きいため、ＬＶ４〜２０ｍ／ｈｒ程度まで循環量を大きくしても、微生物を保持して安定して処理を行うことができる。
As a result of intensive studies to solve the above problems, the present inventors have made anaerobic adhesion on the surface of the carrier while circulating a part of the treated water in anaerobic treatment of distilled condensed water of alcohol production wastewater. By applying an upflow fluidized bed type anaerobic reaction tank that treats with microorganisms, it is not necessary to form granules, and good treatment can be performed, and treated water for raw water (condensed water) It has been found that by increasing the amount of circulation, the alkalinity of the treated water can be used for neutralization of the organic acid in the raw water, and the required amount of alkaline agent can be greatly reduced.
The treated water is circulated by the UASB method and EGSB method using granules. However, increasing the circulation rate increases the upward flow velocity (LV) in the anaerobic reaction tank, and the granules are likely to flow out. The circulation rate can only be increased to about LV 2-4 m / hr, but in the treatment using the carrier, the sedimentation rate of the carrier is 200 to 500 m / hr, which is significantly higher than the granule sedimentation rate 50 to 80 m / hr. Therefore, even if the circulation rate is increased to about LV 4 to 20 m / hr, microorganisms can be retained and processing can be performed stably.
本発明はこのような知見に基づいて達成されたものであり、以下を要旨とする。 The present invention has been achieved based on such findings, and the gist thereof is as follows.
［１］ アルコール製造排水の製造工程から排出される有機性排水を蒸留処理して得られる凝縮水を嫌気性処理するアルコール製造排水の処理装置において、処理水の一部を循環水として循環させながら、担体の表面に付着した嫌気性微生物により処理を行う上向流式流動床型嫌気反応槽を備えるアルコール製造排水の処理装置であって、前記凝縮水が、ＣＯＤ Ｃｒ ５００〜２０，０００ｍｇ／Ｌで、全ＣＯＤ Ｃｒ 中有機酸成分を３０〜９０％含む有機酸含有水であり、前記嫌気反応槽で処理される前記凝縮水量に対する前記循環水量の比（循環水量／凝縮水量）で算出される循環比が５以上であることを特徴とするアルコール製造排水の処理装置。 [1] In an alcohol production wastewater treatment apparatus for anaerobically treating condensed water obtained by distillation treatment of organic wastewater discharged from the production process of alcohol production wastewater, while circulating a part of the treated water as circulating water An apparatus for treating wastewater from alcohol production comprising an upward flow fluidized bed type anaerobic reaction tank that performs treatment with anaerobic microorganisms adhering to the surface of the carrier , wherein the condensed water is COD Cr 500-20,000 mg / L The organic acid-containing water containing 30 to 90% of the organic acid component in the total COD Cr , and calculated by the ratio of the circulating water amount to the condensed water amount treated in the anaerobic reaction tank (circulating water amount / condensed water amount). A treatment apparatus for alcohol production waste water, wherein the circulation ratio is 5 or more .
［２］ ［１］において、前記嫌気反応槽の上向流速（ＬＶ）が４〜２０ｍ／ｈｒであることを特徴とするアルコール製造排水の処理装置。 [2] [1] Oite in the anaerobic upward flow rate of the reaction vessel (LV) is processing apparatus alcohol production wastewater, which is a 4 to 20 m / hr.
［３］[3]
［１］又は［２］において、前記担体は、比重１．１〜１．３、平均粒径１〜３０ｍｍであり、前記上向流式流動床型嫌気反応槽の担体充填率が１０〜８０％であることを特徴とするアルコール製造排水の処理装置。In [1] or [2], the carrier has a specific gravity of 1.1 to 1.3 and an average particle size of 1 to 30 mm, and a carrier filling rate of the upward flow type fluidized bed anaerobic reaction tank is 10 to 80. % Of alcohol wastewater treatment equipment.
［４］[4]
［１］ないし［３］のいずれかにおいて、前記上向流式流動床型嫌気反応槽における嫌気性処理条件が、温度２０〜６０℃、ｐＨ６〜８、槽負荷２〜４０ｋｇ−ＣＯＤIn any one of [1] to [3], the anaerobic treatment conditions in the upward flow type fluidized bed type anaerobic reaction tank are as follows: temperature 20 to 60 ° C., pH 6 to 8, tank load 2 to 40 kg-COD.
ＣｒCr
／ｍ/ M
３3
／ｄａｙであることを特徴とするアルコール製造排水の処理装置。/ Day is an apparatus for treating wastewater from alcohol production.
［５］[5]
［１］ないし［４］のいずれかにおいて、前記循環水は、前記凝縮水中の有機酸が分解されることで生成した重炭酸を含み、該凝縮水は、アルカリが添加されると共に、該循環水のアルカリ度を利用してｐＨ調整されることを特徴とするアルコール製造排水の処理装置。In any one of [1] to [4], the circulating water includes bicarbonate generated by decomposing an organic acid in the condensed water, and the condensed water is added with alkali and the circulating water. An apparatus for treating wastewater from alcohol production, wherein the pH is adjusted using the alkalinity of water.
［６］ アルコール製造排水の製造工程から排出される有機性排水を蒸留処理して得られる凝縮水を嫌気性処理するアルコール製造排水の処理方法において、該凝縮水を、処理水の一部を循環水として循環させながら、担体の表面に付着した嫌気性微生物により処理を行う上向流式流動床型嫌気反応槽に導入して嫌気性処理するアルコール製造排水の処理方法であて、前記凝縮水が、ＣＯＤ Ｃｒ ５００〜２０，０００ｍｇ／Ｌで、全ＣＯＤ Ｃｒ 中有機酸成分を３０〜９０％含む有機酸含有水であり、前記嫌気反応槽で処理される前記凝縮水量に対する前記循環水量の比（循環水量／凝縮水量）で算出される循環比を５以上とすることを特徴とするアルコール製造排水の処理方法。 [ 6 ] In an alcohol production wastewater treatment method for anaerobically treating condensed water obtained by distillation treatment of organic wastewater discharged from the production process of alcohol production wastewater, the condensed water is circulated through a part of the treated water. An alcohol production wastewater treatment method for introducing an anaerobic treatment into an upward flow fluidized bed type anaerobic reaction tank that performs treatment with anaerobic microorganisms attached to the surface of the carrier while circulating as water , wherein the condensed water is COD Cr 500-20,000 mg / L, organic acid-containing water containing 30-90% organic acid components in the total COD Cr , and the ratio of the circulating water amount to the condensed water amount treated in the anaerobic reaction tank ( A method of treating alcohol production wastewater, characterized in that the circulation ratio calculated by (circulated water amount / condensed water amount) is 5 or more .
［７］ ［６］において、前記嫌気反応槽の上向流速（ＬＶ）を４〜２０ｍ／ｈｒとすることを特徴とするアルコール製造排水の処理方法。 [7] The method for treating wastewater from alcohol production according to [ 6], wherein an upward flow velocity (LV) of the anaerobic reaction tank is 4 to 20 m / hr.
［８］[8]
［６］又は［７］において、前記担体は、比重１．１〜１．３、平均粒径１〜３０ｍｍであり、前記上向流式流動床型嫌気反応槽の担体充填率を１０〜８０％とすることを特徴とするアルコール製造排水の処理方法。In [6] or [7], the carrier has a specific gravity of 1.1 to 1.3 and an average particle size of 1 to 30 mm, and a carrier filling rate of the upward flow type fluidized bed anaerobic reaction tank is 10 to 80. % Of alcohol production wastewater.
［９］[9]
［６］ないし［８］のいずれかにおいて、前記上向流式流動床型嫌気反応槽における嫌気性処理条件が、温度２０〜６０℃、ｐＨ６〜８、槽負荷２〜４０ｋｇ−ＣＯＤIn any one of [6] to [8], the anaerobic treatment conditions in the upward flow type fluidized bed type anaerobic reaction tank are a temperature of 20 to 60 ° C., a pH of 6 to 8, and a tank load of 2 to 40 kg-COD.
ＣｒCr
／ｍ/ M
３3
／ｄａｙであることを特徴とするアルコール製造排水の処理方法。/ Day of alcohol production wastewater treatment method.
［１０］[10]
［６］ないし［９］のいずれかにおいて、前記循環水は、前記凝縮水中の有機酸が分解されることで生成した重炭酸を含み、該凝縮水にアルカリを添加すると共に、該循環水のアルカリ度を利用してｐＨ調整することを特徴とするアルコール製造排水の処理方法。In any one of [6] to [9], the circulating water contains bicarbonate generated by decomposing an organic acid in the condensed water, an alkali is added to the condensed water, and the circulating water is added. A method for treating wastewater from alcohol production, wherein the pH is adjusted using alkalinity.
本発明によれば、アルコール製造排水の蒸留凝縮水の嫌気処理において、アルカリ剤の消費量を抑えると共に、高負荷かつ安定した処理を行って、良好な水質の処理水を効率的に得ることができる。また、上向流式流動床型嫌気反応槽であれば、従来の嫌気ラグーンのように広大なスペースを必要とすることなく、臭気や排出ガスの問題も軽減される。 According to the present invention, in anaerobic treatment of distilled condensed water of alcohol production wastewater, while reducing the consumption of alkaline agent, it is possible to efficiently obtain high quality treated water by performing high load and stable treatment. it can. Further, in the upward flow type fluidized bed type anaerobic reaction tank, the problem of odor and exhaust gas is reduced without requiring a vast space like a conventional anaerobic lagoon.
以下に本発明の実施の形態を、図面を参照して詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
本発明で嫌気性処理する、アルコール製造排水の製造工程から排出される有機性排水を蒸留処理して得られる凝縮水とは、穀物などを糖化して得られた炭素源を酵母により発酵させて得られるアルコールを含有する発酵液を濃縮、蒸留し、必要に応じて更に精製することによりアルコールを製造するプロセスにおいて、発酵液の蒸留工程で蒸留塔の缶出液として排出される高濃度ＣＯＤ含有排水を蒸留した際に、濃縮残渣である蒸留塔缶出液を分離して得られるものであり、通常、高濃度ＣＯＤ含有排水を蒸留する蒸留塔の塔頂流出ガスを凝縮されて得られる。 The condensed water obtained by subjecting the organic wastewater discharged from the production process of the alcohol production wastewater to anaerobic treatment in the present invention is obtained by fermenting a carbon source obtained by saccharifying grains and the like with yeast. Containing high-concentration COD discharged as a bottom of the distillation column in the fermentation liquid distillation process in the process of producing alcohol by concentrating and distilling the resulting alcohol-containing fermentation liquid and further purifying as necessary When the waste water is distilled, it is obtained by separating the distillation column bottoms, which is a concentrated residue, and is usually obtained by condensing the tower top effluent gas of the distillation tower that distills the high concentration COD-containing waste water.
この凝縮水は、酢酸、プロピオン酸などの有機酸を主体とし、即ち、全ＣＯＤＣｒ中有機酸成分を３０〜９０％程度含み、ＣＯＤＣｒ濃度５００〜２０，０００ｍｇ／Ｌ程度で、ｐＨ３〜５程度の有機性排水である。 This condensed water is mainly composed of organic acids such as acetic acid and propionic acid, that is, contains about 30 to 90% of organic acid components in the total COD Cr , has a COD Cr concentration of about 500 to 20,000 mg / L, and a pH of 3 to 5. Organic drainage to the extent.
本発明においては、このような凝縮水を原水として、上向流式流動床型嫌気反応槽で嫌気性処理する。 In the present invention, such condensed water is used as raw water and an anaerobic treatment is performed in an upward flow type fluidized bed type anaerobic reaction tank.
図１は、本発明に係る上向流式流動床型嫌気反応槽を有する本発明のアルコール製造排水の処理装置の実施の形態を示す系統図である。
図１において、１はｐＨ調整槽、２は上向流式流動床型嫌気反応槽、３は処理水槽である。
ｐＨ調整槽１には、配管１１より原水である凝縮水が導入されると共に、処理水槽３から配管１２を経て処理水の一部が循環水として導入される。このｐＨ調整槽１には配管１３よりアルカリ剤が添加されｐＨ調整が行われる。
FIG. 1 is a system diagram showing an embodiment of a treatment apparatus for alcohol production wastewater of the present invention having an upward flow type fluidized bed anaerobic reaction tank according to the present invention.
In FIG. 1, 1 is a pH adjustment tank, 2 is an upward flow type fluidized bed type anaerobic reaction tank, and 3 is a treated water tank.
Condensed water, which is raw water, is introduced into the pH adjusting tank 1 from the
ｐＨ調整槽１でｐＨ調整された水は、配管１４より上向流式流動床型嫌気反応槽２の底部に導入される。嫌気反応槽２内には担体４が充填されており、嫌気反応槽２内に導入された水は、槽内を上向流で通水される過程で槽内の担体４を流動させつつ、この担体４に付着した嫌気性微生物により処理され、処理水は配管１５より処理水槽３に導入される。
The water whose pH is adjusted in the pH adjusting tank 1 is introduced into the bottom of the upward flow type fluidized bed type anaerobic reaction tank 2 through the
処理水槽３には、嫌気反応槽２から流出した担体を嫌気反応槽２に返送するための水中ポンプ５と返送配管１６が設けられており、流出担体は配管１６より嫌気反応槽２に返送される。また、処理水槽３内の処理水流出口近傍には、担体流出防止用のスクリーン６が設けられている。このスクリーン６を通過した処理水が配管１７より取り出され、一部が配管１２を経て循環水としてｐＨ調整槽１に循環され、残部は系外へ排出される。７は、スクリーン６の閉塞を防止するためにスクリーンを曝気洗浄するためのブロワであり、ブロワガスとしては、空気又は窒素ガスなどが用いられる。
The treated water tank 3 is provided with a submersible pump 5 and a
なお、図１は本発明のアルコール製造排水の処理装置の一例を示すものであって、本発明のアルコール製造排水の処理装置は何ら図示のものに限定されるものではない。
例えば、ｐＨ調整槽は必ずしも必要とされず、原水を嫌気反応槽の底部に導入する配管に循環水の循環配管を接続して循環水をライン注入してもよい。また、逆に、処理水の一部を嫌気反応槽底部に循環する循環配管に原水をライン注入してもよい。この場合、ｐＨ調整のためのアルカリ剤は、これらの配管にライン注入することができる。
In addition, FIG. 1 shows an example of the treatment apparatus for alcohol production waste water of the present invention, and the treatment apparatus for alcohol production waste water of the present invention is not limited to the illustrated one.
For example, the pH adjusting tank is not necessarily required, and the circulating water may be line-injected by connecting the circulating water circulating pipe to the pipe for introducing the raw water into the bottom of the anaerobic reaction tank. Conversely, the raw water may be injected into a circulation pipe that circulates a part of the treated water to the bottom of the anaerobic reaction tank. In this case, the alkaline agent for pH adjustment can be line-injected into these pipes.
また、処理水槽も必ずしも必要とされず、これを省略して、処理水の取出配管から分岐する循環水の循環配管で、処理水の一部を嫌気反応槽に循環させることもできる。この場合、担体の流出防止用のスクリーンは、嫌気反応槽内の処理水の取出口の近傍に設けられ、このスクリーンの閉塞防止用のブロワのブロワガスとしては、嫌気反応槽内の嫌気状態を維持するために窒素ガス等の酸素を含まないガスが用いられる。
また、更に嫌気反応槽の前段に中和槽や酸生成槽を設けることもできる。
Further, the treated water tank is not necessarily required, and a part of the treated water can be circulated to the anaerobic reaction tank by a circulating water circulating pipe branched from the treated water take-out pipe. In this case, the screen for preventing the carrier from flowing out is provided in the vicinity of the outlet for the treated water in the anaerobic reaction tank, and the blower gas of the blower for preventing the clogging of the screen is maintained in the anaerobic state in the anaerobic reaction tank. For this purpose, a gas not containing oxygen such as nitrogen gas is used.
Further, a neutralization tank and an acid generation tank can be provided upstream of the anaerobic reaction tank.
本発明において、上向流式流動床型嫌気反応槽に充填する担体の素材、形状、大きさ等は特に限定されないが、ポリオレフィン、ポリプロピレン等の樹脂製のものが好ましく、比重は１．１〜１．３程度の水よりも若干比重が大きいものが好ましい。また、担体の大きさは、平均粒径で１〜３０ｍｍ、特に３〜１０ｍｍ程度であることが好ましい。なお、ここで、粒径とは、担体が球形の場合はその直径であり、立方体であれば一辺の長さに該当するが、その他の異形形状の場合は、担体を２枚の平行な板で挟んだときに、その板の間隔が最も大きくなる部位の長さをさす。担体の形状としては、球形、立方体、直方体、棒状、筒状、盤状等各種のものを用いることができる。 In the present invention, the material, shape, size and the like of the carrier filled in the upward flow type fluidized bed type anaerobic reaction tank are not particularly limited, but those made of resin such as polyolefin and polypropylene are preferable, and the specific gravity is 1.1 to What has a specific gravity slightly larger than about 1.3 water is preferable. The size of the carrier is preferably about 1 to 30 mm, particularly about 3 to 10 mm in terms of average particle diameter. Here, the particle diameter is the diameter when the carrier is spherical, and corresponds to the length of one side if it is a cube, but in the case of other irregular shapes, the carrier is divided into two parallel plates. The length of the part where the interval between the plates is the largest when sandwiched between. Various shapes such as a spherical shape, a cubic shape, a rectangular parallelepiped shape, a rod shape, a cylindrical shape, and a disk shape can be used as the shape of the carrier.
また、上向流式流動床型嫌気反応槽の担体充填率（嫌気反応槽の有効容積に占める充填された担体の合計体積（見掛け体積）の割合）は、１０〜８０％、特に４０〜６０％程度とすることが処理効率の面で好ましい。 Further, the carrier filling rate of the upward flow type fluidized bed type anaerobic reaction tank (the ratio of the total volume (apparent volume) of the filled carrier to the effective volume of the anaerobic reaction tank) is 10 to 80%, particularly 40 to 60%. It is preferable in terms of processing efficiency to be about%.
このような上向流式流動床型嫌気反応槽における嫌気性処理において、原水（凝縮水）量に対する循環水量の比（循環水量／原水量）で算出される循環比が５以上、特に１０以上となるように処理水の一部を循環させることにより、処理水のアルカリ度を原水の中和に利用することの効果を有効に発揮させることができ、原水のｐＨ調整に必要なアルカリ剤の使用量を顕著に低減することができる。即ち、原水である凝縮水は、通常ｐＨ３〜５程度の酸性であるが、その嫌気処理水は、有機酸が分解除去されることで生成する重炭酸（アルカリ度）を含むため、処理水を原水のｐＨ調整に利用することができる。ただし、この循環比を過度に大きくすると処理効率が低下し、また、大容量の循環ポンプを必要とすることになるため、循環比は２０以下とすることが好ましい。 In such an anaerobic treatment in the upward flow type fluidized bed type anaerobic reaction tank, the circulation ratio calculated by the ratio of the circulating water amount to the raw water (condensed water) amount (circulating water amount / raw water amount) is 5 or more, particularly 10 or more. By circulating a part of the treated water so as to be, the effect of utilizing the alkalinity of the treated water for neutralizing the raw water can be effectively exhibited, and the alkaline agent necessary for adjusting the pH of the raw water The amount used can be significantly reduced. That is, the condensed water, which is raw water, is usually acidic at a pH of about 3 to 5, but the anaerobic treated water contains bicarbonate (alkalinity) produced by the decomposition and removal of the organic acid. It can be used for pH adjustment of raw water. However, if the circulation ratio is excessively increased, the processing efficiency is lowered and a large-capacity circulation pump is required. Therefore, the circulation ratio is preferably 20 or less.
その他の嫌気性処理条件は特に制限されるものではないが、以下のような条件を採用することが処理効率の面で好ましい。
温度：２０〜６０℃、好ましくは２５〜３８℃又は５０〜５５℃
ｐＨ：６〜８
槽負荷：２〜４０ｋｇ−ＣＯＤＣｒ／ｍ３／ｄａｙ
上向流速（ＬＶ）：４〜２０ｍ／ｈｒ
Other anaerobic treatment conditions are not particularly limited, but it is preferable in terms of treatment efficiency to adopt the following conditions.
Temperature: 20-60 ° C, preferably 25-38 ° C or 50-55 ° C
pH: 6-8
Tank load: 2 to 40 kg-COD Cr / m 3 / day
Upward flow velocity (LV): 4-20m / hr
以下に実施例を挙げて本発明をより具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to examples.
［実施例１］
バイオエタノール製造排水を蒸留処理して得られた下記水質の凝縮水を原水として、槽容量４Ｌ（直径１０ｃｍ×高さ５０ｃｍの円筒状）の上向流式流動床型嫌気反応槽を用いた図１に示す処理装置により、以下の条件で嫌気性処理を行った。
[Example 1]
A diagram using an upflow type fluidized bed type anaerobic reaction tank with a tank capacity of 4 L (diameter 10 cm × height 50 cm cylindrical) using the following water quality condensed water obtained by distillation treatment of bioethanol production wastewater as raw water An anaerobic treatment was performed under the following conditions using the treatment apparatus shown in FIG.
＜原水水質＞
ｐＨ：４〜５
ＣＯＤＣｒ：５０００〜６０００ｍｇ／Ｌ
（ＣＯＤＣｒに占める酢酸、プロピオン酸等の有機酸の割合は６０〜８０％）
<Raw water quality>
pH: 4-5
COD Cr : 5000 to 6000 mg / L
(The proportion of organic acids such as acetic acid and propionic acid in COD Cr is 60-80%)
＜嫌気性処理条件＞
原水処理量：１６Ｌ／ｄａｙ
温度：３５℃
担体：菌体が付着したポリプロピレン製円筒状担体
担体の大きさ：直径３ｍｍ×長さ５ｍｍ
担体充填量：１．６Ｌ
担体充填率：４０％
嫌気反応槽の槽負荷：２０ｋｇ−ＣＯＤＣｒ／ｍ３／ｄａｙ
<Anaerobic treatment conditions>
Raw water treatment amount: 16L / day
Temperature: 35 ° C
Carrier: Polypropylene cylindrical carrier with bacterial cells attached
Carrier size: 3mm diameter x 5mm length
Carrier filling amount: 1.6L
Carrier filling rate: 40%
Tank load of anaerobic reaction tank: 20 kg-COD Cr / m 3 / day
ｐＨ調整槽では２Ｎ ＮａＯＨを添加してｐＨ６．５に調整した。 In the pH adjusting tank, 2N NaOH was added to adjust the pH to 6.5.
処理水の循環比を０（循環を行わず）、１（原水と同量の循環）、４、８、１０、１５、２０の数段階で変えて、ＬＶ０．７〜１４ｍ／ｈｒの範囲で処理を行ったところ、いずれの条件においても、処理水のＣＯＤＣｒは１，０００ｍｇ／Ｌ以下となり、８０％以上の除去率が得られた。
各循環比におけるｐＨ調整槽におけるＮａＯＨ消費量を表１に示す。
Change the treatment water circulation ratio to 0 (no circulation), 1 (circulation in the same amount as raw water), 4, 8, 10, 15, 20 in several stages, and in the range of LV 0.7-14 m / hr When the treatment was performed, the COD Cr of the treated water was 1,000 mg / L or less under any condition, and a removal rate of 80% or more was obtained.
Table 1 shows the NaOH consumption in the pH adjusting tank at each circulation ratio.
表１より、循環比が高いほどＮａＯＨ消費量が少なくなり、循環比１０以上では処理水を循環しない場合のＮａＯＨ消費量の２０％以下に低減できることが分かる。 From Table 1, it can be seen that the higher the circulation ratio, the less the NaOH consumption, and a circulation ratio of 10 or more can be reduced to 20% or less of the NaOH consumption when the treated water is not circulated.
１ ｐＨ調整槽
２ 上向流式流動床型嫌気反応槽
３ 処理水槽
４ 担体
５ 水中ポンプ
６ スクリーン
７ ブロワ
DESCRIPTION OF SYMBOLS 1 pH adjustment tank 2 Upflow type fluidized bed type anaerobic reaction tank 3 Treated water tank 4 Carrier 5 Submersible pump 6
Claims (10)
前記凝縮水が、ＣＯＤ Ｃｒ ５００〜２０，０００ｍｇ／Ｌで、全ＣＯＤ Ｃｒ 中有機酸成分を３０〜９０％含む有機酸含有水であり、
前記嫌気反応槽で処理される前記凝縮水量に対する前記循環水量の比（循環水量／凝縮水量）で算出される循環比が５以上であることを特徴とするアルコール製造排水の処理装置。 In an alcohol production wastewater treatment device that anaerobically treats condensed water obtained by distillation treatment of organic wastewater discharged from the production process of alcohol production wastewater, while circulating a part of the treated water as circulating water, An apparatus for treating wastewater from alcohol production comprising an upward flow fluidized bed type anaerobic reaction tank that performs treatment with anaerobic microorganisms attached to the surface ,
The condensed water is COD Cr 500-20,000 mg / L, and is an organic acid-containing water containing 30-90% of an organic acid component in the total COD Cr ;
An apparatus for treating alcohol production wastewater, wherein a circulation ratio calculated by a ratio of the amount of circulating water to the amount of condensed water to be treated in the anaerobic reaction tank (circulating water amount / condensed water amount) is 5 or more .
前記凝縮水が、ＣＯＤ Ｃｒ ５００〜２０，０００ｍｇ／Ｌで、全ＣＯＤ Ｃｒ 中有機酸成分を３０〜９０％含む有機酸含有水であり、
前記嫌気反応槽で処理される前記凝縮水量に対する前記循環水量の比（循環水量／凝縮水量）で算出される循環比を５以上とすることを特徴とするアルコール製造排水の処理方法。 In an alcohol production wastewater treatment method for anaerobically treating condensed water obtained by distillation treatment of organic wastewater discharged from the production process of alcohol production wastewater, the condensed water is circulated using a part of the treated water as circulating water. A method for treating alcohol production wastewater that is introduced into an upward flow fluidized bed type anaerobic reaction tank that is treated with anaerobic microorganisms attached to the surface of the carrier and anaerobically treated ,
The condensed water is COD Cr 500-20,000 mg / L, and is an organic acid-containing water containing 30-90% of an organic acid component in the total COD Cr ;
A method for treating alcohol production wastewater, wherein a circulation ratio calculated by a ratio of the amount of circulating water to the amount of condensed water treated in the anaerobic reaction tank (circulating water amount / condensed water amount) is 5 or more .
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| JP2013121861A JP5846160B2 (en) | 2013-06-10 | 2013-06-10 | Alcohol production wastewater treatment device and treatment method |
| MYPI2015704497A MY169243A (en) | 2013-06-10 | 2014-06-10 | Apparatus and method for treating alcohol-production wastewater |
| PCT/JP2014/065308 WO2014199972A1 (en) | 2013-06-10 | 2014-06-10 | Alcohol production waste water treatment device, and treatment method |
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| JP4184021B2 (en) * | 2002-09-30 | 2008-11-19 | 月島機械株式会社 | Method for producing alcohol |
| JP4350495B2 (en) * | 2003-12-15 | 2009-10-21 | 住友重機械エンバイロメント株式会社 | Organic sludge volume reduction device and wastewater treatment device |
| JP5017725B2 (en) * | 2007-12-20 | 2012-09-05 | 水ｉｎｇ株式会社 | Anaerobic treatment method and apparatus |
| JP5114780B2 (en) * | 2008-08-12 | 2013-01-09 | 水ｉｎｇ株式会社 | Anaerobic treatment method and apparatus |
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