TW201631147A - Manufacturing method and use of nutritional composition for anaerobic microorganisms to buffer pH value of water - Google Patents

Manufacturing method and use of nutritional composition for anaerobic microorganisms to buffer pH value of water Download PDF

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TW201631147A
TW201631147A TW104105727A TW104105727A TW201631147A TW 201631147 A TW201631147 A TW 201631147A TW 104105727 A TW104105727 A TW 104105727A TW 104105727 A TW104105727 A TW 104105727A TW 201631147 A TW201631147 A TW 201631147A
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anaerobic
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microbial nutrient
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TWI546378B (en
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林漢福
梁書豪
簡華逸
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台灣氯乙烯工業股份有限公司
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Abstract

A manufacturing method and a use of a nutritional composition for anaerobic microorganisms to buffer pH value of water are provided. The nutritional composition mainly contains organic nutritional substrate and further contains Mg(OH)2 which is mixed with fatty acids of oils in the organic nutritional substrate to react and form magnesium salts of fatty acids and glycerol. Both of the magnesium salts of fatty acids and glycerol can be used as a long-acting buffering substance to provide a long-term pH buffering function for releasing OH<SP>-</SP>. Thus, when the nutritional composition is injected into the underground water for accelerating in-situ anaerobic microorganisms to degrade chlorinated organic contaminants, the nutritional composition can efficiently neutralize organic acids generated by anaerobic reactions of the anaerobic microorganisms, and maintain the neutral pH environment of the underground water for a long time, so that it is suitable for the anaerobic microorganisms to grow well.

Description

緩衝水體酸鹼值之厭養微生物營養基質及其用途 Anti-microbial nutrient substrate buffering water pH value and use thereof

本發明係關於一種緩衝水體酸鹼值之厭養微生物營養基質及其用途,特別是關於一種藉由氫氧化鎂產生之緩衝物質以供緩衝地下水體酸鹼值之厭養微生物可利用的營養基質及其用途。 The present invention relates to a pH-reducing microbial nutrient matrix for buffering water body and its use, and particularly relates to a nutrient matrix which can be utilized by a buffer substance produced by magnesium hydroxide for buffering the pH value of the groundwater body. And its use.

各種微生物都有其專屬最適合生長之pH值環境,雖然在低(高)pH值環境中之嗜酸(鹼)菌已被篩出,但大多數之微生物皆適於中性環境(pH值6-8),中性之pH有利於提升微生物生長反應效率。例如,目前已知許多可進行還原脫氯之重要菌群亦適於中性生長環境,如Dehalococcoides脫鹵菌群,其中已知能夠降解乙烯、四氯乙烯的一種脫鹵菌群之生長pH值介於6.8-7.5之間。相似的,數種可降解氯乙烯、乙烷之Desulfitobacterium脫鹵脫亞硫酸菌群之最適pH值範圍亦是接近中性的。因此,維持一個穩定的pH環境是促進脫氯反應一個重要的環節。 All microorganisms have their own pH environment that is most suitable for growth. Although the acidophilic (alkali) bacteria have been screened out in low (high) pH environments, most of the microorganisms are suitable for neutral environment (pH value). 6-8), the neutral pH is beneficial to enhance the efficiency of microbial growth reaction. For example, many important microflora that can be subjected to reductive dechlorination are also known to be suitable for neutral growth environments, such as Dehalococcoides dehalogenating bacteria, in which the growth pH of a dehalogenating group capable of degrading ethylene and tetrachloroethylene is known. Between 6.8-7.5. Similarly, the optimum pH range for several Desulfitobacterium dehalogenated desulfurous bacteria groups that degrade vinyl chloride and ethane is also near neutral. Therefore, maintaining a stable pH environment is an important part of promoting dechlorination.

厭氧微生物之還原脫氯反應為一產酸反應,其必須有足夠的pH緩衝物質來維持反應發生。在天然水體環境中,pH緩衝系統通常為碳酸/重碳酸系統,在還原脫氯反應進行時,鹽酸的產生會使重碳酸鹽生成二氧化碳(碳酸),且不易逸散致大氣而殘留於水體中:HCl+HCO3 - → H2CO3+Cl- The reductive dechlorination reaction of anaerobic microorganisms is an acidogenic reaction, which must have sufficient pH buffering material to maintain the reaction. In a natural water environment, the pH buffer system is usually a carbonic acid/dicarbonate system. When the reductive dechlorination reaction is carried out, the production of hydrochloric acid causes the bicarbonate to form carbon dioxide (carbonic acid), which is not easily dissipated into the atmosphere and remains in the water. :HCl+HCO 3 - → H 2 CO 3 +Cl -

重碳酸鹽濃度的降低及碳酸的產生皆伴隨造成pH值的降低:H2O+CO2 → H2CO3 → H++HCO3 - The decrease in bicarbonate concentration and the production of carbonic acid are accompanied by a decrease in pH: H 2 O+CO 2 → H 2 CO 3 → H + + HCO 3 -

此外,當多數有機物經發酵產生氫後,也會形成醋酸並降低 pH值:CH3COOH → H++CH3COO- In addition, when most organic matter is fermented to produce hydrogen, acetic acid is also formed and the pH is lowered: CH 3 COOH → H + +CH 3 COO -

在原始地下水環境中,pH值通常不易變動,大部分pH值發生變動之原因係例如:生物降解產生酸性物質、現地化學氧化劑注入及電子供給者注入環境中等情況。過去為了提高地下水之緩衝能力通常須注入高溶解性基質或鹼(酸)性物質,來提高地下水之鹼(酸)度,但並無法長時間穩定維持。因此,在一般地下水之厭氧生物復育工法施作中,除了會以灌注有機基質進行現地微生物培養外,若有pH調整問題則需額外添加pH緩衝藥劑。 In the original groundwater environment, the pH value is usually not easy to change, and most of the pH changes are caused by, for example, biodegradation to produce acidic substances, local chemical oxidant injection, and electron donor injection into the environment. In the past, in order to improve the buffer capacity of groundwater, it is usually necessary to inject a highly soluble matrix or an alkali (acid) substance to increase the alkali (acid) degree of groundwater, but it cannot be stably maintained for a long time. Therefore, in the general anaerobic biological rehabilitative method of groundwater, in addition to the in-situ microbial culture with the infusion of the organic substrate, if there is a pH adjustment problem, an additional pH buffering agent is required.

在目前地下水厭氧生物復育工法施作中,最常見的pH調整藥劑為氫氧化鈉(NaOH)及氫氧化鉀(KOH),於其他工程領域中,此兩者也被經常被使用為pH調整的藥劑。然而,氫氧化鈉及氫氧化鉀對於施作中的工人皆具有安全危害,施作不當可能造成腐蝕性的職業傷害;另外,若其使用劑量控制不當,可能會造成含水層pH值過高,不利於微生物反應;此外,地下含水層中氫氧化錯合物沉澱也會造成地下水井之井篩阻塞和透水性降低;且長期大量使用氫氧化鈉或氫氧化鉀也會造成地下水體中鈉或鉀離子濃度偏高,導致存在使地下水層及土層鹽化的疑慮,對於下游不慎取水飲用的居民恐有健康之危害。另一方面,碳酸鈉(Na2CO3)及碳酸氫鈉(NaHCO3)雖也可用於地下水體中提供低鹼度的酸鹼緩衝能力,但由於鹼度提供量較低,因此其用量必需提高,然而長期大量使用後同樣會造成鈉離子濃度偏高,致使水層、土層鹽化。 In the current groundwater anaerobic bioremediation method, the most common pH adjusting agents are sodium hydroxide (NaOH) and potassium hydroxide (KOH). In other engineering fields, the two are often used for pH adjustment. Pharmacy. However, sodium hydroxide and potassium hydroxide are safe for workers in the application. Improper application may cause corrosive occupational injuries. In addition, improper use of dose control may cause the pH of the aquifer to be too high, which is not conducive to Microbial reaction; in addition, the precipitation of hydroxide complex in the underground aquifer will also cause the well screen obstruction and water permeability of the groundwater well; and the long-term use of sodium hydroxide or potassium hydroxide will also cause sodium or potassium ions in the groundwater. The high concentration leads to doubts about the salinization of the groundwater layer and the soil layer, which may pose a health hazard to residents who are inadvertently taking water downstream. On the other hand, sodium carbonate (Na 2 CO 3 ) and sodium bicarbonate (NaHCO 3 ) can be used to provide low alkalinity acid-base buffering capacity in groundwater, but because of the low alkalinity supply, the amount must be It is improved, but after a long period of heavy use, the sodium ion concentration is also high, causing the water layer and the soil layer to be salinized.

故,有必要提供一種能夠緩衝水體酸鹼值之厭養微生物營養基質,以解決上述習用技術所存在的問題。 Therefore, it is necessary to provide an anaesthetic microbial nutrient substrate capable of buffering the pH value of a water body to solve the problems of the above conventional techniques.

本發明之主要目的在於提供一種緩衝水體酸鹼值之厭養微生物營養基質及其用途,該厭養微生物營養基質係以有機厭氧基質為基礎進一步添加氫氧化鎂(Mg(OH)2),藉由氫氧化鎂與有機厭氧基質之脂肪酸混 和生成脂肪酸鎂鹽及甘油,利用脂肪酸鎂鹽及甘油做為長效緩衝物質,以提供長期緩慢釋放鹼度之pH緩衝能力,因而可以在注入地下水中促使現地厭氧微生物(如Dehalococcoides sp.)降解水中含氯有機污染物時,有效的中和厭氧微生物反應產生之有機酸,並且長時間的維持水體中最適合厭氧微生物反應之中性pH值環境。 The main object of the present invention is to provide a anaerobic microbial nutrient matrix for buffering water body pH value, and the anatrophic microbial nutrient matrix is further added with magnesium hydroxide (Mg(OH) 2 ) based on organic anaerobic substances. By mixing magnesium hydroxide with organic anaerobic fatty acids to form fatty acid magnesium salts and glycerol, and using fatty acid magnesium salts and glycerin as long-acting buffer substances to provide long-term slow release alkalinity pH buffering capacity, it is possible to inject groundwater. Inducing local anaerobic microorganisms (such as Dehalococcoides sp. ) to effectively neutralize organic acids produced by anaerobic microbial reactions when degrading chlorinated organic pollutants in water, and maintaining the most suitable anaerobic microbial reaction in water for a long time. pH environment.

為達上述之目的,本發明提供一種緩衝水體酸鹼值之厭養微生物營養基質,其包含46~55重量份之植物油、0.46~0.5重量份之氫氧化鎂(Mg(OH)2)、3.7~5重量份之生物可分解界面活性劑、2.3~4重量份之維生素及46~50重量份之水;在該厭養微生物營養基質中,氫氧化鎂與植物油之脂肪酸混和生成脂肪酸鎂鹽及甘油,該厭養微生物營養基質以脂肪酸鎂鹽及甘油做為長效緩衝物質,用以提供一長期pH緩衝能力。 In order to achieve the above object, the present invention provides a anaerobic microbial nutrient substrate for buffering water body pH, comprising 46 to 55 parts by weight of vegetable oil, 0.46 to 0.5 parts by weight of magnesium hydroxide (Mg(OH) 2 ), 3.7. ~5 parts by weight of biodegradable surfactant, 2.3 to 4 parts by weight of vitamins and 46 to 50 parts by weight of water; in the anatrophic microbial nutrient matrix, magnesium hydroxide is mixed with vegetable oil fatty acid to form fatty acid magnesium salt and Glycerin, the anatrophic microbial nutrient matrix uses fatty acid magnesium salts and glycerin as long-acting buffers to provide a long-term pH buffering capacity.

在本發明之一實施例中,該厭養微生物營養基質包含46重量份之植物油、0.46重量份之氫氧化鎂、3.7重量份之生物可分解界面活性劑、2.3重量份之維生素及46重量份之水。 In an embodiment of the invention, the anatrophic microbial nutrient substrate comprises 46 parts by weight of vegetable oil, 0.46 parts by weight of magnesium hydroxide, 3.7 parts by weight of biodegradable surfactant, 2.3 parts by weight of vitamins and 46 parts by weight. Water.

在本發明之一實施例中,該厭養微生物營養基質係具有一油滴懸浮液之形式,該油滴懸浮液中懸浮有數個油滴微粒。 In one embodiment of the invention, the anatrophic microbial nutrient substrate is in the form of an oil droplet suspension in which a plurality of oil droplet particles are suspended.

在本發明之一實施例中,該脂肪酸鎂鹽及甘油混於該油滴懸浮液之數個油滴中。 In one embodiment of the invention, the fatty acid magnesium salt and glycerin are mixed in a plurality of oil droplets of the oil droplet suspension.

在本發明之一實施例中,該油滴微粒具有一粒徑範圍介於1-2μm(微米)。 In one embodiment of the invention, the oil droplet particles have a particle size ranging from 1-2 [mu]m (micrometers).

在本發明之一實施例中,該維生素例如為維生素B群。 In an embodiment of the invention, the vitamin is, for example, a vitamin B group.

在本發明之一實施例中,該維生素B群主要包含維生素B12。 In one embodiment of the invention, the vitamin B population comprises primarily vitamin B12.

在本發明之一實施例中,該生物可分解界面活性劑係選自親油性界面活性劑或親水性界面活性劑。 In one embodiment of the invention, the biodegradable surfactant is selected from the group consisting of lipophilic surfactants or hydrophilic surfactants.

在本發明之一實施例中,該親油性界面活性劑係選自卵磷脂。 In one embodiment of the invention, the lipophilic surfactant is selected from the group consisting of lecithin.

在本發明之一實施例中,該親水性界面活性劑係選自丁基溶纖劑或無患子萃取物皂甙。 In one embodiment of the invention, the hydrophilic surfactant is selected from the group consisting of butyl cellosolve or sapindus extract saponin.

再者,本發明提供另一種緩衝水體酸鹼值之厭養微生物營養基質,其包含植物油、氫氧化鎂、生物可分解界面活性劑、維生素及水,其中氫氧化鎂佔該厭養微生物營養基質之總重量的0.46~0.5wt%;在該厭養微生物營養基質中,氫氧化鎂與植物油之脂肪酸混和生成脂肪酸鎂鹽及甘油,該厭養微生物營養基質以脂肪酸鎂鹽及甘油做為長效緩衝物質,用以提供一長期pH緩衝能力。 Furthermore, the present invention provides another anaerobic microbial nutrient matrix for buffering water pH, which comprises vegetable oil, magnesium hydroxide, biodegradable surfactant, vitamins and water, wherein magnesium hydroxide occupies the nutrient matrix of the anatrophic microorganism The total weight is 0.46~0.5wt%; in the anatrophic microbial nutrient matrix, the magnesium hydroxide is mixed with the fatty acid of the vegetable oil to form the fatty acid magnesium salt and the glycerin, and the anatrophic microbial nutrient matrix is long-acting with the fatty acid magnesium salt and glycerin. Buffer material to provide a long-term pH buffering capacity.

另外,本發明提供一種緩衝水體酸鹼值之厭養微生物營養基質之用途,其係將上述厭養微生物營養基質經由一地下水井注入一地下水含水層中,以促使現地厭氧微生物降解地下水中之含氯有機污染物,其中該厭養微生物營養基質以脂肪酸鎂鹽及甘油做為長效緩衝物質,用以提供一長期pH緩衝能力,以便有效的中和厭氧微生物反應產生之有機酸,並且長時間的維持水體中最適合厭氧微生物反應之中性pH值環境。 In addition, the present invention provides a use of a buffered water body pH value of an anatomic microbial nutrient substrate, which is injected into a groundwater aquifer via a groundwater well to promote local anaerobic microorganisms to degrade groundwater. a chlorinated organic contaminant, wherein the anatrophic microbial nutrient substrate uses a fatty acid magnesium salt and glycerin as a long-acting buffer material to provide a long-term pH buffering capacity for effectively neutralizing the organic acid produced by the anaerobic microbial reaction, and Long-term maintenance of the water is most suitable for anaerobic microbial reactions in a neutral pH environment.

在本發明之一實施例中,該含氯有機污染物係為三氯乙烯。 In one embodiment of the invention, the chlorine-containing organic contaminant is trichloroethylene.

在本發明之一實施例中,該厭氧微生物之代表性菌種係為脫鹵菌群(Dehalococcoides sp.)。 In an embodiment of the present invention, the representative strain of the anaerobic microorganism is Dehalococcoides sp .

為了讓本發明之上述及其他目的、特徵、優點能更明顯易懂,下文將特舉本發明較佳實施例,作詳細說明如下。 The above and other objects, features, and advantages of the present invention will become more apparent from

根據本發明之一較佳實施例,本發明提供一種用以緩衝水體酸鹼值之厭養微生物營養基質,其主要用途係應用於生物復育法之綠色整治技術領域中,以提供厭養微生物生長所需之營養源,用於刺激(bio-stimulation)現地原生菌之數量,進而加速生物降解有機污染物之效率,達到環境友善、綠色整治及生物復育等目的,本發明之厭養微生物營養基質可以在注入地下水中促使現地厭氧微生物(如Dehalococcoides sp.)降解水中含氯有機污染物時,有效的中和厭氧微生物反應產生之有機酸,並且長時間的維持水體中最適合厭氧微生物反應之中性pH值環境,以加強地下水目標污染物之生物降解能力及緩和因厭氧反應造成pH降低之土壞酸化問題。上述有機污染物例如為重質非水相溶液(dense non-aqueous phase liquids,DNAPL)中之含氯有機污染物,特別是指氯乙烯(vinyl chloride,VC)、二氯 乙烯(dichloroethylene,DCE)、三氯乙烯(trichloroethylene,TCE)、四氯乙烯(tetrachloroethylene,PCE)、二氯甲烷(dichloromethane)或氯仿(chloroform)等,但並不限於此。上述之綠色整治主要指地下水遭受污染之現地整治,例如為受DNAPL(特別是VC、DCE、TCE)污染地下水之現地整治。 According to a preferred embodiment of the present invention, the present invention provides a anaesthetic microbial nutrient substrate for buffering water pH value, and the main use thereof is applied to the field of green remediation technology of biological rejuvenation method to provide anatrophic microorganisms. The nutrient source required for growth, used for stimulating (bio-stimulation) the number of native protozoa, thereby accelerating the efficiency of biodegradable organic pollutants, achieving environmental friendliness, green remediation and biological rejuvenation, etc., the anatrophic microorganism of the present invention The nutrient substrate can effectively neutralize the organic acids produced by the anaerobic microbial reaction when the in situ anaerobic microorganisms (such as Dehalococcoides sp. ) degrade the chlorinated organic pollutants in the water, and maintain the most suitable water in the water for a long time. The oxygen microbial reaction neutralizes the neutral pH environment to enhance the biodegradability of the groundwater target pollutants and to alleviate the problem of soil acidification caused by anaerobic reaction. The above organic pollutants are, for example, chlorine-containing organic pollutants in dense non-aqueous phase liquids (DNAPL), especially vinyl chloride (VC), dichloroethylene (DCE), Trichloroethylene (TCE), tetrachloroethylene (PCE), dichloromethane or chloroform, but not limited thereto. The above-mentioned green remediation mainly refers to the remediation of groundwater contaminated, for example, the remediation of groundwater contaminated by DNAPL (especially VC, DCE, TCE).

地下水之厭氧生物復育工法施作中,常會以灌注有機基質進行現地微生物培養,若有pH調整問題則需額外添加緩衝藥劑。本發明之厭養微生物營養基質,主要應用即針對緩衝能力不佳之現地地下水環境,由於本發明之厭養微生物營養基質是以有機厭氧基質為基礎再額外添加氫氧化鎂(Mg(OH)2),因此可釋放氫氧根離子直接進行緩衝,同時也可藉由氫氧化鎂預先與有機厭氧基質中之脂肪酸混和生成脂肪酸鎂鹽及甘油,再進一步利用脂肪酸鎂鹽及甘油做為另一長效緩衝物質,以便在整治地下水環境時長期緩慢釋放鹼度(如OH-),因而具有長時間的維持水體中最適合厭氧微生物反應之中性pH值環境之長效緩衝能力,也就是可以在厭氧微生物(如Dehalococcoides sp.)對有機厭氧基質進行厭氧反應酸化水解釋放出有機酸時,中和該厭氧反應所產生之有機酸,以長期維持中性pH環境。 In the application of anaerobic biological rehabilitative methods for groundwater, in-situ microbial culture is often carried out by infusion of organic substrates. If pH adjustment is required, additional buffering agents are required. The anaesthetic microbial nutrient substrate of the present invention is mainly applied to a local groundwater environment with poor buffering capacity, and the anatrophic microbial nutrient substrate of the present invention is additionally added with magnesium hydroxide (Mg(OH) 2 based on organic anaerobic materials). Therefore, the hydroxide ion can be directly buffered, and the magnesium salt and the glycerin can be formed by mixing the fatty acid in the organic anaerobic substance with magnesium hydroxide, and further using the fatty acid magnesium salt and glycerin as another Long-acting buffer material for long-term slow release of alkalinity (such as OH - ) during remediation of the groundwater environment, thus having a long-term buffering capacity to maintain the neutral pH environment most suitable for anaerobic microbial reactions in water, ie When an organic acid is released by an anaerobic reaction of an anaerobic microorganism (such as Dehalococcoides sp. ) to release an organic acid, the organic acid produced by the anaerobic reaction is neutralized to maintain a neutral pH environment for a long period of time.

C3H5(COOC17H35)3+3Mg(OH)2 → 3C17H35COOMg+C3H5(OH)2 C 3 H 5 (COOC 17 H 35 ) 3 +3Mg(OH) 2 → 3C 17 H 35 COOMg+C 3 H 5 (OH) 2

更詳細來說,本發明之厭養微生物營養基質包含:46~55重量份之植物油、0.46~0.5重量份之氫氧化鎂(Mg(OH)2)、3.7~5重量份之生物可分解界面活性劑、2.3~4重量份之維生素及46~50重量份之水,且上述成份加以充份混合後並具有一油滴懸浮液之形式,該油滴懸浮液中懸浮有數個油滴微粒,亦即其中之植物油與生物可分解界面活性劑(及維生素)會形成油滴狀物(即油滴微粒)均勻懸浮分散於液態水中,而氫氧化鎂與植物油油滴混和生成之脂肪酸鎂鹽及甘油。 In more detail, the anatrophic microbial nutrient substrate of the present invention comprises: 46 to 55 parts by weight of vegetable oil, 0.46 to 0.5 parts by weight of magnesium hydroxide (Mg(OH) 2 ), and 3.7 to 5 parts by weight of a biodegradable interface. An active agent, 2.3 to 4 parts by weight of vitamins and 46 to 50 parts by weight of water, and the above ingredients are sufficiently mixed and have an oil droplet suspension in which a plurality of oil droplet particles are suspended. That is, the vegetable oil and the biodegradable surfactant (and vitamin) form oil droplets (ie, oil droplets) uniformly dispersed and dispersed in liquid water, and the fatty acid magnesium salt formed by mixing magnesium hydroxide with vegetable oil oil and glycerin.

在本發明之厭養微生物營養基質中,植物油可以選自大豆油、花生油、葵花油、芥花油、橄欖油、棕櫚油、苦茶油、芝麻油、紅花籽油、玉米油、玄米油、胡桃油或葡萄籽油等各種不同碳鏈長度之脂肪族植物性油類,其提供現地厭氧微生物生長所需之主要有機營養源,用於刺激現地原生菌之數量。該植物油之使用量可為46~55重量份,例如48、50、52或54等,但不限於此。 In the anatrophic microbial nutrient matrix of the present invention, the vegetable oil may be selected from the group consisting of soybean oil, peanut oil, sunflower oil, canola oil, olive oil, palm oil, bitter tea oil, sesame oil, safflower seed oil, corn oil, black rice oil, and walnut. Alien vegetable oils of various carbon chain lengths, such as oil or grape seed oil, provide the main source of organic nutrients needed for the growth of anaerobic microorganisms in the field to stimulate the number of native protozoa. The vegetable oil may be used in an amount of 46 to 55 parts by weight, such as 48, 50, 52 or 54, etc., but is not limited thereto.

再者,該生物可分解界面活性劑可選自親油性界面活性劑或親水性界面活性劑,其中該親油性界面活性劑較佳係選自卵磷脂;該親水性界面活性劑較佳係選自丁基溶纖劑(Simple Green,SG,又稱為2-丁氧基乙醇)或天然無患子萃取物皂甙,但並不限於此。該生物可分解界面活性劑之使用量可為3.7~5重量份,例如3.8、4.0、4.2、4.4、4.5、4.6或4.8等,但不限於此。 Furthermore, the biodegradable surfactant may be selected from a lipophilic surfactant or a hydrophilic surfactant, wherein the lipophilic surfactant is preferably selected from lecithin; and the hydrophilic surfactant is preferably selected. It is not limited to butyl cellosolve (Simple Green, SG, also known as 2-butoxyethanol) or natural sapindus extract saponin. The biodegradable surfactant may be used in an amount of 3.7 to 5 parts by weight, such as 3.8, 4.0, 4.2, 4.4, 4.5, 4.6 or 4.8, etc., but is not limited thereto.

另外,在本發明一實施例中,依地下水遭受污染之現地土壤的土質或其微生物種類的不同,該緩釋型複合基質另可選擇性包含維生素,該維生素例如為維生素B群,特別是維生素B12。該維生素用以作為現地微生物之營養物質,以促進其生長,其溶於該油滴狀懸浮微粒中或液態水中。該維生素之使用量可為2.3~4重量份,例如2.4、2.6、2.8、3.0、3.2、3.4、3.6或3.8等,但不限於此。在一實施例中,該維生素例如包含維生素A、維生素D3、維生素E、維生素K3、維生素B12、維生素B6、維生素B2、維生素B3及維生素B5。 In addition, in an embodiment of the present invention, the sustained-release composite matrix may further comprise a vitamin, such as a vitamin B group, particularly a vitamin, depending on the soil quality of the soil in which the groundwater is contaminated or the microorganism species thereof. B12. The vitamin is used as a nutrient for the microorganisms in the field to promote its growth, and it is dissolved in the oil droplets or in liquid water. The vitamin may be used in an amount of 2.3 to 4 parts by weight, such as 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6 or 3.8, etc., but is not limited thereto. In one embodiment, the vitamin comprises, for example, vitamin A, vitamin D3, vitamin E, vitamin K3, vitamin B12, vitamin B6, vitamin B2, vitamin B3, and vitamin B5.

此外,本發明之厭養微生物營養基質是以有機厭氧基質為基礎再額外添加0.46~0.5重量份之氫氧化鎂(Mg(OH)2),其可釋放氫氧根離子直接進行緩衝,同時也可藉由氫氧化鎂預先與有機厭氧基質中之脂肪酸混和生成脂肪酸鎂鹽及甘油,以做為另一長效緩衝物質。該氫氧化鎂之使用量可為0.46~0.5重量份,例如0.47、0.48或0.49等,但不限於此。 In addition, the anatrophic microbial nutrient substrate of the present invention further adds 0.46-0.5 parts by weight of magnesium hydroxide (Mg(OH) 2 ) based on the organic anaerobic substance, which can directly release the hydroxide ions and buffer. It is also possible to form a long-acting buffer substance by mixing magnesium hydroxide with a fatty acid in an organic anaerobic substance to form a fatty acid magnesium salt and glycerin. The magnesium hydroxide may be used in an amount of 0.46 to 0.5 parts by weight, such as 0.47, 0.48 or 0.49, etc., but is not limited thereto.

再者,本發明之厭養微生物營養基質包含46~50重量份之水,例如47、48或49等,但不限於此。水主要係用以充份混合上述成份,特別是使該生物可分解界面活性劑係與植物油在水中混合形成一油滴懸浮液,其中植物油與生物可分解界面活性劑(及維生素)會形成油滴狀物(即油滴微粒)均勻懸浮分散於液態水中,而氫氧化鎂與植物油(脂肪酸)混和生成之脂肪酸鎂鹽及甘油亦混於該油滴微粒中。在一實施例中,該油滴微粒之粒徑範圍為1-2μm(微米),例如為1.1、1.2、1.3、1.4、1.5、1.6、1.7、1.8或1.9μm,但不限於此。 Furthermore, the anatrophic microbial nutrient substrate of the present invention contains 46 to 50 parts by weight of water, such as 47, 48 or 49, etc., but is not limited thereto. The water is mainly used to fully mix the above components, in particular, the biodegradable surfactant system and the vegetable oil are mixed in water to form an oil droplet suspension, wherein the vegetable oil and the biodegradable surfactant (and vitamin) form an oil. The drops (ie, oil droplets) are uniformly suspended and dispersed in the liquid water, and the fatty acid magnesium salt and glycerin formed by mixing the magnesium hydroxide with the vegetable oil (fatty acid) are also mixed in the oil droplet particles. In one embodiment, the oil droplet particles have a particle size ranging from 1-2 [mu]m (micrometers), such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8 or 1.9 [mu]m, but are not limited thereto.

在本發明一第一實施例中,本發明提供一種緩衝水體酸鹼值之厭養微生物營養基質之製造方法,其大致包含下述步驟:首先,依序在 一容器中加入大豆油0.46g(公克)、氫氧化鎂0.046g、卵磷脂0.037g、維生素0.023克及純水0.46ml(亦即包含46重量份之植物油、4.6重量份之氫氧化鎂、3.7重量份之生物可分解界面活性劑、2.3重量份之維生素及46重量份之水),初步混合後以均質機在25℃及轉速12,000rpm下進行攪拌15分鐘,使上述成份被充份研磨並均勻混合,如此即可製得具油滴狀懸浮液形式之厭養微生物營養基質,其中該油滴狀懸浮液中之油滴微粒具有一粒徑範圍約為1至2μm。上述維生素例如包含以重量百分比計0.26%之維生素A、0.98%之維生素D3、0.05%之維生素E、0.01%之維生素K3、98.19%之維生素B12、0.06%之維生素B6、0.35%之維生素B2、0.07%之維生素B3及0.03%之維生素B5。 In a first embodiment of the present invention, the present invention provides a method for producing a pH-reducing microbial nutrient matrix for buffering a water body, which comprises the following steps: First, in sequence Soybean oil 0.46g (g), magnesium hydroxide 0.046g, lecithin 0.037g, vitamin 0.023g and pure water 0.46ml (ie containing 46 parts by weight of vegetable oil, 4.6 parts by weight of magnesium hydroxide, 3.7) Parts by weight of biodegradable surfactant, 2.3 parts by weight of vitamins and 46 parts by weight of water), after preliminary mixing, stirring with a homogenizer at 25 ° C and 12,000 rpm for 15 minutes, so that the above ingredients are thoroughly ground and By uniformly mixing, an anaesthetic microbial nutrient substrate in the form of an oil droplet suspension is obtained, wherein the oil droplet particles in the oil droplet suspension have a particle size ranging from about 1 to 2 μm. The above vitamins include, for example, 0.26% by weight of vitamin A, 0.98% of vitamin D3, 0.05% of vitamin E, 0.01% of vitamin K3, 98.19% of vitamin B12, 0.06% of vitamin B6, and 0.35% of vitamin B2. 0.07% of vitamin B3 and 0.03% of vitamin B5.

在本發明一第二實施例之製造方法中,其係在一容器中加入大豆油0.55g(公克)、氫氧化鎂0.005g、卵磷脂0.05g、維生素0.04克及純水0.5mL(亦即包含55重量份之植物油、0.5重量份之氫氧化鎂、5重量份之生物可分解界面活性劑、4重量份之維生素及50重量份之水),初步混合後以均質機在25℃及轉速12,000rpm下進行攪拌15分鐘,使上述成份被充份研磨並均勻混合,以製得具油滴狀懸浮液形式之厭養微生物營養基質,其中該油滴狀懸浮液中之油滴微粒具有一粒徑範圍約為1至2μm。該維生素之組成係與上一實施例相同。 In a manufacturing method according to a second embodiment of the present invention, 0.55 g (g) of soybean oil, 0.005 g of magnesium hydroxide, 0.05 g of lecithin, 0.04 g of vitamins and 0.5 mL of pure water are added to a container (ie, Containing 55 parts by weight of vegetable oil, 0.5 parts by weight of magnesium hydroxide, 5 parts by weight of biodegradable surfactant, 4 parts by weight of vitamins and 50 parts by weight of water), after preliminary mixing, using a homogenizer at 25 ° C and a rotation speed Stirring at 12,000 rpm for 15 minutes, the above ingredients are thoroughly ground and uniformly mixed to obtain an anaesthetic microbial nutrient substrate in the form of an oil droplet suspension, wherein the oil droplet particles in the oil droplet suspension have one The particle size ranges from about 1 to 2 μm. The composition of the vitamin is the same as in the previous embodiment.

在本發明一第三實施例之製造方法中,其係在一容器中加入大豆油0.5g(公克)、氫氧化鎂0.0048g、卵磷脂0.04g、維生素0.03克及純水0.48ml(亦即包含50重量份之植物油、0.48重量份之氫氧化鎂、4重量份之生物可分解界面活性劑、3重量份之維生素及48重量份之水),初步混合後以均質機在25℃及轉速12,000rpm下進行攪拌15分鐘,使上述成份被充份研磨並均勻混合,以製得具油滴狀懸浮液形式之厭養微生物營養基質,其中該油滴狀懸浮液中之油滴微粒具有一粒徑範圍約為1至2μm。該維生素之組成係與前二實施例相同。 In a manufacturing method according to a third embodiment of the present invention, a soybean oil is added with 0.5 g (g) of soybean oil, 0.0048 g of magnesium hydroxide, 0.04 g of lecithin, 0.03 g of vitamins, and 0.48 ml of pure water (that is, Containing 50 parts by weight of vegetable oil, 0.48 parts by weight of magnesium hydroxide, 4 parts by weight of biodegradable surfactant, 3 parts by weight of vitamins and 48 parts by weight of water), after preliminary mixing, using a homogenizer at 25 ° C and a rotation speed Stirring at 12,000 rpm for 15 minutes, the above ingredients are thoroughly ground and uniformly mixed to obtain an anaesthetic microbial nutrient substrate in the form of an oil droplet suspension, wherein the oil droplet particles in the oil droplet suspension have one The particle size ranges from about 1 to 2 μm. The composition of the vitamin is the same as in the first embodiment.

本發明之緩衝水體酸鹼值之厭養微生物營養基質係可於欲使用於現址整治前內再行製作,以確保其保有一油滴狀懸浮液之形式,且產品於陰涼處最多可保存約30天。在完成製作後及使用於現址整治前,可 先加水稀釋約10~30倍(實際稀釋倍數視現地含水層通透性而定),再經由地下水井注入地下水含水層中。 The buffered water body pH value of the anaerobic microbial nutrient matrix can be re-prepared before use in the current site to ensure that it retains the form of an oil-drop suspension, and the product can be preserved in a cool place. About 30 days. After the completion of the production and before the remediation of the site, Diluted with water by about 10 to 30 times (the actual dilution ratio depends on the permeability of the existing aquifer), and then injected into the groundwater aquifer through the groundwater well.

當本發明進行以下降解實驗時,首先準備如下表1所示之材料,其中無菌控制組包含TCE(1mg/L)、地下水(150mL)、土壤(50g)、NaN3(0.5mg)、HgCl2(0.25mg),該NaN3及HgCl2用以做為殺菌劑;現有厭氧基質之對照組包含TCE(1mg/L)、地下水(150mL)、土壤(50g)、現有厭氧基質(0.1g),該現有厭氧基質中包含約1wt%之乳酸鈉;及本發明緩衝厭氧基質之實驗組包含TCE(1mg/L)、地下水(150mL)、土壤(50g)、本發明緩衝厭氧基質(0.1g),本發明在此使用上述第一實施例中之緩衝厭氧基質配製比例進行配製(亦即包含46重量份之植物油、0.46重量份之氫氧化鎂、3.7重量份之生物可分解界面活性劑、2.3重量份之維生素及46重量份之水)。另外,無菌控制組、現有厭氧基質對照組及本發明緩衝厭氧基質實驗組之內容物皆另包含還原劑Na2S及厭氧指示劑刃天青(resazurin)。 When the present invention was subjected to the following degradation experiments, the materials shown in Table 1 below were first prepared, wherein the aseptic control group contained TCE (1 mg/L), ground water (150 mL), soil (50 g), NaN 3 (0.5 mg), HgCl 2 . (0.25 mg), the NaN 3 and HgCl 2 are used as a bactericide; the existing anaerobic control group contains TCE (1 mg/L), ground water (150 mL), soil (50 g), and existing anaerobic substance (0.1 g). The existing anaerobic substance comprises about 1% by weight of sodium lactate; and the experimental group of the buffered anaerobic substance of the invention comprises TCE (1 mg/L), ground water (150 mL), soil (50 g), buffer anaerobic substance of the invention ( 0.1 g), the present invention is herein prepared using the buffered anaerobic formulation ratio of the above first embodiment (that is, comprising 46 parts by weight of vegetable oil, 0.46 parts by weight of magnesium hydroxide, and 3.7 parts by weight of biodegradable interface). Active agent, 2.3 parts by weight of vitamins and 46 parts by weight of water). In addition, the contents of the aseptic control group, the existing anaerobic control group and the buffered anaerobic test group of the present invention further comprise a reducing agent Na 2 S and an anaerobic indicator resazurin.

現有厭氧基質(對照組,含乳酸鈉,乳酸鈉)及本發明緩衝厭氧基質(實驗組,添加氫氧化鎂)進行微生物批次降解試驗時,含氯污染物選擇以三氯乙烯(TCE)為代表,對照組及實驗組裝瓶後於厭氧箱內暗室培養80天,溫度維持在室溫25℃。本實驗中之地下水及土壤係取自高雄林園工業區台灣氯乙烯公司氯乙烯廠(高雄市林園區工業一路1號),其係為一鄰海之含氯有機物污染場址(取樣之場址距離高屏溪河床最近約150~200公尺,及距離高屏溪河口最近約2000公尺),而Dehalococcoides sp.脫鹵菌群為現地含水層土壤中之原生厭氧菌,並非額外添加者,其對氯烯類、氯烷類、氯 酚類及氯苯類具有良好的厭氧還原脫氯效果,故可用以做為代表降解含氯有機污染物的厭氧微生物之指標型菌種。 When the existing anaerobic substance (control group, sodium lactate, sodium lactate) and the buffered anaerobic substance of the invention (experimental group, magnesium hydroxide added) were subjected to microbial batch degradation test, the chlorine-containing contaminant was selected to be trichloroethylene (TCE). Representative, control group and experimental assembled bottles were incubated in the dark chamber of the anaerobic chamber for 80 days, and the temperature was maintained at room temperature of 25 °C. The groundwater and soil system in this experiment was taken from the vinyl chloride plant of Taiwan's vinyl chloride company in Kaohsiung Linyuan Industrial Zone (No. 1 Industrial Road, Linyuan, Kaohsiung City), which is a chlorinated organic pollution site adjacent to the sea (sampling site) The site is about 150~200 meters away from the Gaopingxi Riverbed and about 2000 meters away from the Gaopingxi River estuary. The Dehalococcoides sp. is a native anaerobic bacterium in the existing aquifer soil, not added. It has a good anaerobic reductive dechlorination effect on chloroolefins, chloroalkanes, chlorophenols and chlorobenzenes, so it can be used as an indicator strain for anaerobic microorganisms degrading chlorinated organic pollutants. .

如下表2所示,其揭示上述無菌控制組、對照組及實驗組培養80天期間量測到的三氯乙烯及其降解副產物含量,其中在現有厭氧基質(含乳酸鈉)之對照組方面,於培養第3天後發現三氯乙烯(TCE)降解後之二種副產物順1,2二氯乙烯(cDCE)及1,1-二氯乙烯(1,1-DCE);於培養到第5天後發現三氯乙烯降解後之另一副產物氯乙烯(VC);於培養到第80天後,氯乙烯濃度仍維持0.09mg/L,三氯乙烯之降解效率僅達到67%。另一方面,本發明緩衝厭氧基質(含氫氧化鎂)之實驗組於培養到第3天後發現三氯乙烯(TCE)降解後之三種副產物順1,2二氯乙烯(cDCE)、1,1二氯乙烯(1,1-DCE)及氯乙烯(VC)同時出現;於培養到第30天時,已無氯乙烯濃度檢出;於培養到第80天後,三氯乙烯之降解效率已達到100%。 As shown in Table 2 below, it discloses the content of trichloroethylene and its degradation by-products measured during the 80-day culture period of the above-mentioned aseptic control group, the control group and the experimental group, wherein the control group of the existing anaerobic substance (including sodium lactate) is used. After the third day of culture, the two by-products of trichloroethylene (TCE) degradation were found to be 1,2 dichloroethylene (cDCE) and 1,1-dichloroethylene (1,1-DCE); After the fifth day, another by-product of vinyl chloride (VC) was found after degradation of trichloroethylene. After the 80th day of culture, the concentration of vinyl chloride was maintained at 0.09 mg/L, and the degradation efficiency of trichloroethylene was only 67%. On the other hand, the experimental group of the buffered anaerobic substance (containing magnesium hydroxide) of the present invention found that after the third day of culture, the three by-products of trichloroethylene (TCE) degradation were cis 1,2 dichloroethylene (cDCE), 1,1 dichloroethylene (1,1-DCE) and vinyl chloride (VC) appeared simultaneously; when the culture reached the 30th day, no vinyl chloride concentration was detected; after the 80th day of cultivation, trichloroethylene The degradation efficiency has reached 100%.

如下表3所示,其揭示上述對照組及實驗組培養80天期間量測到的pH值變化趨勢,其中現有厭氧基質(含乳酸鈉)之對照組於培養到第5天時,pH值呈現弱酸性(5.8),且隨著時間持續下降;於培養到第80天時,pH直降至酸性(4.5),顯示因厭氧降解反應造成酸化水解產生有機酸累積。另一方面,本發明緩衝厭氧基質(含氫氧化鎂)之實驗組雖因基質遭到微生物利用而使pH逐漸降低,但直到培養第80天時,pH值仍維持約呈中性(6.9)。比對上表2及3之結果顯示,現有厭氧基質(含乳酸鈉)之對照組因pH值下降較多,較不利於還原脫鹵菌生長與繁殖,不但造成三氯乙烯(TCE)之降解副產物順1,2二氯乙烯(cDCE)、1,1二氯乙烯(1,1-DCE)及氯乙烯(VC)產生並累積未能進一步降解,而且三氯乙烯整體降解效率亦不佳。另一方面,本發明緩衝厭氧基質(含氫氧化鎂)之實驗組因可維持地下水及土壤環境中之pH值為接近中性,較適合脫鹵菌長期生長與繁殖,因此三氯乙烯(TCE)之降解副產物順1,2二氯乙烯(cDCE)、1,1二氯乙烯(1,1-DCE)及氯乙烯(VC)並未累積過量,同時三氯乙烯整體降解效果亦較佳。 As shown in Table 3 below, it reveals the change trend of the pH value measured during the 80-day culture period of the above control group and the experimental group, wherein the pH value of the control group of the existing anaerobic substance (sodium lactate-containing) is cultured until the fifth day. It is weakly acidic (5.8) and continues to decrease with time; when cultured to the 80th day, the pH is directly reduced to acidity (4.5), indicating that acidification hydrolysis causes organic acid accumulation due to anaerobic degradation reaction. On the other hand, in the experimental group for buffering anaerobic substances (including magnesium hydroxide) of the present invention, the pH was gradually lowered due to the use of the substrate by microorganisms, but the pH remained approximately neutral until the 80th day of culture (6.9). ). Comparing the results of Tables 2 and 3 above, the control group of the existing anaerobic (sodium lactate) decreased the pH value, which was not conducive to the growth and reproduction of the reduced-halogen bacteria, which not only caused the degradation of trichloroethylene (TCE). The by-products of cis 1,2 dichloroethylene (cDCE), 1,1 dichloroethylene (1,1-DCE) and vinyl chloride (VC) are produced and accumulated without further degradation, and the overall degradation efficiency of trichloroethylene is also poor. . On the other hand, the experimental group for buffering anaerobic substances (including magnesium hydroxide) of the present invention is suitable for maintaining the pH value of groundwater and soil environment close to neutral, and is more suitable for long-term growth and reproduction of dehalogenating bacteria, and thus trichloroethylene ( The degradation by-products of TCE), cis 1,2 dichloroethylene (cDCE), 1,1 dichloroethylene (1,1-DCE) and vinyl chloride (VC), are not cumulatively excessive, and the overall degradation effect of trichloroethylene is also higher. good.

如下表4所示,其揭示上述對照組及實驗組培養80天期間量測到的有機碳濃度變化趨勢,其中在相同之1%厭氧基質添加量下,本發明緩衝厭氧基質(含氫氧化鎂)相對於現有厭氧基質(含乳酸鈉)具有較高之有機碳濃度,因此顯示出使用本發明緩衝厭氧基質於厭氧反應上更為長效。 As shown in Table 4 below, it reveals the change trend of the organic carbon concentration measured during the 80-day culture period of the above control group and the experimental group, wherein the buffered anaerobic substance (hydrogen-containing) of the present invention is added at the same 1% anaerobic amount. Magnesium oxide) has a higher organic carbon concentration than the existing anaerobic materials (sodium lactate containing), and thus exhibits a longer-lasting effect on the anaerobic reaction using the buffered anaerobic substance of the present invention.

表4、對照組及實驗組在培養80天期間量測到的有機碳濃 Table 4, control group and experimental group measured organic carbon concentration during 80 days of culture

如下表5所示,其揭示上述無菌控制組、對照組及實驗組之量測數據,其中無菌控制組在0天及80天之菌數皆為0;添加現有厭氧基質(含乳酸鈉)之對照組由0天至第80天之菌數增長比例約為296倍;而添加本發明緩衝厭氧基質(含氫氧化鎂)之實驗組由0天至第80天之菌數增長比例約為6474倍,明顯提升為對照組之菌數增長比例的近22倍。由本結果可知,本發明緩衝厭氧基質(含氫氧化鎂)之實驗組有利於維持pH酸鹼值在中性,因此經厭氧微生物(以Dehalococcoides為代表)長時間進行降解反應後之pH酸鹼值變化量仍不大,因此適合讓Dehalococcoides脫鹵菌群等厭氧微生物穩定成長及繁殖,故測得之菌數量及成長比例均較現有厭氧基質(含乳酸鈉)來得高出許多。 As shown in Table 5 below, it discloses the measurement data of the above-mentioned aseptic control group, the control group and the experimental group, wherein the number of bacteria in the aseptic control group at 0 days and 80 days is 0; the existing anaerobic substance (containing sodium lactate) is added. In the control group, the growth rate of bacteria from 0 days to 80 days was about 296 times; and the growth rate of the number of bacteria from 0 days to 80 days in the experimental group to which the buffered anaerobic substance (containing magnesium hydroxide) of the present invention was added was about 6474 times, significantly increased to nearly 22 times the growth rate of the control group. From the results, it can be seen that the experimental group of the buffered anaerobic substance (containing magnesium hydroxide) of the present invention is advantageous for maintaining the pH value of the pH in the neutral state, and therefore the pH acid after the long-term degradation reaction by the anaerobic microorganism (represented by Dehalococcoides ) The amount of change in alkali value is still small, so it is suitable for the anaerobic microorganisms such as Dehalococcoides dehalogenating bacteria to grow and multiply stably. Therefore, the number of bacteria measured and the growth ratio are much higher than those of existing anaerobic substances (including sodium lactate).

相較現有技術,本發明具有緩衝功能之厭氧有機基質是以有機厭氧基質為基礎再額外添加氫氧化鎂(Mg(OH)2),因此可釋放氫氧根離子進行緩衝,同時也可藉由氫氧化鎂與有機厭氧基質中之脂肪酸混和生成脂肪酸鎂鹽及甘油,利用脂肪酸鎂鹽及甘油進一步做為長效緩衝物質,以便 在整治地下水環境時具有長時間(約可達80天)的維持水體中最適合厭氧微生物反應之中性pH值環境之緩衝能力,也就是可以在厭氧微生物對有機厭氧基質進行厭氧反應酸化水解釋放出有機酸時,中和該厭氧反應所產生之有機酸,以利長期維持中性pH環境。而且,本發明具有緩衝功能之厭氧有機基質僅需一次灌注至地下水含水層中即足以長期補充培養現地厭氧微生物所需之碳源及具備長期緩衝能力。 Compared with the prior art, the anaerobic organic matrix with buffer function of the invention is additionally added with magnesium hydroxide (Mg(OH) 2 ) based on organic anaerobic materials, so that hydroxide ions can be released for buffering, and at the same time, By mixing magnesium hydroxide with fatty acids in organic anaerobics to form fatty acid magnesium salts and glycerin, fatty acid magnesium salts and glycerin are further used as long-acting buffer substances for long time in remediation of groundwater environment (about 80 days) Maintaining the buffering capacity of the water body that is most suitable for the neutral pH environment of anaerobic microbial reactions, that is, neutralizing the anaerobic when the anaerobic microorganisms anaerobic reaction of the organic anaerobic acid to release the organic acid The organic acid produced by the reaction is used to maintain a neutral pH environment for a long time. Moreover, the buffered anaerobic organic matrix of the present invention requires only one infusion into the groundwater aquifer, which is sufficient to supplement the carbon source required for the cultivation of the existing anaerobic microorganisms for a long period of time and has a long-term buffering capacity.

再者,本發明之配方係以植物油(如大豆油)中添加Mg(OH)2混和,再分別添加生物可分解界面活性劑(如卵磷脂),添加後以均質機攪拌均勻,即可成為成品。成品具有一油滴懸浮液之形式,亦即植物油與生物可分解界面活性劑(及維生素)會形成油滴微粒均勻懸浮分散於液態水中,而氫氧化鎂與植物油(脂肪酸)混和生成之脂肪酸鎂鹽及甘油亦混於該油滴中,且產品於陰涼處最多可保存約30天。可以在完成製作後及欲使用前,再加水稀釋約10~30倍(實際稀釋倍數視現地含水層通透性而定)經由地下水井注入地下水含水層中使用。因此,在製程及使用上皆極為簡便。 Furthermore, the formulation of the present invention is a mixture of Mg(OH) 2 added to a vegetable oil (such as soybean oil), and then a biodegradable surfactant (such as lecithin) is added separately, and after being added, the mixture is uniformly stirred by a homogenizer to become Finished product. The finished product has the form of an oil droplet suspension, that is, the vegetable oil and the biodegradable surfactant (and vitamins) form oil droplets uniformly dispersed and dispersed in the liquid water, and the magnesium hydroxide and the vegetable oil (fatty acid) are mixed to form the fatty acid magnesium. Salt and glycerin are also mixed in the oil droplets, and the product can be stored for up to about 30 days in a cool place. It can be diluted into the groundwater aquifer through the groundwater well after the completion of the production and before use, and then diluted with water by about 10 to 30 times (the actual dilution ratio depends on the permeability of the existing aquifer). Therefore, it is extremely simple in terms of process and use.

因此,如上所述,在一實施例中,本發明可提供一種緩衝水體酸鹼值之厭養微生物營養基質之用途,其可將上述厭養微生物營養基質(46~55重量份之植物油、0.46~0.5重量份之氫氧化鎂、3.7~5重量份之生物可分解界面活性劑、2.3~4重量份之維生素及46~50重量份之水)經由重力流、低壓或高壓灌注等方式通過一含氯有機物污染場址之一地下水井注入一地下水含水層中,以促使現地厭氧微生物降解地下水中之含氯有機污染物,其中該厭養微生物營養基質以脂肪酸鎂鹽及甘油做為長效緩衝物質,用以提供一長期pH緩衝能力,以便有效的中和厭氧微生物(如Dehalococcoides脫鹵菌群)反應產生之有機酸,並且長時間的維持水體中最適合厭氧微生物反應之中性pH值環境。該含氯有機物污染場址較佳係一鄰海之含氯有機物污染場址,例如為高雄林園工業區,特別是高雄林園工業區之台灣氯乙烯公司氯乙烯廠(高雄市林園區工業一路1號),其係為一鄰海之含氯有機物污染場址(取樣之場址距離高屏溪河床最近約150~200公尺,及距離高屏溪河口最近約2000公尺)。上述台灣氯乙烯公司之林園氯乙烯廠主要係由乙烯及二氯乙烷(ethylene dichloride,EDC)來合成氯乙烯(vinyl chloride,VC),當氯乙烯或二氯乙烷經由工廠廢水排放或儲槽、管線的意外洩漏而存在於工廠之廢水、土壤或地下水中時,容易增加土壤污染之深度及範圍,因此必需加以進行整治。該林園氯乙烯廠自1992年開始營運至今已22年,因此該場址地下水中的原生厭氧微生物在長期接觸該地環境中的氯乙烯(及/或二氯乙烷)之下,原本即具有較佳之氯乙烯或二氯乙烷降解效率,同時也因鄰近河口,故該地的原生厭氧微生物也較能適應鄰海河口土壤的環境因素(如季節溫度變化、鹽度、土壤組成、含氯有機污染物濃物、地下水量及深度、其他有機/無機污染物等…);若進一步將本發明厭氧有機基質經由一地下水井注入其地下水含水層中,將可以促使現地厭氧微生物降解地下水中之含氯有機污染物,並藉由脂肪酸鎂鹽及甘油做為長效緩衝物質,用以提供一長期pH緩衝能力,以便有效的中和厭氧微生物(如Dehalococcoides脫鹵菌群)反應產生之有機酸,長時間的維持該含氯有機物污染場址之地下水體中最適合厭氧微生物反應之中性pH值環境。 Therefore, as described above, in one embodiment, the present invention can provide a use of a water-reducing microbial nutrient matrix for buffering water pH, which can be used for the above-mentioned microbial nutrient substrate (46 to 55 parts by weight of vegetable oil, 0.46). ~0.5 parts by weight of magnesium hydroxide, 3.7 to 5 parts by weight of biodegradable surfactant, 2.3 to 4 parts by weight of vitamins and 46 to 50 parts by weight of water) pass through gravity flow, low pressure or high pressure perfusion A groundwater well of a chlorinated organic contaminated site is injected into a groundwater aquifer to cause local anaerobic microorganisms to degrade chlorinated organic pollutants in groundwater, wherein the anatrophic microbial nutrient matrix is long-acting with fatty acid magnesium salts and glycerol Buffer material to provide a long-term pH buffering capacity to effectively neutralize the organic acids produced by the reaction of anaerobic microorganisms (such as Dehalococcoides dehalogenating bacteria), and maintain the most suitable anaerobic microbial reaction in water for a long time. pH environment. The chlorinated organic contaminated site is preferably a chlorinated organic contaminated site adjacent to the sea, such as the Kaohsiung Linyuan Industrial Zone, especially the Taiwan Vinyl Chloride Company's vinyl chloride plant in Kaohsiung Linyuan Industrial Zone (Kaohsiung City Forest Park Industry) No.1), which is a chlorinated organic pollution site adjacent to the sea (the sampling site is about 150~200 meters away from Gaopingxi Riverbed and about 2000 meters away from Gaopingxihekou). The above-mentioned Taiwan vinyl chloride plant Linyuan vinyl chloride plant mainly uses ethylene and ethylene dichloride (EDC) to synthesize vinyl chloride (VC), when vinyl chloride or dichloroethane is discharged through factory wastewater or When the accidental leakage of the storage tank or pipeline exists in the wastewater, soil or groundwater of the factory, it is easy to increase the depth and extent of the soil pollution, so it must be rectified. The Linyuan vinyl chloride plant has been in operation for 22 years since its operation in 1992. Therefore, the original anaerobic microorganisms in the groundwater of the site are exposed to vinyl chloride (and/or dichloroethane) in the environment for a long time. That is to say, it has better degradation efficiency of vinyl chloride or dichloroethane, and because of its proximity to the estuary, the native anaerobic microorganisms in the area are also more adaptable to the environmental factors of the adjacent estuary soil (such as seasonal temperature change, salinity, soil composition). , chlorinated organic pollutant concentrates, groundwater volume and depth, other organic/inorganic pollutants, etc.); if the anaerobic organic matrix of the present invention is further injected into its groundwater aquifer via a groundwater well, it will promote local anaerobic Microbial degradation of chlorinated organic contaminants in groundwater and use of fatty acid magnesium salts and glycerol as long-acting buffers to provide a long-term pH buffering capacity for effective neutralization of anaerobic microorganisms (eg Dehalococcoides dehalogenating bacteria) The organic acid produced by the reaction, which is the most suitable environment for the anaerobic microbial reaction in the groundwater body which maintains the contaminated site of the chlorine-containing organic substance for a long time.

值得注意的是,本發明上文提及的「%」若無特定說明皆指「重量百分比(wt%)」;數值範圍(如10%~11%的A)若無特定說明皆包含上、下限值(即10%≦A≦11%);數值範圍若未界定下限值(如低於0.2%的B,或0.2%以下的B),則皆指其下限值可能為0(即0%≦B≦0.2%);各成份的「重量份」之比例關係亦可在換算後改為「重量百分比」的比例關係。 It should be noted that the "%" mentioned above in the present invention refers to "% by weight (wt%)" unless otherwise specified; the range of values (such as 10% to 11% of A) is included unless otherwise specified. The lower limit value (ie 10% ≦A ≦ 11%); if the value range does not define the lower limit value (such as B below 0.2%, or B below 0.2%), it means that the lower limit value may be 0 ( That is, 0% ≦ B ≦ 0.2%); the proportional relationship of the "weight parts" of each component can also be changed to the "weight percentage" proportional relationship after conversion.

雖然本發明已以較佳實施例揭露,然其並非用以限制本發明,任何熟習此項技藝之人士,在不脫離本發明之精神和範圍內,當可作各種更動與修飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。 The present invention has been disclosed in its preferred embodiments, and is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.

Claims (12)

一種緩衝水體酸鹼值之厭養微生物營養基質,其包含:46~55重量份之植物油、0.46~0.5重量份之氫氧化鎂、3.7~5重量份之生物可分解界面活性劑、2.3~4重量份之維生素及46~50重量份之水;在該厭養微生物營養基質中,氫氧化鎂與植物油之脂肪酸混和生成脂肪酸鎂鹽及甘油,該厭養微生物營養基質以脂肪酸鎂鹽及甘油做為長效緩衝物質,以提供pH緩衝能力。 An anaerobic microbial nutrient substrate for buffering water pH value, comprising: 46-55 parts by weight of vegetable oil, 0.46-0.5 parts by weight of magnesium hydroxide, 3.7-5 parts by weight of biodegradable surfactant, 2.3~4 a part by weight of vitamins and 46 to 50 parts by weight of water; in the anatrophic microbial nutrient matrix, magnesium hydroxide is mixed with fatty acids of vegetable oil to form fatty acid magnesium salt and glycerin, and the anatrophic microbial nutrient substrate is made of fatty acid magnesium salt and glycerin It is a long-acting buffer material to provide pH buffering capacity. 如申請專利範圍第1項所述之緩衝水體酸鹼值之厭養微生物營養基質,其中該厭養微生物營養基質包含46重量份之植物油、0.46重量份之氫氧化鎂、3.7重量份之生物可分解界面活性劑、2.3重量份之維生素及46重量份之水。 The anaerobic microbial nutrient substrate of the buffered water pH value according to claim 1, wherein the anatrophic microbial nutrient substrate comprises 46 parts by weight of vegetable oil, 0.46 parts by weight of magnesium hydroxide, and 3.7 parts by weight of the living organism. The surfactant was decomposed, 2.3 parts by weight of vitamins and 46 parts by weight of water. 如申請專利範圍第1項所述之緩衝水體酸鹼值之厭養微生物營養基質,其中該厭養微生物營養基質係具有一油滴懸浮液之形式,該油滴懸浮液中懸浮有數個油滴微粒。 The anaerobic microbial nutrient substrate of the buffered water pH value according to claim 1, wherein the anatrophic microbial nutrient substrate has the form of an oil droplet suspension in which a plurality of oil droplets are suspended. particle. 如申請專利範圍第3項所述之緩衝水體酸鹼值之厭養微生物營養基質,其中該脂肪酸鎂鹽及甘油混於該油滴懸浮液之數個油滴中。 The anaerobic microbial nutrient substrate of the buffered water pH value according to claim 3, wherein the fatty acid magnesium salt and glycerin are mixed in a plurality of oil droplets of the oil droplet suspension. 如申請專利範圍第3或4項所述之緩衝水體酸鹼值之厭養微生物營養基質,其中該油滴微粒具有一粒徑範圍介於1~2微米。 The anaerobic microbial nutrient substrate of the buffered water pH value according to claim 3 or 4, wherein the oil droplet particles have a particle size ranging from 1 to 2 micrometers. 如申請專利範圍第1項所述之緩衝水體酸鹼值之厭養微生物營養基質,其中該維生素係為維生素B群。 The anaesthetic microbial nutrient matrix of the buffered water pH value according to claim 1, wherein the vitamin is a vitamin B group. 如申請專利範圍第6項所述之緩衝水體酸鹼值之厭養微生物營養基質,其中該維生素B群包含維生素B12。 The absorbing microbial nutrient substrate of the buffered water pH value according to claim 6, wherein the vitamin B group comprises vitamin B12. 如申請專利範圍第1項所述之緩衝水體酸鹼值之厭養微生 物營養基質,其中該生物可分解界面活性劑係選自親油性界面活性劑或親水性界面活性劑。 As the application of the patent scope of the first item of the buffer water pH value of the ill-health A nutrient substrate, wherein the biodegradable surfactant is selected from the group consisting of lipophilic surfactants or hydrophilic surfactants. 如申請專利範圍第8項所述之緩衝水體酸鹼值之厭養微生物營養基質,其中該親油性界面活性劑係選自卵磷脂;該親水性界面活性劑係選自丁基溶纖劑或無患子萃取物皂甙。 The buffered water pH-valued anaesthetic microbial nutrient substrate according to claim 8, wherein the lipophilic surfactant is selected from the group consisting of lecithin; the hydrophilic surfactant is selected from the group consisting of butyl cellosolve or sapindus extraction. Saponin. 一種緩衝水體酸鹼值之厭養微生物營養基質,其包含植物油、氫氧化鎂、生物可分解界面活性劑、維生素及水,其中氫氧化鎂佔該厭養微生物營養基質之總重量的0.46~0.5wt%;在該厭養微生物營養基質中,氫氧化鎂與植物油之脂肪酸混和生成脂肪酸鎂鹽及甘油,該厭養微生物營養基質以脂肪酸鎂鹽及甘油做為長效緩衝物質,以提供pH緩衝能力。 An anaerobic microbial nutrient matrix for buffering water body pH, comprising vegetable oil, magnesium hydroxide, biodegradable surfactant, vitamins and water, wherein magnesium hydroxide accounts for 0.46-0.5 of the total weight of the nutrient substrate of the anatrophic microorganism Gt%; in the anatrophic microbial nutrient matrix, magnesium hydroxide is mixed with fatty acids of vegetable oil to form fatty acid magnesium salt and glycerin, and the anatrophic microbial nutrient substrate uses fatty acid magnesium salt and glycerin as long-acting buffer substances to provide pH buffer ability. 一種緩衝水體酸鹼值之厭養微生物營養基質之用途,其係將如申請專利範圍第1或10項所述之厭養微生物營養基質經由一地下水井注入一地下水含水層中,以促使現地厭氧微生物降解地下水中之含氯有機污染物,其中該厭養微生物營養基質以脂肪酸鎂鹽及甘油做為長效緩衝物質,以提供pH緩衝能力,以便中和厭氧微生物反應產生之有機酸,並且維持水體中適合厭氧微生物反應之中性pH值環境。 The use of a water-reducing microbial nutrient matrix for absorbing water pH value, which is to inject a anaerobic microbial nutrient substrate according to claim 1 or 10 into a groundwater aquifer through a groundwater well to promote the local anatomy Oxygen microorganisms degrade chlorinated organic pollutants in groundwater, wherein the anatrophic microbial nutrient matrix uses fatty acid magnesium salts and glycerin as long-acting buffer substances to provide pH buffering capacity to neutralize organic acids produced by anaerobic microbial reactions, And maintain a neutral pH environment suitable for anaerobic microbial reactions in water. 如申請專利範圍第11項所述之緩衝水體酸鹼值之厭養微生物營養基質之用途,其中該含氯有機污染物係為三氯乙烯。 The use of the buffered water pH value of the anaerobic microbial nutrient substrate according to claim 11, wherein the chlorine-containing organic pollutant is trichloroethylene.
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