TWI616409B - Emulsive composition and method of preparing the same - Google Patents

Emulsive composition and method of preparing the same Download PDF

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TWI616409B
TWI616409B TW104138252A TW104138252A TWI616409B TW I616409 B TWI616409 B TW I616409B TW 104138252 A TW104138252 A TW 104138252A TW 104138252 A TW104138252 A TW 104138252A TW I616409 B TWI616409 B TW I616409B
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latex composition
weight
acid
biodegradable surfactant
base buffer
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TW104138252A
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TW201718415A (en
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高志明
連博仁
劉原宏
張育祺
劉治平
許藝騰
洛 史倫伯力
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裕山環境工程股份有限公司
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Abstract

本發明提供一種乳膠組合物,該乳膠組合物包含一植物油、一生物可分解界面活性劑、一酸鹼緩衝劑以及其餘為水。該生物可分解界面活性劑包含卵磷脂,且該生物可分解界面活性劑以重量計為該乳膠組合物之4.5~10.1%。此外,本發明亦提供一種乳膠組合物的製造方法,利用超聲波來進行一乳化作用,使該乳膠組合物具有0.2至0.5微米的平均乳化粒徑。 The present invention provides a latex composition comprising a vegetable oil, a biodegradable surfactant, an acid-base buffer, and the balance water. The biodegradable surfactant comprises lecithin and the biodegradable surfactant is from 4.5 to 10.1% by weight of the latex composition. Further, the present invention also provides a method for producing a latex composition which is subjected to an emulsification by ultrasonic waves so that the latex composition has an average emulsified particle diameter of 0.2 to 0.5 μm.

Description

乳膠組合物及其製造方法 Latex composition and method of producing the same

本發明係關於一種乳膠組合物及其製造方法,特別是關於一種用於含氯有機物污染整治之乳膠組合物及其製造方法。 The present invention relates to a latex composition and a method of producing the same, and more particularly to a latex composition for use in the treatment of chlorine-containing organic matter contamination and a method of producing the same.

土壤與地下水的污染防治在環境資源的永續發展與利用中是極為重要的一環。當環境遭受到污染並且持續擴張,將會危害到我們生活的環境甚至破壞自然生態等。近年來由於工業快速發展,含氯脂肪族碳氫化合物(chlorinated aliphatic hydrocarbons,CAHs)對脂類具有高溶解力、低可燃、低沸點及高蒸氣壓等特性,因此被大量廣泛使用於工業上金屬及電子零件之清洗、脫脂、表面黏著及乾洗等作業,又因其比重大於水,溶解度亦較低,亦被稱為重質非水相液體(dense non-aqueous phase liquid,DNAPL),其中以三氯乙烯(trichloroethylene,TCE)及四氯乙烯(terachloroethylene,PCE)最為常見,其造成土水嚴重污染及不易整治等問題,為近年許多研究持續不斷努力之目標。 The prevention and control of soil and groundwater pollution is an extremely important part in the sustainable development and utilization of environmental resources. When the environment is polluted and continues to expand, it will endanger the environment in which we live and even destroy the natural ecology. In recent years, due to the rapid development of industry, chlorinated aliphatic hydrocarbons (CAHs) have high solubility, low flammability, low boiling point and high vapor pressure. Therefore, they are widely used in industrial metals. And the cleaning, degreasing, surface adhesion and dry cleaning of electronic parts, and because of its higher specific gravity than water, the solubility is also low, also known as dense non-aqueous phase liquid (DNAPL), of which three Trichloroethylene (TCE) and terachloroethylene (PCE) are the most common, causing serious pollution of soil water and difficulty in remediation. This is the goal of continuous research in many studies in recent years.

在綠色整治(green remediation)的原則下,污染場址之調查與整治規劃必須有著和傳統不同之思維。現今國內外學者運用厭氧生物整治技術(bioremediation)處理受污染場址之案例已十分普遍,以自然生 物復育作為整治優先之選擇,亦是綠色整治概念及對環境友善之目標。雖然生物復育程序的整體反應速率較低,但長期而言,生物復育對場址的破壞性較小,較符合「復育」的需求。在現地應用上,由於自然衰減之整體反應速率較低,因此加強式生物復育技術備受重視,加強式生物復育是將生物復育技術加以改善、強化,其反應速率更合於工程化的需求。因此,在適當條件下為了加速生物分解速率,大部分係以添加營養源於地下水體中,使地下水產生足夠的氫氣與低分子脂肪酸,藉此提供碳源及提高厭氧生物分解之能力,以便處理受污染之土壤及地下水,此類營養源具有可溶性、低黏性、固態性及多樣試驗性等特性。 Under the principle of green remediation, the investigation and remediation planning of polluted sites must have different thinking from the traditional. It is very common for domestic and foreign scholars to use anaerobic bioremediation to treat contaminated sites. As a priority for remediation, rejuvenation is also the goal of green remediation and environmental friendliness. Although the overall response rate of the biological rehabilitative program is low, in the long run, bioremediation is less destructive to the site and more in line with the need for "re-education." In the field application, due to the low overall reaction rate of natural attenuation, enhanced bioremediation technology has received much attention. Enhanced bioremediation is to improve and strengthen bioremediation technology, and its reaction rate is more integrated with engineering. Demand. Therefore, in order to accelerate the rate of biodegradation under appropriate conditions, most of the nutrients are added to the groundwater body to make the groundwater produce sufficient hydrogen and low molecular weight fatty acids, thereby providing carbon sources and improving the ability of anaerobic biolysis. Treatment of contaminated soil and groundwater, such nutrient sources are soluble, low viscosity, solid and diverse experimental properties.

目前常見加強生物分解的方式大致可分為:(1)添加生物可分解之營養鹽或電子接受者於污染場址,活化場址內既有的微生物族群;(2)在污染場址內直接添加對污染物具有分解能力的特殊菌種,或利用基因工程技術,發展具特定污染物分解能力之基因重組微生物;(3)利用生物處理將污染物經通氣或土壤洗滌後送至特殊生物反應器或是生物濾床、生物洗滌塔去除污染物,或是採用地耕法、堆肥處理。 At present, the common methods of enhancing biodegradation can be roughly divided into: (1) adding biodegradable nutrient salts or electron acceptors to the contaminated site, and activating the existing microbial population within the site; (2) directly in the contaminated site Add special strains that have the ability to decompose pollutants, or use genetic engineering techniques to develop genetically modified microorganisms with specific pollutant decomposition capabilities; (3) use biological treatment to transport pollutants to specific biological reactions after aeration or soil washing The device is either a biological filter bed or a biological washing tower to remove pollutants, or is subjected to ground cultivation or composting.

當不同階段的還原脫氯產生時,反應所生成能量則可能被微生物所利用,並促進微生物生長能有效降解污染物之效率。有許多的微生物已被證實,在電子提供的情況下可進行脫氯作用,如產乙烯脫鹵擬球菌(Dehalococcoides ethenogenes)利用H2作為電子提供者,Dehalococcoides ethenogenes和一種脫鹵桿菌(Dehalobacter restrictus)能藉由脫氯呼吸作用獲得能量;另有甲烷生成菌(methanogenic producing microorganisms)、乙酸生成菌(acetogenic producing microorganisms)及硫酸鹽還原菌 (sulfate-reducing microorganisms)等亦能以共代謝方式降解TCE。 When reductive dechlorination occurs at different stages, the energy generated by the reaction may be utilized by the microorganisms and promote the efficiency of microbial growth to effectively degrade the contaminants. A number of microorganisms have been demonstrated to dechlorinate in the case of electrons, such as Dehalococcoides ethenogenes using H 2 as an electron provider, Dehalococcoides ethenogenes and a Dehalobacter restrictus Energy can be obtained by dechlorination respiration; other methanogenic producing microorganisms, acetogenic producing microorganisms, and sulfate-reducing microorganisms can also degrade TCE by co-metabolism.

然而,即使有許多微生物可在厭氧環境下進行脫氯作用,在生物轉換過程中,氯乙烯(vinyl chloride,VC)經由共代謝轉換成乙烯的過程相當緩慢,且作用通常是不完全的,因此易導致VC的累積,而VC為已知之致癌物質。如Dehalococcoides菌種內Dehalococcoides sp.strain FL2還原脫氯代謝TCE轉換成VC;另外strain CBDB1(Ernest et al.,2013)、strain BAV1(Löffler et al.,2013)及strain GT(Chambonet al.,2013)等菌株皆有文獻證實可將PCE和TCE還原脫氯形成VC。然而,僅有屬於Dehalococcoides ethenogenesstrain 195BAV1GT等菌株可將VC完全脫氯成乙烯之無害產物。 However, even if many microorganisms can dechlorinate under anaerobic conditions, the process of converting vinyl chloride (VC) into ethylene via co-metabolism during biotransformation is quite slow, and the effect is usually incomplete. Therefore, it is easy to cause accumulation of VC, and VC is a known carcinogen. For example, Dehalococcoides sp. strain FL2 in Dehalococcoides species converts dechlorination metabolism TCE into VC; in addition, strain CBDB1 (Ernest et al., 2013), strain BAV1 (Löffler et al., 2013) and strain GT (Chambonet al., 2013) All strains have been confirmed by literature to dechlorinate PCE and TCE to form VC. However, only strains belonging to Dehalococcoides ethenogenes , strain 195 , BAV1 and GT can completely dechlorinate VC to ethylene as a harmless product.

目前已有許多種營養基質被廣泛應用於現地厭氧生物降解技術,如醣類(糖蜜)、有機酸(乳酸鹽、甲酸鹽、酪酸鹽、丙酸鹽及苯甲酸鹽)、醇類(甲醇和乙醇)及酵母萃取物,可使降解效率提高。但這些營養基質必須具有高溶解性和高生物分解性,且需經常添加補充以促進微生物之生長。此外,注入之營養基質會造成地下水阻塞及酸化等問題,且硫酸鹽還原作用產生硫化物之臭味問題,也造成該些營養基質的傳輸效果不佳、地下水質不佳及操作維護費用增加的問題。 Numerous nutrient substrates have been widely used in on-site anaerobic biodegradation technologies, such as sugars (molasses), organic acids (lactate, formate, butyrate, propionate and benzoate), alcohols. (Methanol and ethanol) and yeast extracts can improve degradation efficiency. However, these nutrient matrices must have high solubility and high biodegradability, and often need to be supplemented to promote the growth of microorganisms. In addition, the nutrient matrix injected may cause problems such as groundwater blockage and acidification, and the problem of sulphate smelting caused by sulfate reduction also causes poor transmission effect of the nutrient substrate, poor groundwater quality and increased operation and maintenance costs. problem.

故,有必要提供一種可用於整治含氯有機污染物之乳膠組合物及其製造方法,以解決習用技術中所存在的問題。 Therefore, it is necessary to provide a latex composition which can be used for remediation of chlorinated organic pollutants and a method for producing the same to solve the problems in the prior art.

本發明之主要目的在於提供一種乳膠組合物,可用於整治含氯有機污染物,例如三氯乙烯、四氯乙烯等。該乳膠組合物為具有緩釋 特性的釋氫乳膠態基質,可形成被動式的生物反應牆,且具有奈米級的平均乳化粒徑及優良的均質性,可在厭氧環境中有效且持續降解含氯有機物,且防止在整治過程中水或土壤的酸化,使整體環境有利於生物降解處理,達到綠色整治的目的,十分適合現地整治使用。 The main object of the present invention is to provide a latex composition which can be used for the remediation of chlorinated organic contaminants such as trichloroethylene, tetrachloroethylene and the like. The latex composition has sustained release The characteristic hydrogen-releasing latex matrix can form a passive bioreactor wall with nanometer average emulsified particle size and excellent homogeneity, which can effectively and continuously degrade chlorinated organic matter in anaerobic environment and prevent remediation. The acidification of water or soil during the process makes the overall environment beneficial to biodegradation treatment and achieves the purpose of green remediation, which is very suitable for local remediation.

本發明之次要目的在於提供一種乳膠組合物的製造方法,可製造具有奈米級的平均乳化粒徑以及優良均質性的乳膠組合物,乳化程度達100%,並且可在短時間內完成製備。 A secondary object of the present invention is to provide a method for producing a latex composition which can produce a latex composition having a nanometer average emulsified particle size and excellent homogeneity, has an emulsification degree of 100%, and can be prepared in a short time. .

為達上述之目的,本發明的一實施例提供一種乳膠組合物,用於整治含氯有機污染物,該乳膠組合物包含一植物油、一生物可分解界面活性劑、一酸鹼緩衝劑以及其餘為水,其中該生物可分解界面活性劑包含卵磷脂,且該生物可分解界面活性劑以重量計為該乳膠組合物之4.5~10.1%。 To achieve the above object, an embodiment of the present invention provides a latex composition for rectifying a chlorine-containing organic contaminant, the latex composition comprising a vegetable oil, a biodegradable surfactant, an acid-base buffer, and the rest Is water, wherein the biodegradable surfactant comprises lecithin, and the biodegradable surfactant is 4.5 to 10.1% by weight of the latex composition.

在本發明之一實施例中,該植物油和該生物可分解界面活性劑的重量比為1.5:1。 In one embodiment of the invention, the weight ratio of the vegetable oil to the biodegradable surfactant is 1.5:1.

在本發明之一實施例中,該植物油以重量計為該乳膠組合物之9~18.2%。 In one embodiment of the invention, the vegetable oil is from 9 to 18.2% by weight of the latex composition.

在本發明之一實施例中,該卵磷脂以重量計為該乳膠組合物之4.5~9.1%。 In one embodiment of the invention, the lecithin is from 4.5 to 9.1% by weight of the latex composition.

在本發明之一實施例中,該生物可分解界面活性劑還包含一丁基溶纖劑,且該丁基溶纖劑以重量計為該乳膠組合物之0~1%。 In one embodiment of the invention, the biodegradable surfactant further comprises a butyl cellosolve, and the butyl cellosolve is from 0 to 1% by weight of the latex composition.

在本發明之一實施例中,該酸鹼緩衝劑以重量計為該乳膠組合物之8~9.5%。 In one embodiment of the invention, the acid-base buffer is from 8 to 9.5% by weight of the latex composition.

在本發明之一實施例中,該酸鹼緩衝劑係選自檸檬酸、磷酸氫二鈉或其混合物。 In one embodiment of the invention, the acid-base buffer is selected from the group consisting of citric acid, disodium hydrogen phosphate, or mixtures thereof.

在本發明之一實施例中,該酸鹼緩衝劑包含檸檬酸與磷酸氫二鈉,且該檸檬酸與該磷酸氫二鈉的重量比是1:9。 In one embodiment of the invention, the acid-base buffer comprises citric acid and disodium hydrogen phosphate, and the weight ratio of the citric acid to the disodium hydrogen phosphate is 1:9.

在本發明之一實施例中,該酸鹼緩衝劑的濃度為0.1M~0.2M。 In one embodiment of the invention, the acid-base buffer has a concentration of from 0.1 M to 0.2 M.

在本發明之一實施例中,該乳膠組合物具有一乳化平均粒徑為0.2~0.5微米。 In one embodiment of the invention, the latex composition has an emulsified average particle size of from 0.2 to 0.5 microns.

再者,本發明的另一實施例提供一種乳膠組合物的製造方法,其包含步驟:混合一植物油、一生物可分解界面活性劑、一酸鹼緩衝劑以及水,以形成一混合物;以及對該混合物施加超聲波,以進行一乳化作用,以形成如上述之乳膠組合物,其中該生物可分解界面活性劑包含卵磷脂,且該生物可分解界面活性劑以重量計為該混合物之4.5~10.1%。 Furthermore, another embodiment of the present invention provides a method of producing a latex composition comprising the steps of: mixing a vegetable oil, a biodegradable surfactant, an acid-base buffer, and water to form a mixture; The mixture is applied with ultrasonic waves to effect an emulsification to form a latex composition as described above, wherein the biodegradable surfactant comprises lecithin, and the biodegradable surfactant is 4.5 to 10.1 by weight of the mixture. %.

在本發明之一實施例中,該超聲波的功率為10~60%。 In an embodiment of the invention, the ultrasonic power is 10 to 60%.

在本發明之一實施例中,施加該超聲波係持續15分鐘。 In one embodiment of the invention, the ultrasound system is applied for 15 minutes.

在本發明之一實施例中,該植物油和該生物可分解界面活性劑的重量比為1.5:1。 In one embodiment of the invention, the weight ratio of the vegetable oil to the biodegradable surfactant is 1.5:1.

在本發明之一實施例中,該植物油以重量計為該混合物之9~18.2%。 In one embodiment of the invention, the vegetable oil is from 9 to 18.2% by weight of the mixture.

在本發明之一實施例中,該卵磷脂以重量計為該混合物之4.5~9.1%。 In one embodiment of the invention, the lecithin is from 4.5 to 9.1% by weight of the mixture.

在本發明之一實施例中,該生物可分解界面活性劑還包含 一丁基溶纖劑,且該丁基溶纖劑以重量計為該混合物之0~1%。 In an embodiment of the invention, the biodegradable surfactant further comprises Monobutyl cellosolve, and the butyl cellosolve is 0 to 1% by weight of the mixture.

在本發明之一實施例中,該酸鹼緩衝劑以重量計為該乳膠組合物之8~9.5%。 In one embodiment of the invention, the acid-base buffer is from 8 to 9.5% by weight of the latex composition.

在本發明之一實施例中,該酸鹼緩衝劑係選自檸檬酸、磷酸氫二鈉或其混合物。 In one embodiment of the invention, the acid-base buffer is selected from the group consisting of citric acid, disodium hydrogen phosphate, or mixtures thereof.

在本發明之一實施例中,該酸鹼緩衝劑包含檸檬酸與磷酸氫二鈉,且該檸檬酸與該磷酸氫二鈉的重量比是1:9。 In one embodiment of the invention, the acid-base buffer comprises citric acid and disodium hydrogen phosphate, and the weight ratio of the citric acid to the disodium hydrogen phosphate is 1:9.

在本發明之一實施例中,該酸鹼緩衝劑的濃度為0.1M~0.2M。 In one embodiment of the invention, the acid-base buffer has a concentration of from 0.1 M to 0.2 M.

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。本發明所提到的單數形式“一”、“一個”和“所述”包括複數引用,除非上下文另有明確規定。例如,術語“一化合物”或“至少一種化合物”可以包括多個化合物,包括其混合物;本發明文中提及的「%」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「重量百分比」之比例關係亦可置換為「重量份」的比例關係。上述用語是用以說明及理解本發明,而非用以限制本發明。 The above and other objects, features, and advantages of the present invention will become more apparent from The singular forms "a", "the", and "the" For example, the term "a compound" or "at least one compound" may include a plurality of compounds, including mixtures thereof; "%" as referred to in the present specification means "percent by weight (wt%)" unless otherwise specified; For example, 10%~11% of A) include upper and lower limits (ie 10% ≦A≦11%) unless otherwise specified; if the value range does not define a lower limit (such as B below 0.2%, or 0.2) B) below B) means that the lower limit may be 0 (ie 0% ≦ B ≦ 0.2%); the proportional relationship of the "weight percentage" of each component may also be replaced by the proportional relationship of "parts by weight". The above terms are used to illustrate and understand the present invention and are not intended to limit the invention.

本發明係提供一種乳膠組合物,用於整治含氯有機污染物,該乳膠組合物主要包含一植物油、一生物可分解界面活性劑、一酸鹼 緩衝劑以及其餘為水,其中該生物可分解界面活性劑包含卵磷脂,該卵磷脂以重量計為該乳膠組合物之4.5~9.1%,可例如是5、8或9%,較佳是8~9.1%。該生物可分解界面活性劑以重量計為該乳膠組合物之4.5~10.1%,可例如是6.5、9.1或10.1%,然不限於此。該乳膠組合物具有一乳化平均粒徑為0.2~0.5微米,可例如是0.28、0.35或0.46微米,然不限於此。 較佳的,該植物油和該生物可分解界面活性劑的重量比為1.5:1,例如,當該植物油以重量計為該乳膠組合物之15%時,該生物可分解界面活性劑則為該乳膠組合物之10%,然不限於此。 The present invention provides a latex composition for treating chlorine-containing organic pollutants, the latex composition mainly comprising a vegetable oil, a biodegradable surfactant, an acid-base The buffering agent and the balance being water, wherein the biodegradable surfactant comprises lecithin, the lecithin being 4.5 to 9.1% by weight of the latex composition, which may be, for example, 5, 8 or 9%, preferably 8 ~9.1%. The biodegradable surfactant is 4.5 to 10.1% by weight of the latex composition, and may be, for example, 6.5, 9.1 or 10.1%, but is not limited thereto. The latex composition has an emulsified average particle diameter of 0.2 to 0.5 μm and may be, for example, 0.28, 0.35 or 0.46 μm, but is not limited thereto. Preferably, the weight ratio of the vegetable oil to the biodegradable surfactant is 1.5:1. For example, when the vegetable oil is 15% by weight of the latex composition, the biodegradable surfactant is 10% of the latex composition is not limited thereto.

在本發明一實施例中,該植物油可例如是大豆油。以整治三氯乙烯(TCE)為例,大豆油對於TCE具有強的吸附能力,可使高濃度的TCE被集中在該乳膠組合物的油滴中,因此當整治初期環境中尚未有厭氧產氫反應發生時,大豆油可有效攔阻TCE溶於水中,待現地微生物增長之後,大豆油的攔阻及微生物厭氧產氫脫氯反應同時發生,即可增強TCE的處理效率。較佳的,該植物油以重量計為該乳膠組合物之9~18.2%,可例如是10.5、13.6或15.8%,然不限於此。較佳的,該植物油以重量計為該乳膠組合物之13~15%。 In an embodiment of the invention, the vegetable oil can be, for example, soybean oil. Taking rectification of trichloroethylene (TCE) as an example, soybean oil has strong adsorption capacity for TCE, so that high concentration of TCE can be concentrated in the oil droplets of the latex composition, so there is no anaerobic production in the initial environment of remediation. When the hydrogen reaction occurs, the soybean oil can effectively block the TCE from being dissolved in the water. After the growth of the existing microorganisms, the hindrance of the soybean oil and the microbial anaerobic hydrogen production dechlorination reaction occur simultaneously, thereby enhancing the treatment efficiency of the TCE. Preferably, the vegetable oil is from 9 to 18.2% by weight of the latex composition, and may be, for example, 10.5, 13.6 or 15.8%, but is not limited thereto. Preferably, the vegetable oil is from 13 to 15% by weight of the latex composition.

再者,該生物可分解界面活性劑中除了卵磷脂外,還可以包含一親水性的界面活性劑,如丁基溶纖劑(2-Butoxyethanol)。由於卵磷脂是屬於一種親油性的界面活性劑,與親水性的該丁基溶纖劑乳化後可產生高包覆性的保護膜,使該乳膠組合物中的油滴型態不容易破裂而造成凝聚使乳化粒徑變大,可維持該乳膠組合物的穩定度。該卵磷脂以重量計可為該乳膠組合物之4.5~9.1%,較佳為8~9.1%,可例如是8.2、8.7或9.1 %,然不限於此。該丁基溶纖劑以重量計可為該乳膠組合物之0~1%,可例如是0、0.5或0.9%,然不限於此,但當該丁基溶纖劑超過1%對於乳化效果及穩定度並沒有幫助。舉例來說,當該生物可分解界面活性劑含有該卵磷脂以重量計為該乳膠組合物之8.2%時,該丁基溶纖劑以重量計可為該乳膠組合物之0.9%,兩者總和為9.1%;或者,僅含有該卵磷脂為該乳膠組合物之9.1%,然不限於此。 Furthermore, in addition to lecithin, the biodegradable surfactant may further comprise a hydrophilic surfactant such as 2-Butoxyethanol. Since lecithin is a lipophilic surfactant, it can produce a high-coating protective film after emulsification with the hydrophilic butyl cellosolve, so that the oil droplet form in the latex composition is not easily broken and causes coagulation. By increasing the emulsified particle size, the stability of the latex composition can be maintained. The lecithin may be from 4.5 to 9.1%, preferably from 8 to 9.1% by weight of the latex composition, and may be, for example, 8.2, 8.7 or 9.1. %, but not limited to this. The butyl cellosolve may be 0 to 1% by weight of the latex composition, and may be, for example, 0, 0.5 or 0.9%, but is not limited thereto, but when the butyl cellosolve exceeds 1%, the emulsification effect and stability are no help. For example, when the biodegradable surfactant contains 8.2% by weight of the lecithin, the butyl cellosolve may be 0.9% by weight of the latex composition, the sum of the two being 9.1%; or, the lecithin alone is 9.1% of the latex composition, but is not limited thereto.

該酸鹼緩衝劑以重量計為該乳膠組合物之8~9.5%。由於微生物厭氧還原脫氯反應是一產酸反應,會使土壤或地下水酸化而抑制現地微生物的生長,故本發明的該乳膠組合物中利用該酸鹼緩衝劑可經水解生成離子態的共軛鹼基對(OH-),來緩衝pH值的變化,維持有利於微生物生長的偏中性環境。該酸鹼緩衝劑係選自檸檬酸、磷酸氫二鈉或兩者之混合物,具有濃度為0.1M~0.2M(體積莫耳濃度),可例如是0.1M、0.15M或0.2M,然不限於此。較佳的,該酸鹼緩衝劑同時包含了檸檬酸與磷酸氫二鈉,且該檸檬酸與該磷酸氫二鈉的重量比是1:9。該酸鹼緩衝劑可使該乳膠組合物的pH值維持在7~7.5左右,例如7.2、7.25或7.5,然不限於此。 The acid-base buffer is from 8 to 9.5% by weight of the latex composition. Since the anaerobic reduction dechlorination reaction of the microorganism is an acidogenic reaction, the soil or the groundwater is acidified to inhibit the growth of the existing microorganisms, so the acid-base buffer of the latex composition of the present invention can be hydrolyzed to form an ionic state. A yoke base pair (OH - ) to buffer changes in pH and maintain a neutral environment conducive to microbial growth. The acid-base buffer is selected from the group consisting of citric acid, disodium hydrogen phosphate or a mixture of the two, and has a concentration of 0.1 M to 0.2 M (volume concentration), which may be, for example, 0.1 M, 0.15 M or 0.2 M, but not Limited to this. Preferably, the acid-base buffer comprises both citric acid and disodium hydrogen phosphate, and the weight ratio of the citric acid to the disodium hydrogen phosphate is 1:9. The acid-base buffer can maintain the pH of the latex composition at about 7 to 7.5, such as 7.2, 7.25 or 7.5, but is not limited thereto.

本發明之另一實施例提供一種乳膠組合物的製造方法,其主要包含步驟:(S01)、混合一植物油、一生物可分解界面活性劑、一酸鹼緩衝劑以及水,以形成一混合物;以及(S02)、對該混合物施加一預設時間的超聲波,以進行一乳化作用,形成上述之該乳膠組合物。本發明將於下文逐一詳細說明較佳實施例之上述各步驟的實施細節及其原理。再者,由於乳化作用是屬於物理狀態的改變,因此該步驟(S01)中的各種成份比例理論上將會大致對應於該乳膠組合物中各成份的重量比,於此合先述明。 Another embodiment of the present invention provides a method for producing a latex composition, which mainly comprises the steps of: (S01), mixing a vegetable oil, a biodegradable surfactant, an acid-base buffer, and water to form a mixture; And (S02), applying ultrasonic waves to the mixture for a predetermined period of time to perform an emulsification to form the latex composition described above. The details of the implementation of the above-described steps of the preferred embodiment and the principles thereof will be described in detail below. Further, since the emulsification is a change in the physical state, the ratio of the various components in the step (S01) will theoretically correspond roughly to the weight ratio of each component in the latex composition, which will be described first.

本發明一實施例之乳膠組合物的製造方法首先係:(S01)、混合一植物油、一生物可分解界面活性劑、一酸鹼緩衝劑以及水,以形成一混合物。在本步驟中,該生物可分解界面活性劑包含卵磷脂,且該生物可分解界面活性劑以重量計為該混合物之4.5~10.1%。該植物油和該生物可分解界面活性劑的重量比為1.5:1,例如,當該植物油以重量計為該乳膠組合物之15%時,該生物可分解界面活性劑則為該混合物之10%,然不限於此。該植物油以重量計為該乳膠組合物之9~18.2%,較佳為13~15%。該卵磷脂以重量計為該混合物之4.5~9.1%,較佳為8~9.1%,可例如是8、8.5或9.1%,然不限於此。該生物可分解界面活性劑還可以包含一丁基溶纖劑,且該丁基溶纖劑以重量計為該混合物之0~1%,可例如是0、0.5或0.9%,然不限於此。舉例來說,當該生物可分解界面活性劑含有該卵磷脂以重量計為該混合物之8.2%時,該丁基溶纖劑以重量計可為該混合物之0.9%,兩者總和為9.1%;或者,僅含有該卵磷脂為該混合物之9.1%,然不限於此。 The method for producing a latex composition according to an embodiment of the present invention is first: (S01), mixing a vegetable oil, a biodegradable surfactant, an acid-base buffer, and water to form a mixture. In this step, the biodegradable surfactant comprises lecithin, and the biodegradable surfactant is 4.5 to 10.1% by weight of the mixture. The weight ratio of the vegetable oil to the biodegradable surfactant is 1.5:1. For example, when the vegetable oil is 15% by weight of the latex composition, the biodegradable surfactant is 10% of the mixture. However, it is not limited to this. The vegetable oil is from 9 to 18.2%, preferably from 13 to 15% by weight of the latex composition. The lecithin is 4.5 to 9.1% by weight, preferably 8 to 9.1% by weight of the mixture, and may be, for example, 8, 8.5 or 9.1%, but is not limited thereto. The biodegradable surfactant may further comprise monobutyl cellosolve, and the butyl cellosolve is 0 to 1% by weight of the mixture, and may be, for example, 0, 0.5 or 0.9%, but is not limited thereto. For example, when the biodegradable surfactant contains 8.2% by weight of the lecithin, the butyl cellosolve may be 0.9% by weight of the mixture, and the sum of the two is 9.1%; or The lecithin alone is 9.1% of the mixture, but is not limited thereto.

此外,在本步驟中,該酸鹼緩衝劑以重量計為該混合物之8~9.5%。該酸鹼緩衝劑可為檸檬酸、磷酸氫二鈉或其混合物,且該酸鹼緩衝劑的濃度可為0.1M~0.2M,可例如是0.1M、0.15M或0.2M,然不限於此。較佳的,該酸鹼緩衝劑同時包含了檸檬酸與磷酸氫二鈉,且該檸檬酸與該磷酸氫二鈉的重量比是1:9。該酸鹼緩衝劑可使該乳膠組合物的pH值維持在7~7.5左右,例如7.2、7.25或7.5,然不限於此。 Further, in this step, the acid-base buffer is from 8 to 9.5% by weight of the mixture. The acid-base buffer may be citric acid, disodium hydrogen phosphate or a mixture thereof, and the concentration of the acid-base buffer may be 0.1M to 0.2M, and may be, for example, 0.1M, 0.15M or 0.2M, but is not limited thereto. . Preferably, the acid-base buffer comprises both citric acid and disodium hydrogen phosphate, and the weight ratio of the citric acid to the disodium hydrogen phosphate is 1:9. The acid-base buffer can maintain the pH of the latex composition at about 7 to 7.5, such as 7.2, 7.25 or 7.5, but is not limited thereto.

本發明一實施例之乳膠組合物的製造方法接著係:(S02)、對該混合物施加超聲波,以進行一乳化作用,形成上述之該乳膠組合物。 在本步驟中,該超聲波可例如是使用一類比式細胞粉碎機(Branson Model 250/450),其原理是利用超聲波之機械及空化作用,使乳化作用的過程產生激烈的顆粒碰撞而產生高溫、高壓及高流動性之細小油滴顆粒。該超聲波的功率可為10~60%,較佳是40~60%,且施加該超聲波的時間係持續約1~15分鐘,較佳是10~15分鐘,然不限於此。該乳膠組合物具有平均乳化粒徑為0.2至0.5微米,例如是0.28微米,然不限於此。且該乳膠組合物的界達電位(Zeda Potential)為負值,有利於土壤孔隙間傳輸。 A method for producing a latex composition according to an embodiment of the present invention is followed by: (S02), applying ultrasonic waves to the mixture to perform an emulsification to form the above-described latex composition. In this step, the ultrasonic wave can be, for example, an analog cell pulverizer (Branson Model 250/450), which uses the mechanical and cavitation effects of ultrasonic waves to cause intense particle collision and high temperature during the emulsification process. Fine oil droplets with high pressure and high fluidity. The ultrasonic power may be 10 to 60%, preferably 40 to 60%, and the time for applying the ultrasonic wave lasts for about 1 to 15 minutes, preferably 10 to 15 minutes, but is not limited thereto. The latex composition has an average emulsified particle diameter of 0.2 to 0.5 μm, for example, 0.28 μm, but is not limited thereto. Moreover, the Zeda Potential of the latex composition has a negative value, which is favorable for transport between soil pores.

本發明為了瞭解該乳膠組合物是否可以有效控制地下水質酸化,以微生態系統模擬反應。實驗所用之地下水為現地未受污染區域,並依照行政院環保署公告(NIEA W103.54B)進行採樣後,以4℃冷藏保存。 其批次實驗設計以微生態系統(microcosm)模擬現地環境。 In order to understand whether the latex composition can effectively control the acidification of groundwater, the present invention simulates the reaction with a micro-ecological system. The groundwater used in the experiment was an unspoiled area in the field and was sampled at 4 °C in accordance with the Environmental Protection Agency's announcement (NIEA W103.54B). Its batch experimental design simulates the local environment with a microcosm system.

首先,將500毫升的細口血清瓶於高溫、高壓下(121℃,15lb/in2)維持30分鐘之滅菌時間,以確保反應瓶呈現無菌狀態,並加入該乳膠組合物,然後以分注器分裝現地地下水500毫升,實驗結果簡要敘述如下。 First, a 500 ml fine-mouthed serum bottle is maintained at a high temperature and high pressure (121 ° C, 15 lb / in 2 ) for 30 minutes sterilization time to ensure that the reaction bottle is sterile, and the latex composition is added, and then the dispenser is added. The underground groundwater is divided into 500 ml. The experimental results are briefly described below.

反應期間pH值初始為7.7,於反應第5天後pH值下降為6.8,反應後期pH值均維持在中性之環境條件(pH值6.8-7.0),推測初期該乳膠組合物經厭氧發酵後所產生之大量H2及低分子有機酸,故造成pH值下降,使水質環境有酸化之虞慮。然而,因該乳膠組合物中含有酸鹼緩衝劑,經水解而生成離子態共軛鹼基對(OH-)之後,能有效達到緩衝水體中H+及OH-離子濃度變化之趨勢。在溶氧方面,初始濃度為1.99mg/L,反應第5天即可降至約0.82mg/L,反應期間溶氧皆維持在0.6mg/L。而氧化還原 電位(ORP)的初始值為163mV,反應第5天降至-163mV,之後反應皆維持在-200到-300mV之間,顯示該乳膠組合物可有效消耗水體中的溶氧,使環境呈現厭氧狀態,可增強還原脫氯之效果。由上述水質趨勢可已得知,該乳膠組合物可在有限之溶氧內刺激微生物反應,並營造厭氧還原脫氯之環境。 During the reaction, the initial pH value was 7.7, and the pH value decreased to 6.8 after the fifth day of the reaction. The pH value was maintained at neutral environmental conditions (pH 6.8-7.0) at the late stage of the reaction. It is speculated that the latex composition was initially subjected to anaerobic fermentation. After the large amount of H 2 and low molecular organic acids produced, the pH value is lowered, and the water quality environment is acidified. However, since the latex composition contains an acid-base buffer and hydrolyzed to form an ionic conjugate base pair (OH - ), the concentration of H + and OH - ions in the buffer water can be effectively changed. In terms of dissolved oxygen, the initial concentration is 1.99 mg/L, and the reaction can be reduced to about 0.82 mg/L on the fifth day, and the dissolved oxygen is maintained at 0.6 mg/L during the reaction. The initial value of the oxidation-reduction potential (ORP) was 163 mV, and the reaction decreased to -163 mV on the fifth day, after which the reaction was maintained between -200 and -300 mV, indicating that the latex composition can effectively consume dissolved oxygen in the water. The environment is anaerobic and enhances the effect of reductive dechlorination. It is known from the above water quality trends that the latex composition can stimulate microbial reactions in a limited amount of dissolved oxygen and create an environment for anaerobic reductive dechlorination.

再者,該乳膠組合物為一種生物可分解之緩釋釋氫基質,其總有機碳(TOC)的初始濃度為253mg/L,反應第10天降低至221mg/L,藉由監測TOC濃度變化趨勢可瞭解該乳膠組合物能有效被微生物利用之情形。分析其總生菌數,初始總菌數5.72×102CFU/mL,反應第10天之總生菌數2.24×105CFU/mL,顯示該乳膠組合物確實可以長期提供微生物生長來源。 Furthermore, the latex composition is a biodegradable sustained release hydrogen release matrix having an initial organic carbon (TOC) concentration of 253 mg/L and a reduction of 221 mg/L on the 10th day of the reaction by monitoring changes in TOC concentration. The trend is to understand the situation in which the latex composition can be effectively utilized by microorganisms. The total number of bacteria was analyzed. The initial total bacterial count was 5.72×10 2 CFU/mL, and the total number of bacteria on the 10th day of the reaction was 2.24×10 5 CFU/mL, indicating that the latex composition can provide a source of microbial growth for a long time.

相較於習知技術,本發明所提供之乳膠組合物及其製造方法,可提供具有細緻乳化粒徑的乳膠組合物,其平均乳化粒徑可達0.2至0.5微米(亦即具有奈米級的平均乳化粒徑),且具有以下優點:(1)利用乳化油滴攔阻污染物,可侷限污染物範圍;(2)可提升現地土壤含水層或地下水的pH緩衝能力,維持利於微生物生長之中性環境;以及(3)可快速營造厭氧環境,提高現地菌種的豐富度。 Compared with the prior art, the latex composition provided by the present invention and the method for producing the same can provide a latex composition having a finely emulsified particle diameter, and the average emulsified particle diameter can be 0.2 to 0.5 μm (that is, having a nanometer level). Average emulsified particle size), and has the following advantages: (1) using emulsified oil droplets to block pollutants, can limit the range of pollutants; (2) can improve the pH buffer capacity of existing soil aquifers or groundwater, and maintain microbial growth Neutral environment; and (3) can quickly create an anaerobic environment and increase the richness of existing strains.

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 (14)

一種乳膠組合物,用於整治含氯有機污染物,該乳膠組合物包含一植物油、一生物可分解界面活性劑、一酸鹼緩衝劑以及其餘為水,其中該生物可分解界面活性劑包含卵磷脂,且該生物可分解界面活性劑以重量計為該乳膠組合物之4.5~10.1%;該植物油以重量計為該乳膠組合物之9~18.2%;該酸鹼緩衝劑以重量計為該乳膠組合物之8~9.5%;該酸鹼緩衝劑同時包含檸檬酸與磷酸氫二鈉;以及該乳膠組合物具有一乳化平均粒徑為0.2~0.5微米。A latex composition for treating a chlorine-containing organic contaminant, the latex composition comprising a vegetable oil, a biodegradable surfactant, an acid-base buffer, and the balance being water, wherein the biodegradable surfactant comprises an egg a phospholipid, and the biodegradable surfactant is 4.5 to 10.1% by weight of the latex composition; the vegetable oil is 9 to 18.2% by weight of the latex composition; the acid-base buffer is by weight 8 to 9.5% of the latex composition; the acid-base buffer comprises both citric acid and disodium hydrogen phosphate; and the latex composition has an emulsified average particle diameter of 0.2 to 0.5 μm. 如申請專利範圍第1項所述之乳膠組合物,其中該植物油和該生物可分解界面活性劑的重量比為1.5:1。The latex composition of claim 1, wherein the weight ratio of the vegetable oil to the biodegradable surfactant is 1.5:1. 如申請專利範圍第1項所述之乳膠組合物,其中該卵磷脂以重量計為該乳膠組合物之4.5~9.1%。The latex composition of claim 1, wherein the lecithin is from 4.5 to 9.1% by weight of the latex composition. 如申請專利範圍第1項所述之乳膠組合物,其中該生物可分解界面活性劑還包含一丁基溶纖劑,且該丁基溶纖劑以重量計為該乳膠組合物之0~1%。The latex composition of claim 1, wherein the biodegradable surfactant further comprises monobutyl cellosolve, and the butyl cellosolve is from 0 to 1% by weight of the latex composition. 如申請專利範圍第1項所述之乳膠組合物,該檸檬酸與該磷酸氫二鈉的重量比是1:9。The latex composition of claim 1, wherein the weight ratio of the citric acid to the disodium hydrogen phosphate is 1:9. 如申請專利範圍第1項所述之乳膠組合物,其中該酸鹼緩衝劑的濃度為0.1M~0.2M。The latex composition of claim 1, wherein the acid-base buffer has a concentration of 0.1 M to 0.2 M. 一種乳膠組合物的製造方法,其包含步驟:混合一植物油、一生物可分解界面活性劑、一酸鹼緩衝劑以及水,以形成一混合物;以及對該混合物施加超聲波,以進行一乳化作用,以形成如申請專利範圍第1項所述之乳膠組合物;其中該生物可分解界面活性劑包含卵磷脂,且該生物可分解界面活性劑以重量計為該混合物之4.5~10.1%;該植物油以重量計為該混合物之9~18.2%;該酸鹼緩衝劑以重量計為該混合物之8~9.5%;該酸鹼緩衝劑同時包含檸檬酸與磷酸氫二鈉。A method for producing a latex composition, comprising the steps of: mixing a vegetable oil, a biodegradable surfactant, an acid-base buffer, and water to form a mixture; and applying ultrasonic waves to the mixture to perform an emulsification, The latex composition according to claim 1, wherein the biodegradable surfactant comprises lecithin, and the biodegradable surfactant is 4.5 to 10.1% by weight of the mixture; the vegetable oil 9 to 18.2% by weight of the mixture; the acid-base buffer is 8 to 9.5% by weight of the mixture; the acid-base buffer contains both citric acid and disodium hydrogen phosphate. 如申請專利範圍第7項所述之乳膠組合物的製造方法,其中該超聲波的功率為10~60%。The method for producing a latex composition according to claim 7, wherein the ultrasonic wave has a power of 10 to 60%. 如申請專利範圍第7項所述之乳膠組合物的製造方法,其中施加該超聲波係持續15分鐘。The method for producing a latex composition according to claim 7, wherein the ultrasonic system is applied for 15 minutes. 如申請專利範圍第7項所述之乳膠組合物的製造方法,其中該植物油和該生物可分解界面活性劑的重量比為1.5:1。The method for producing a latex composition according to claim 7, wherein the weight ratio of the vegetable oil to the biodegradable surfactant is 1.5:1. 如申請專利範圍第7項所述之乳膠組合物的製造方法,其中該卵磷脂以重量計為該混合物之4.5~9.1%。The method for producing a latex composition according to claim 7, wherein the lecithin is 4.5 to 9.1% by weight of the mixture. 如申請專利範圍第7項所述之乳膠組合物的製造方法,其中該生物可分解界面活性劑還包含一丁基溶纖劑,且該丁基溶纖劑以重量計為該混合物之0~1%。The method for producing a latex composition according to claim 7, wherein the biodegradable surfactant further comprises monobutyl cellosolve, and the butyl cellosolve is from 0 to 1% by weight of the mixture. 如申請專利範圍第7項所述之乳膠組合物的製造方法,其中該檸檬酸與該磷酸氫二鈉的重量比是1:9。The method for producing a latex composition according to claim 7, wherein the weight ratio of the citric acid to the disodium hydrogen phosphate is 1:9. 如申請專利範圍第7項所述之乳膠組合物的製造方法,其中該酸鹼緩衝劑的濃度為0.1M~0.2M。The method for producing a latex composition according to claim 7, wherein the acid-base buffer has a concentration of 0.1 M to 0.2 M.
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