TW202134425A - Nutrient matrix for biological remediation of soil contaminated by total petroleum hydrocarbons (carbon-based bioremediation agent & carbon-based bioremediation enhancing agent) - Google Patents

Abstract

A surfactant and a nutrient matrix composition are described, which is suitable for soil remediation. The surfactant composition includes: fatty acid methyl ester ethoxylate greater than zero and less than or equal to 10 parts by weight; polyoxyethylene sorbitan alkyl ester greater than zero and less than or equal to 20 parts by weight; polyoxyethylene alkyl ester greater than zero and less than or equal to 20 parts by weight; and alkyl polyglycoside greater than zero and less than or equal to 10 parts by weight.

Description

A nutrient substrate for enhancing biological remediation of soil contaminated by total petroleum hydrocarbons (carbon-based biological incubation agent 　&　

The present invention relates to the field of environmental protection, particularly to a surfactant and nutritional matrix composition, and when necessary, oleophilic strains (or oleophilic bacteria liquid) can be added to the nutritional matrix composition.

In order to solve the total petroleum hydrocarbon (TPH) pollution that leaked into the soil due to human activities in the process of industrialization, it is necessary to develop economically effective and environmentally friendly remediation methods.

In addition, it is known that some microorganisms existing in soil and/or groundwater have the ability to decompose or degrade the aforementioned petroleum-based pollutants such as gasoline and diesel. Therefore, in recent years, some experts and scholars have suggested that these microorganisms can decompose petroleum-based pollutants into harmless compounds to solve the problem of petroleum-based chemicals in soil and/or groundwater caused by crude oil, gasoline, diesel, and heavy oil. The problem of pollution.

However, the efficiency of existing methods of using microorganisms to solve oil-contaminated soil still needs to be strengthened. Therefore, it is necessary to provide a surface active agent and a nutrient base, if necessary, to add a composition of oleophilic bacteria liquid to solve the problems of the conventional technology.

One object of the present invention is to provide a surfactant and nutrient matrix composition, which uses a specific composition to accelerate the efficiency of microbial decomposition of total petroleum hydrocarbons (TPH) in the soil. In addition, oleophilic strains (or oleophilic bacteria liquid) can be added to the nutrient matrix composition when needed. For example, for "Total Petroleum Hydrocarbons" (TPH) contaminated sites, where the pollution concentration is high and the construction period is short In the case, when only using local microorganisms is not enough to achieve the remediation goal, additional oleophilic strains (or oleophilic bacteria liquid) can be added to improve the remediation efficiency (which can reduce the construction period).

In order to achieve the above objective, the present invention provides a surfactant suitable for soil remediation, the surfactant comprising: greater than zero and less than or equal to 10 parts by weight of fatty acid methyl ester ethoxylate (Fatty acid methyl ester ethoxylate; FMEE) Greater than zero and less than 20 parts by weight of polyoxyethylene sorbitan alkyl ester (commonly known as tween); greater than zero and less than or equal to 20 parts by weight of polyoxyethylene alkyl ether; and greater than zero and less than Equal to 10 parts by weight of alkyl glycoside (Alkyl Polyglycoside; APG for short).

In an embodiment of the present invention, the fatty acid methyl ester ethoxylate has the following general formula: RCO-(OCH ₂ CH ₂ ) _n -OCH ₃ , where R is an alkyl group and n is a positive integer greater than zero.

In an embodiment of the present invention, the polyoxyethylene sorbitan alkyl ester comprises at least one of tween-80 and tween-20.

In an embodiment of the present invention, the polyoxyethylene alkyl ether has the following general formula: RO-(CH ₂ CH ₂ O) _m -H, where R is an alkyl group, and m is a positive integer greater than zero.

To achieve the above objective, the present invention provides a nutrient matrix composition comprising: the surfactant as described in any of the above embodiments; molasses fermentation broth; lecithin; nitrogen nutrients; trace elements; and water, wherein The total weight of the nutrient base composition is 100 wt%, the surfactant system is between 1 to 5 wt%, the nitrogen nutrient salt is between 10 wt% and 20 wt%, and the molasses fermentation broth The lecithin is between 1 and 10 wt%, the lecithin is between 1 and 10 wt%, the trace element is between 1 wt% and 5 wt%, and the rest is water.

In an embodiment of the present invention, the trace element is microbiotic B group.

In an embodiment of the present invention, the nutrient base composition further comprises oleophilic strains, wherein based on the total weight of the nutrient base composition being 100 wt%, the oleophilic strain is between 0.1 to 1 wt%.

In an embodiment of the present invention, the nitrogen nutrient salt includes at least one of _{NH 4} Cl, NH ₄ NO ₃ and (NH ₄ ) ₂ HPO _3.

In order to make the above and other objectives, features, and advantages of the present invention more obvious and understandable, the preferred embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings. Furthermore, the directional terms mentioned in the present invention, such as up, down, top, bottom, front, back, left, right, inside, outside, side, surrounding, center, horizontal, horizontal, vertical, vertical, axial, The radial direction, the uppermost layer or the lowermost layer, etc., are only the direction of reference to the attached drawings. Therefore, the directional terms used are used to describe and understand the present invention, rather than to limit the present invention.

The surfactant of an embodiment of the present invention is suitable for soil remediation. The surfactant includes: greater than zero and less than or equal to 10 parts by weight of fatty acid methyl ester ethoxylates (such as 1, 2, 3, 4, 5, 6). , 7, 8, or 9 parts by weight); greater than zero and less than or equal to 20 parts by weight of polyoxyethylene sorbitan alkyl ester (for example, 2, 4, 6, 8, 10, 12, 14, 16 or 18 parts by weight) ); greater than zero and less than or equal to 20 parts by weight of polyoxyethylene alkyl ether (for example, 2, 4, 6, 8, 10, 12, 14, 16 or 18 parts by weight); and greater than zero and less than or equal to 10 parts by weight Alkyl glycoside (for example, 1, 2, 3, 4, 5, 6, 7, 8, or 9 parts by weight). In one embodiment, the surfactant in the embodiment of the present invention can basically consist of the above four compounds. In another embodiment, the surfactant of the embodiment of the present invention is composed of the above four compounds.

In one embodiment, the fatty acid methyl ester ethoxylate ((Fatty acid methyl ester ethoxylate; FMEE) has the following general formula: RCO-(OCH ₂ CH ₂ ) _n -OCH ₃ , where R is an alkyl group and n is A positive integer greater than 0. In one example, R can be a methyl group, an ethyl group, a propyl group, a butanyl group, or an alkyl group with more than 4 C numbers. In another example, n can be 1, 2 , 3 or a positive integer greater than 3.

In one embodiment, the polyoxyethylene sorbitan alkyl ester (commonly known as tween) comprises tween-80 (also known as polyoxyethylene sorbitan monooleate) and tween-20 (also known as At least one of polyoxyethylene sorbitan monolaurate).

In one embodiment, the polyoxyethylene alkyl ether has the following general formula: RO-(CH ₂ CH ₂ O) _m -H, wherein R is an alkyl group, and m is a positive integer greater than zero. In an example, R can be a methyl group, an ethyl group, a propyl group, a butanyl group, or an alkyl group with more than 4 C numbers. In another example, m can be 1, 2, 3, or a positive integer greater than 3.

In one embodiment, the surfactant is a biodegradable surfactant, which helps reduce environmental pollution.

It should be mentioned that when the surface active agent of the embodiment of the present invention is applied to soil remediation, it can accelerate the efficiency of microbial decomposition of total petroleum hydrocarbon (TPH) in the soil. It is further explained that the above-mentioned effects are mainly achieved by using specific ratios and specific types of compositions in the surfactants of the embodiments of the present invention. The relevant experimental analysis will be described in the following paragraphs.

Another embodiment of the present invention provides a nutrient matrix composition (in some cases, the nutrient matrix composition of the present invention may also be referred to as a carbon-based biological incubator), comprising: the surface activity of any of the above-mentioned embodiments of the present invention Molasses fermentation broth; lecithin; nitrogen nutrient salts; trace elements; and water, wherein, based on the total weight of the nutrient matrix composition as 100 wt%, the surfactant is between 1 to 5 wt% (E.g. 1.5, 2, 2.5, 3, 3.5, 4, or 4.5 wt%), the nitrogen nutrient is between 10 wt% to 20 wt% (e.g. 11, 12, 13, 14, 15, 16, 17 , 18 or 19 wt%), the molasses fermentation broth is between 1 and 10 wt% (for example, 1, 2, 3, 4, 5, 6, 7, 8, or 9 wt%), and the lecithin is between 1 and 10 wt% 10 wt% (e.g. 1, 2, 3, 4, 5, 6, 7, 8 or 9 wt%), the trace element is between 1 wt% to 5 wt% (e.g. 1.5, 2, 2.5, 3, 3.5, 4, or 4.5 wt%), and the rest is water. In one embodiment, the nutrient matrix composition of the embodiment of the present invention can basically consist of the above-mentioned surfactants, molasses fermentation broth, lecithin, nitrogen nutrients, trace elements and water. In another embodiment, the surfactant of the embodiment of the present invention is composed of the above-mentioned surfactant, molasses fermentation broth, lecithin, nitrogen nutrients, trace elements, and water.

In one embodiment, the molasses fermentation broth mainly provides a carbon source and is mainly used as a nutrient source for microorganisms. The molasses fermentation broth can be formed, for example, by using molasses as the main raw material, and then adding fermentation strains to a medium composed of nutrient elements such as honey, nitrogen, phosphorus, calcium, sodium, trace elements, vitamins, etc., in the fermentation tank Closed fermentation is carried out under sterile conditions. After that, the culture medium after extraction and fermentation undergoes low-temperature dehydration, evaporation and concentration to form a molasses fermentation broth.

In another embodiment, the nitrogen nutrient salt can be used as a nitrogen source, mainly as a nutrient source for microorganisms. In some examples, the nitrogen nutrient salt includes at least one of _{NH 4} Cl, NH ₄ NO ₃ and (NH ₄ ) ₂ HPO _3.

It should be mentioned that when the nutrient matrix composition of the embodiment of the present invention is applied to soil remediation, the surfactant can accelerate the efficiency of microbial decomposition of total petroleum hydrocarbon (TPH) in the soil. On the other hand, molasses fermentation broth, lecithin, nitrogen nutrients, and trace elements can be used as nutrient sources for microorganisms, which can further accelerate the efficiency of microorganisms in the soil to decompose total petroleum hydrocarbons (TPH).

In one embodiment, the micronutrient group B can be used to provide nutrients to microorganisms.

In another embodiment, the nutrient matrix composition further comprises oleophilic strains (also called oleophilic bacteria liquid), wherein based on the total weight of the nutrient matrix composition being 100 wt%, the oleophilic strain is between 0.1 To 1 wt%. Specifically, in the "Total Petroleum Hydrocarbons" (TPH) contaminated site, when the pollution concentration is high and the construction period is short, and the use of local microorganisms is not enough to achieve the remediation goals, additional oils can be added Strains (for example, between 0.1 to 1 wt%) to accelerate the remediation rate. It is worth mentioning that, in some cases, the nutrient matrix composition of the present invention can also be referred to as a carbon-based biological rejuvenation enhancer after adding oleophilic strains.

The following examples and comparative examples are given to illustrate that the surfactant and nutrient matrix composition of the examples of the present invention can indeed accelerate the efficiency of microbial decomposition of total petroleum hydrocarbons (TPH) in the soil.

Example 1 (Carbon-based biological incubator)

First, a surfactant is provided, which contains more than zero and less than or equal to 10 parts by weight of fatty acid methyl ester ethoxylate (for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 parts by weight, This embodiment uses, for example, 5 parts by weight, but other parts by weight can also be used, and can achieve a similar effect of 5 parts by weight); greater than zero and less than or equal to 20 parts by weight of polyoxyethylene sorbitan alkyl ester (for example, 2 , 4, 6, 8, 10, 12, 14, 16, 18 or 20 parts by weight, this embodiment uses 10 parts by weight, for example, but other parts by weight can also be used, and a similar effect of 10 parts by weight can be achieved); Zero and less than or equal to 20 parts by weight of polyoxyethylene alkyl ether (for example, 2, 4, 6, 8, 10, 12, 14, 16, 18 or 20 parts by weight, this embodiment uses 10 parts by weight, but other parts by weight Parts can also be used, and can achieve a similar effect of 10 parts by weight); and more than zero and less than or equal to 10 parts by weight of alkyl glycosides (for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 Or 10 parts by weight, for example, 5 parts by weight is used in this embodiment, but other parts by weight can also be used, and an effect similar to 5 parts by weight can be achieved). Afterwards, the surfactant, molasses fermentation broth, lecithin, nitrogen nutrients, trace elements and water are mixed to obtain a nutrient matrix composition, wherein the total weight of the nutrient matrix composition is 100 wt%, the surface active The agent system is between 1 to 5 wt% (for example, 1.5, 2, 2.5, 3, 3.5, 4, or 4.5 wt%. For example, 2.5 wt% is used in this embodiment, but other wt% can also be used, and similar results can be achieved. 2.5 wt% effect), the nitrogen nutrient is between 10 wt% and 20 wt% (for example, 11, 12, 13, 14, 15, 16, 17, 18, or 19 wt%). In this embodiment, for example, 15 wt%, but other wt% can also be used, and can achieve a similar effect of 15 wt%), the molasses fermentation broth is between 1 to 10 wt% (for example, 1, 2, 3, 4, 5, 6, 7, 8 or 9 wt%, for example, 5 wt% is used in this embodiment, but other wt% can also be used, and a similar effect of 5 wt% can be achieved), the lecithin system is between 1 to 10 wt% (for example, 1 , 2, 3, 4, 5, 6, 7, 8, or 9 wt%, this embodiment uses, for example, 5 wt%, but other wt% can also be used, and an effect similar to 5 wt% can be achieved), the trace element It is between 1 wt% and 5 wt% (for example, 1.5, 2, 2.5, 3, 3.5, 4, or 4.5 wt%. In this embodiment, 2.5 wt% is used, but other wt% can also be used, and similar results can be achieved. 2.5 wt% effect), and the rest is water.

Mix the above nutrient matrix composition into a crude soil contaminated with oil (the TPH concentration of the original soil is about 5139 mg/kg), and then measure the TPH concentration of the original soil on 7 days, 14 days and 28 days. Divide rate. The analysis method of the removal rate of the above TPH concentration can refer to the analysis method published by the Environmental Inspection Agency of the Republic of China (Detection Method of Total Petroleum Hydrocarbons in Soil-Gas Chromatography/Flame Ionization Detector Method; NIEA S703.62B ). Please refer to Figure 1 for the analysis results of Example 1.

Example 2 (Carbon-based biological incubation enhancer)

The preparation method of the nutritional matrix composition of Example 2 is roughly the same as that of Example 1, except that the nutritional matrix composition also contains oleophilic strains, wherein the total weight of the nutritional matrix composition is 100 wt%. The oleophilic strain is between 0.1 and 1 wt% (for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9 wt%. In this embodiment, 0.5 wt% is used, but other wt% can also be used. And can achieve an effect similar to 0.5 wt%).

Mix the above nutrient matrix composition into a crude soil contaminated with oil (the TPH concentration of the original soil is about 5139 mg/kg), and then measure the TPH concentration of the original soil on 7 days, 14 days and 28 days. Divide rate. The analysis method of the removal rate of the above TPH concentration can refer to the analysis method published by the Environmental Inspection Agency of the Republic of China (Detection Method of Total Petroleum Hydrocarbons in Soil-Gas Chromatography/Flame Ionization Detector Method; NIEA S703.62B ). Please refer to Figure 1 for the analysis results of Example 2.

Comparative example 1

Provide a nutrient. The nutrient is based on 100 parts by weight, and the nutrient includes about 95 parts by weight of water and about 5 parts by weight of a commercially available nutrient base. The total weight of the nutrient base is 100 wt%, and the nutrient base contains 47.7 wt% of NH ₄ Cl, 34.6 wt% of Na ₂ HPO ₄ , 14.3 wt% of KH ₂ PO ₄ 600 g, and 3.4 wt% of NaCl .

Mix the above nutrients into a crude soil contaminated with oil (the TPH concentration of the original soil is about 5139 mg/kg), and then measure the removal rate of the TPH concentration of the original soil on 7 days, 14 days and 28 days. . The analysis method of the removal rate of the above TPH concentration can refer to the analysis method published by the Environmental Inspection Agency of the Republic of China (detection method of total petroleum hydrocarbons in soil: gas chromatograph/flame ionization detector method; NIEA S703.62B ). Please refer to Figure 1 for the analysis results of Comparative Example 1.

It can be seen from Fig. 1 that the present invention can have a TPH removal efficiency superior to that of only adding general commercial nutrient bases by adding specific types and specific ratios of compounds. In particular, the treatment effect in the early stage (for example, 7 days and 14 days) has been significantly improved (for example, 3.5% and 3.81%, respectively). In addition, the treatment effects for 28 days in Example 1 and Comparative Example 1 are roughly the same. It is presumed that the nutrient substrate as a carbon source/nitrogen source has been consumed by microorganisms, so a similar removal efficiency is reached around 28 days ( For example, about 50 to 53%). Therefore, if appropriate amounts of the nutrient base composition and nutrient base are added to Example 1 and Comparative Example 1 in about 14 days, Example 1 can still have better TPH removal efficiency than Comparative Example 1.

In addition, comparing Example 2 with Comparative Example 1, it can be seen that adding specific types and specific ratios of compounds, and adding additional specific ratios of oleophilic strains, can have a TPH migration superior to that of only adding general commercially available nutrient substrates. In addition to efficiency. In particular, the treatment effect in the early stage (for example, 7 days and 14 days) has been significantly improved (for example, an increase of 16.36% and 9.02%, respectively). In addition, the treatment effects for 28 days in Example 2 and Comparative Example 1 are roughly the same. It is presumed that the nutrient substrate as a carbon source/nitrogen source has been consumed by microorganisms, so a similar removal efficiency is reached around 28 days ( For example, about 50 to 53%). Therefore, if appropriate amounts of the nutrient base composition and nutrient base are added to Example 2 and Comparative Example 1 in about 14 days, Example 2 can still have better TPH removal efficiency than Comparative Example 1.

It is worth mentioning that the removal efficiency of Embodiment 2 is also better than that of Embodiment 1. It can be seen that adding a specific ratio of oleophilic strains will also help improve the TPH removal efficiency in the early stage (for example, the treatment effect for 7 days or 14 days).

It can be seen that the present invention utilizes specific types and specific ratios of surfactants to achieve excellent TPH removal efficiency. In addition, the present invention also provides a nutrient matrix composition, which has a specific ratio of the surfactant, nutrient ingredients and water of the present invention, which can be used for soil remediation. In other words, the combination of specific types of surfactants and specific types of nutrients (molasses fermentation broth; lecithin; nitrogen nutrients and trace elements) enables microorganisms to have excellent TPH removal efficiency.

Although the present invention has been disclosed in preferred embodiments, it is not intended to limit the present invention. Anyone familiar with the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the present invention The scope of protection shall be subject to the scope of the attached patent application.

without

Figure 1 is a graph showing the analysis results of Example 1, Example 2 and Comparative Example 1.

Claims (8)

A surface active agent suitable for soil remediation, the surface active agent contains: More than zero and less than or equal to 10 parts by weight of fatty acid methyl ester ethoxylate; More than zero and less than or equal to 20 parts by weight of polyoxyethylene sorbitan alkyl ester; More than zero and less than or equal to 20 parts by weight of polyoxyethylene alkyl ether; and The alkyl glycoside is greater than zero and less than or equal to 10 parts by weight. The surfactant according to claim 1, wherein the fatty acid methyl ester ethoxylate has the following general formula: RCO-(OCH ₂ CH ₂ ) _n -OCH ₃ , wherein R is an alkyl group and n is a normal value greater than 0 Integer. The surfactant according to claim 1, wherein the polyoxyethylene sorbitan alkyl ester comprises at least one of tween-80 and tween-20. The surfactant according to claim 1, wherein the polyoxyethylene alkyl ether has the following general formula: RO-(CH ₂ CH ₂ O) _m -H, wherein R is an alkyl group, and m is a positive integer greater than 0 . A nutritional matrix composition comprising: The surfactant according to any one of claims 1 to 4; Molasses fermentation broth; Lecithin Nitrogen nutrient Trace elements; and water, Wherein, based on the total weight of the nutritional matrix composition being 100 wt%, the surfactant is between 1 and 5 wt%, the nitrogen nutrient is between 10 wt% and 20 wt%, and the The molasses fermentation broth is between 1 and 10 wt%, the lecithin is between 1 and 10 wt%, the trace element is between 1 wt% and 5 wt%, and the rest is water. The nutrient matrix composition according to claim 5, wherein the trace element is microbiotic B group. The nutritional matrix composition according to claim 5, further comprising oleophilic strains, wherein based on the total weight of the nutritional matrix composition as 100 wt%, the oleophilic strains are between 0.1 to 1 wt%. The nutrient matrix composition according to claim 5, wherein the nitrogen nutrient salt comprises at least one of _{NH 4} Cl, NH ₄ NO ₃ and (NH ₄ ) ₂ HPO _3.

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