TWI558671B - Emulsion solution for treating environment and method for treating polluted environment - Google Patents

Description

Emulsified stock solution for environmental remediation and treatment method for polluted environment

The application relates to an emulsified stock solution and a method for using the same to rectify the environment, in particular, an emulsified stock solution for environmental remediation and a remediation method for a polluted environment.

In soil and sediment, hydrophobic substances are usually the most difficult to remove or recover. In terms of sediment pollution, hydrophobic substances are easily reduced in solubility due to their hydrophobic properties and adsorbed in soil or sediment. The organic matter becomes a persistent organic pollutant. Therefore, the river sediment remediation system is an important part of environmental protection work. At present, all countries have different technologies to solve related remediation problems. At present, the methods for remediation of river sediments commonly found in various countries include methods such as sputum method, water burial method, and underwater burial method, which are summarized as follows.

The dredging method is to remove the contaminated bottom mud by mechanical tools, and then transport the excavated bottom mud to a qualified processing facility for treatment or after a series of treatments as a final ocean disposal (Palermo et al., 2008). However, when the excavation is carried out, it is easy to cause the high-concentration concentration of the sediment to rise and migrate with the river to the downstream and side, causing the pollution area to expand.

The confined disposal facility constructs a reinforced concrete structure near the site of the highly polluted sediment, which is closed after being buried, that is, the contaminated sediment is no longer excavated, but the final disposal is carried out near the contaminated site. Not treated (Netzband, 2002), may cause perpetual river and sea pollution.

Confined aquatic disposal is a method of digging a groove in the sediment under the surface of the water, placing the contaminated sediment in the groove, and covering it with clean sand, stones, etc. Cover it up (Thomas and Concord, 2005). It does not need to be disposed of in the highlands like the water burial method, but construction materials must be used on land to be buried.

The above-mentioned conventional sediment treatment methods have their own limitations or there is a risk of secondary pollution. For the special environment of river terrain, such as Taiwan, the situation of river sediment pollution is facing an increasingly serious trend. Most of the pollution types include heavy metals, polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). Polycyclic aromatic hydrocarbons (PAHs), etc., if the above-mentioned conventional sediment treatment technology is directly used, the effect may be poor and may cause secondary pollution. At the same time, due to the high degree of hydrophobicity of the above-mentioned organic pollutants, the pollutants of such pollutants become the notorious persistent organic pollutants (known as persistent organic pollutants, POPs) which are easily accumulated in the sediment. Therefore, how to effectively remediate contaminated sediments is the direction of the industry.

In view of this, the present application proposes an emulsified stock solution for environmental remediation, a preparation method thereof and a method for remediating a polluted environment, and provides an oil phase for re-distribution to effectively enrich the eucommia using a highly hydrophobic property of the POP. These pollutants; use active and effective demulsifier to separate and remove the oil phase rich in pollutants; a small part of the residual oil can provide microbial degradation of pollutants, to effectively break down biodegradation methods, only suitable for low to medium pollution The bottleneck of the object and the destruction of the existing ecosystem (including the microbial ecosystem) by the high-intensity physicochemical oxidation method, and the environmental remediation method can be used to recover or remove the hydrophobic substances in the soil to protect the environment and ecology. efficacy.

One aspect of the present invention is to provide an emulsified stock solution for environmental remediation, which comprises a nonionic surfactant, an oil solute, and water.

The nonionic surfactant contains from polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene-polyoxypropenol, polyoxyethylene fatty acid ester, trialkylamine oxide and mixtures thereof. Forming at least one of the selected groups.

The oil solute contains at least one selected from the group consisting of soybean oil, peanut oil, coconut oil, olive oil, grape seed oil, cottonseed oil, sunflower oil, palm oil, food grade oil, and mixtures thereof.

In one embodiment, the emulsified stock solution for environmental remediation of the present invention is a non-nano-doped (o/w) oil-in-water type, and the content of the oil solute is greater than 40%.

In one embodiment, the surfactant comprises polyethylene glycol, polyoxyethylene sorbitan, polyoxyethylene sorbitan monooleate, hexaol laurate, and mono-9-octadecenoic acid dehydration. The sorbitol ester comprises at least one selected from the group consisting of mixtures thereof.

In one embodiment, the emulsified liquid system for environmental remediation of the present invention further comprises at least one of an oil-water fusion agent, an emulsion stabilizer, an emulsion accelerator, an antioxidant, or a combination thereof for promoting emulsification between oil solute and water. effect.

In one embodiment, the oil particles of the emulsified stock solution for environmental remediation of the present invention have an average particle diameter in the range of 1 nm to 1000 nm.

In one embodiment, the oil particles of the emulsified stock solution for environmental remediation of the present invention have an average particle diameter in the range of 300 nm to 400 nm.

Another aspect of the present invention provides a method for preparing an emulsified stock solution for environmental remediation, which comprises: 15 to 75 parts by weight of water, 25 to 55 parts by weight of an oil solute, and the remaining part of a nonionic surfactant; The mixture was thoroughly stirred and mixed to prepare an emulsified stock solution.

The nonionic surfactant contains from polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene-polyoxypropenol, polyoxyethylene fatty acid ester, trialkylamine oxide and mixtures thereof. Forming at least one of the selected groups.

The oil solute contains at least one selected from the group consisting of soybean oil, peanut oil, coconut oil, olive oil, grape seed oil, cottonseed oil, sunflower oil, palm oil, food grade oil, and mixtures thereof.

A further aspect of the present invention provides a method for remediating a contaminated environment, which comprises: injecting the aforementioned emulsified stock solution for environmental remediation into a contaminated environment and thoroughly stirring the contaminated environment including pollutants, soil, sediment, Natural water or groundwater. Next, the demulsifier is added and thoroughly stirred, and the demulsifier is an ionic demulsifier or a nonionic demulsifier. Finally, the oil slick that has been concentrated or enriched with contaminants is recovered.

In one embodiment, the ionic demulsifier is at least one selected from the group consisting of sodium carbonate, calcium carbonate, copper sulfate, magnesium sulfate, aluminum sulfate, sodium chloride, calcium chloride, sodium benzoate, and combinations thereof.

In one embodiment, the nonionic demulsifier is at least one selected from the group consisting of SP type demulsifiers, AP type demulsifiers, AE type demulsifiers, AR type demulsifiers, and mixtures thereof.

In an embodiment, prior to the step of recovering the oil slick, the air is further introduced to sufficiently perform aeration.

In one embodiment, the aeration system is a multi-stage aeration.

In one embodiment, the method of recovering the oil slick includes at least one selected from the group consisting of surface floatation, stripping, mechanical oil scraping, and combinations thereof.

10‧‧‧Environmental remediation system

100‧‧‧Remediation unit

110‧‧‧ Inflow channel

120‧‧‧ outflow channel

130‧‧‧Mixed device

131‧‧‧Agitator

140‧‧‧Remediation tank

150‧‧‧Remediation Control Unit

151‧‧‧Steam recovery controller

152‧‧‧Detection unit

153‧‧‧ data processing device

154‧‧‧Switching device

155‧‧‧Communication device

156‧‧‧Remote computing device

157‧‧‧ Terminal devices

158‧‧‧Remote control system

159‧‧‧Cloud Control System

Fm‧‧‧detection signal

Om‧‧‧Steam recovery signal

LK‧‧‧Communication Link

SC1, SC2, SC3‧‧‧ control signals

S10, S20, S30, S40‧‧‧ steps

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic block diagram showing a method of remediation of a contaminated environment of the present invention.

Figure 2 is a schematic block diagram showing the environmental remediation system of the present invention.

3 is a schematic block diagram showing an environmental remediation system of other embodiments of the present invention.

Fig. 4 is a graph showing changes in BaP concentration with time in the treatment method of the contaminated environment of the present invention.

In order to make the various aspects and the aspects of the invention described above more readily apparent, the detailed description will be described in the accompanying drawings.

The above and other technical contents, features, and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments. The directional terms mentioned in the following embodiments, such as upper, lower, left, right, front or rear, etc., are only used to refer to the directions of the accompanying drawings. Therefore, the directional terms are used for illustration only and are not intended to limit the invention.

The following describes various embodiments of the emulsified stock solution for environmental remediation, the preparation method thereof, the remediation method of the contaminated environment, and the environmental remediation system.

According to one aspect of the present invention, an embodiment of an emulsified stock solution for environmental remediation is proposed, which is suitable for use in remediation of a contaminated environment. In this embodiment, the emulsified stock solution for environmental remediation includes at least a nonionic surfactant, an oil solute, and water.

The physical properties of the emulsified stock solution for environmental remediation according to this embodiment are as follows. The average particle diameter of the oil particles of the emulsified stock solution may be in the range of 1 nm to 1000 nm; preferably in the range of 300 nm to 400 nm. Further, the emulsified stock solution may be a non-nano (o/w) oil-in-water type. The oil-in-water type refers to an emulsified stock solution in which water is a dispersion and oil droplets are present in water. However, the embodiments of the present invention are not limited thereto.

In this embodiment, the nonionic surfactant is not dissociated in water, and is a hydrocarbon having a hydroxyl group (-OH) or an ether bond (R-O-R ' ) as a hydrophilic group and having 8 to 18 carbon atoms. The chain is a lipophilic structural molecule. The nonionic surfactant has a hydrophile-lipophile balance (HLB) of between 1 and 24. Since the nonionic surfactant is not present in the ionic state in the solution, it has high stability, is not easily affected by the presence of strong electrolytes, and is not easily affected by acids and alkalis, and can be mixed with other types of surfactants. Good compatibility, good solubility in various solvents, no strong adsorption on solid surfaces.

For example, the nonionic surfactant contains polyoxyethylene alkyl ether, polyoxyethylene tridecyl ether, polyoxyethylene oleyl ether, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, poly Oxyethylene vinyl stearyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol lauryl ether, polyethylene glycol cetyl ether, polyethylene glycol stearyl ether, alkyl phenol polyoxyl Polyoxyethylenes such as vinyl ether, polyoxyethylene-polyoxypropylene alcohol, polyoxyethylene fatty acid ester, high carbon fatty alcohol polyoxyethylene ether, trialkylamine oxide, surfactant of the following Table 1, and mixtures thereof Forming at least one of the selected groups. A preferred nonionic surfactant comprises at least one selected from the group consisting of polyoxyethylenes, polyols, alkyl ketamines, and mixtures thereof. However, it is not limited to this in the field of the invention. The nonionic surfactant of the polyol type comprises polyethylene glycol, polyoxyethylene sorbitan, polyoxyethylene sorbitan monooleate, hexaol laurate, mono-9-octadecenoic acid The sorbitan esters and at least one of the mixture selected from the group consisting of the mixture.

For another example, the oil solute contains at least one selected from the group consisting of soybean oil, peanut oil, coconut oil, olive oil, grape seed oil, cottonseed oil, sunflower oil, palm oil, food grade oil, and mixtures thereof. . However, it is not limited thereto in the field of the present invention, and animal oil, vegetable oil, mineral oil, or synthetic fat may be used as the oil solute. In one embodiment, the preferred oil solutes are, for example, soybean oil.

Preferably, the emulsified stock solution may further comprise an oil-water fusion agent, an emulsion stabilizer or an emulsification accelerator to enhance the emulsification between the oil solute and the water, increase the speed of oil-water fusion, and stabilize the composition properties of the emulsion. . However, the present invention is not limited thereto, and may further contain an antioxidant, a deodorant, a disinfectant, a microbial nutritional supplement, or the like. Among them, the antioxidant can prevent oxidation of the emulsified stock solution and rancidity. For example, the antioxidant may include dibutyl hydroxyl toluene (BHT), butylated hydroxyl anisole (BHA) or other substances having similar functions but not causing environmental pollution.

In addition, in order to make the residual unrecovered emulsified liquid suitable for microbial growth, nitrogen, phosphorus and other trace elements, so-called microbial nutritional supplements, may be additionally added to the emulsified stock solution. However, it must be determined according to the content of microbial nutrient additives contained in the environmental medium to be rectified. If the environmental medium does not contain any microbial nutrient additives, microbial nutrient additives must be added to the environmental medium; otherwise, no need to add .

According to another aspect of the present invention, an embodiment of a method for preparing an emulsified stock solution for environmental conditioning of the above emulsified stock solution is proposed.

In this embodiment, the preparation method of the emulsified stock solution for environmental remediation comprises at least: mixing 15 to 75 parts by weight of water, 25 to 55 parts by weight of the oil solute, and the remaining part of the nonionic surfactant, and utilizing The agitator is sufficiently stirred to cause emulsification, thereby preparing an emulsified stock solution such as a non-nano (o/w) oil-in-water type. Preferably, 40 to 60 parts by weight of water, 30 to 50 parts by weight of an oil solute, and 10 to 30 parts by weight of a nonionic surfactant are sufficiently stirred and mixed. Here, the component characteristics of the emulsified stock solution for environmental remediation have been described in detail in the foregoing embodiments, and will not be described herein.

Additives may be further added during the emulsification process, for example, oil-water fusion agents, emulsion stabilizers, emulsification accelerators, antioxidants, deodorants, disinfectants, microbial nutritional supplements, and the like. However, in this embodiment, it is not limited to this. Here, the characteristics of the above-mentioned add-ons have been described in detail in the foregoing embodiments, and are not described herein again.

The main procedures of the emulsification include, for example, at least: (1) the nonionic surfactant utilizes the affinity between the hydrophobic group and the hydrophilic group and the emulsified material to reduce the surface tension between the oil and the water, and enters between the oil and the water. , the oil and water are connected by means of a non-ionic surfactant; (2) as the surface tension between the oil and water decreases, the emulsified oil or water gradually becomes thinner, and the non-ionic surfactant is transmitted. And widely distributed on the surface of another liquid; (3) under the action of the hydrophobicity and hydrophilicity of the nonionic surfactant, the emulsified oil and the water gradually emulsification promoter are split, so that the oil or water is Emulsified and evenly dispersed in other liquids. But in the preparation of the present invention In the method, it is not limited to this.

The physical properties of the emulsified stock solution for environmental remediation prepared according to the preparation method of the present embodiment are as follows. The average particle diameter of the oil particles of the emulsified stock solution may be in the range of 1 nm to 1000 nm; preferably 300 nm to 400 nm. The scope.

According to still another aspect of the present invention, an embodiment of a method for remediating a contaminated environment in which a emulsified stock solution is used for remediation and purification of a contaminated environment is proposed to recover oil slick in a polluted environment.

Please refer to FIG. 1, which shows a schematic block diagram of a method for remediating a contaminated environment of the present invention. As shown in Figure 1, the method of remediation of the contaminated environment includes at least the following steps. As shown in step S10, an emulsified stock solution is prepared by a method for preparing an emulsified stock solution for environmental remediation. Next, as shown in step S20, the prepared emulsified stock solution is poured into a contaminated environment to obtain a premix, and the premix (that is, the contaminated environment in which the emulsified stock solution is added) is sufficiently stirred and mixed by a stirrer. The contaminated environment may include, for example, contaminants, soil, sediment, natural water or groundwater. Then, as shown in step S30, a demulsifier of a specific concentration is added to the premix to form a mixed milk, and the mixture is sufficiently stirred. After the milk is completely demulsified, an oil moisture layer is present, and the oil floats on the upper surface of the liquid, and the oil slick is recovered as shown in step S40.

The demulsifier can destroy the emulsified liquid structure to achieve the separation of the phases in the emulsion. In this embodiment, the demulsifier may include, for example, an ionic demulsifier, a nonionic demulsifier. For example, the ionic demulsifier is at least one selected from the group consisting of sodium carbonate, calcium carbonate, copper sulfate, magnesium sulfate, aluminum sulfate, sodium chloride, calcium chloride, sodium benzoate, and combinations thereof. An example of a preferred ionic demulsifier can be sodium carbonate.

The nonionic demulsifier is, for example, at least one selected from the group consisting of a SP type demulsifier, an AP type demulsifier, an AE type demulsifier, an AR type demulsifier, and a mixture thereof. Specifically, the main component of the SP type demulsifier is polyoxyethylene polyoxypropylene stearyl ether. The AP type demulsifier is a polyoxyethylene polyoxypropylene polyether which is a polyamine polyamine as an initiator amine. AE type demulsifier is based on multiple B A polyoxyethylene polyoxypropylene polyether having an olefin polyamine as an initiator. AR type demulsifier is a new oil-soluble nonionic demulsifier which is polymerized from alkyl phenolic resin, polyoxyethylene and polyoxypropylene. However, it is not limited to this in the field of the invention.

In this embodiment, the oil slick is a substance that is lighter in specific gravity than water and floats on the surface of the water to be separated from the water. By using the method of pressurizing and decompressing the inside of the tank, the air bubbles are attached to the outer surface of the rubber feather, and the extrusion process of the floating rubber feather is concentrated, and has a floating effect. For example, the method of recovering the oil slick includes, for example, at least one selected from the group consisting of surface floatation, stripping, mechanical oil scraping, and combinations thereof. For example, reference can be made to the specific gravity, flow rate, concentration of the wastewater, the specific gravity of the oil, the emulsification and the place of use to estimate the oil-water separation rate, and then select a suitable oil-water separator, such as an advection (API), parallel plate (PPI), Oil-water separator such as inclined plate type (CPI). However, it is not limited to this in the field of the invention.

For example, the log Kow value of a contaminant in a contaminated environment is, for example, 1.0 or more. Contaminants include, for example, tetrachloroethylene, trichloroethylene, cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, 1,1-dichloroethylene, vinyl chloride, trichloroethane. ,chloroethane, 1,1-dichloroethane, 1,2-dichloroethane, carbon tetrachloride, chloroform (chloroform), dichloromethane, methyl chloride, polychlorinated biphenyls, polybromine Diphenyl ethers, dioxins, chlorobenzenes, chlorophenols, benzene, toluene, ethylbenzene, xylene, phenols, 2,4-di (2,4-D), Carbofuran, Da Li Diazinon, Metahamidophos, Paraquat, Parathion, Aldrin, Chlordane, Dichlorodiphenyltrichloroethane ( DDT, 4,4'-Dichlorodiphenyl-trichloroethane) and its derivatives, Dieldrin, Endrin, Heptachlor, Toxaphene, Endosulfan; Fluoranthene, fluorene, Anthracene, dibenzo(a,h)anthracene, 茚(1,2,3-cd)芘(Indeno( 1,2,3-cd)pyrene), naphthalene, Phenothrene, pyrene, Acenaphthene, terpene Acenaphthylene), (Chrysene), Benzene (a) 骈蒽 (Benz (a) anthracene), Benzene (a) 骈芘 (Benzo (a) pyrene), Benzene (b) Benzene (Benzo (b) fluoranthene), Benzene (g , h, i) polycyclic aromatic hydrocarbons such as Benzo (g, h, i) perylene), Benzo (k) fluoranthene, etc.; 1,2-dichloropropane (1, 2-Dichloropropane), 1,2-Dichlorobenzene, 1,3-Dichlorobenzene, 3,3'-dichlorobenzidine (3,3'- Dichlorobenzidine), Hexachlorobenzene, Pentachlorophenol, 2,4,5-Trichlorophenol, 2,4,6-trichlorophenol (2,4, 6-Trichlorophenol), Di(2-ethylhexyl)phthalate (DEHP, Di(2-ethylhexyl)phthalate), Di-n-butylphthalate (DBP), O-Benzene Diethylphthalate (DEP) and Butyl benzyl phthalate (BBP) form at least one selected from the group, or a mixture thereof. For example, the contaminant is, for example, at least one selected from the group consisting of polychlorinated biphenyls, polybrominated diphenyl ethers, benzene (a) quinones, polycyclic aromatic hydrocarbons, and combinations thereof. However, it is not limited to this in the field of the invention.

In addition, in order to more easily destroy the stability of the emulsion, and to facilitate the demulsification of the emulsion and the emergence of the oil slick, the embodiment may further perform the aeration step after the addition of the demulsifier. Aeration can cause proper disturbance to the polluted environment, and the sediment particles can be contacted with the oil particles by the disturbance. For example, the aeration step may be implemented by a multi-stage aeration or a plug flow aeration, and the aeration may be assisted by an aeration form such as a blower in the form of a diffuser disk, a surface aerator or an oxidized deep channel. For example, a plurality of stages of aeration may be utilized to perform the aeration step to allow the air to flow in a plurality of vertical streams or a plurality of parallel streams or the like. However, in the field of the present invention, it is not limited thereto, and aeration may be performed using nitrogen gas or other gas containing no oxygen.

[Examples]

Hereinafter, a nano-sized emulsified stock solution needle prepared in accordance with the above-described method for preparing an emulsified stock solution for environmental remediation will be described by way of Example 1 to Example 3. In addition, the inventors of the present invention used the emulsified stock solution A prepared in Example 1 to treat the sediment taken from Errenxi in Tainan City. The treatment process of the remediation of the sediment is explained by the following Example 4 to Example 10. Further, in the case of Example 11 and Example 12, the biodegradation of the contaminant BaP by the emulsified recovered sediment and the non-emulsified recovered sludge will be described. Hereinafter, the present invention will be described by way of examples, but the invention is not limited to the examples.

Example 1: Preparation of emulsified stock solution A

At room temperature, 340 ml of sorbitan monooleate (Span 80) and 1020 ml of soybean oil were added to the test bottle and mixed uniformly, and then added to 1085.4 ml of deionized water (DI water) and dehydrated with 21.6 ml of polyoxyethylene. Sorbitol monolaurate (Tween 20) is mixed into 2% Tween 20 liquid to form an emulsified system. The emulsion system was stirred with a stirrer for 30 minutes to obtain an emulsified stock solution A, and the appearance was thick and milky white. The average particle diameter was measured using a Zetasizer® Nano ZS (Malvern Instruments, Worcestershire, UK) and found to be 345.7 nm.

Example 2: Preparation of emulsified stock solution B

5 ml of sorbitan monooleate (Span 80) and 1 ml of soybean oil were added to the test bottle at room temperature, thoroughly mixed with Vortex for 20 seconds, and added to 10.8 ml of DI water and 0.21 ml. Polyoxyethylene sorbitan monolaurate (Tween 20) was mixed and mixed with 2% Tween 20 liquid to form an emulsified system. The ultrasonic breaker was placed in a test bottle, and the emulsion system was subjected to ultrasonic vibration for 30 seconds to obtain an emulsified stock solution B, and the appearance was white milk. The average particle size was measured using a Zetasizer® Nano ZS and found to be 389 nm.

Example 3: Preparation of emulsified stock solution C

14.4 ml of polyoxyethylene sorbitan monolaurate (Tween 20), polyoxyethylene sorbitan monooleate (Tween 80), 7.8 ml of sorbitan monooleate (Span 80) at room temperature Add 1ml of soybean oil to the test bottle and 3ml of soybean oil to the test bottle, stir evenly to become an emulsion system. Add 95ml of deionized water to the emulsion system and continue to stir. The emulsion system will gradually transform into an aqueous phase. After heating at 85C, stir and cool for 12 hours. Reverse. The emulsified stock solution C was obtained, and the appearance was a translucent liquid. The average particle size was measured using a Zetasizer® Nano ZS and found to be 35.5 nm.

Example 4: Treatment of sediment containing brominated diphenyl ethers

The scale was taken to a dry weight of 12.35 Kg into the remediation tank of the environmental remediation system of Figure 2, and 1 ppm of bromodiphenyl ether (BDE209) was added to the sediment. The premix was obtained by adding the emulsified stock solution A to the sediment at a ratio of the dry weight of the sediment relative to the amount of the emulsified stock solution A of 1:0.84, and the mixture was stirred by a stirrer for 7 minutes. Then, 4.56 ml of a 0.78 M sodium carbonate demulsifier was added, and after stirring well for 30 minutes, it was allowed to stand for 16 hours to wait for the demulsification to occur. The waste oil is allowed to float on the surface of the liquid system and stratified with the liquid system, and the surface oil is used to recover the oil. The amount of oil collected and recovered was calculated by calculating the amount of BDE209 to obtain a recovery rate of 48.3%.

Example 5: Treatment of sediment containing brominated diphenyl ethers

The scale was taken to a dry weight of 12.35 Kg into the remediation tank of the environmental remediation system of Figure 2, and 1 ppm of BDE209 was added to the sediment. The premix was obtained by adding the emulsified stock solution A to the sediment at a ratio of the dry weight of the sediment relative to the amount of the emulsified stock solution A of 1:0.84, and the mixture was stirred by a stirrer for 7 minutes. Then, 4.56 L of a 0.78 M sodium carbonate demulsifier was added, and aeration was carried out for 30 minutes while stirring, and then allowed to stand for 16 hours to wait for the demulsification to occur. The waste oil is allowed to float on the surface of the liquid system and stratified with the liquid system, and the surface oil is used to recover the oil. The amount of oil collected and recovered was calculated by the amount of BDE 209 to obtain a recovery rate of 82%.

Example 6: Treatment of sediment containing polybrominated diphenyl ethers

The scale was taken to a dry weight of 12.35 Kg into the remediation tank of the environmental remediation system of Figure 2, and 1 ppm of polybrominated diphenyl ethers (PBDEs) were added to the sediment. The premix was obtained by adding the emulsified stock solution A to the sediment at a ratio of the dry weight of the sediment relative to the amount of the emulsified stock solution A of 1:0.84, and the mixture was stirred by a stirrer for 7 minutes. Then, a 0.78 M sodium carbonate demulsifier of 4.56 L was added, and aeration was carried out for 30 minutes while stirring, and then allowed to stand for 16 hours to wait for the demulsification. Health. The waste oil is allowed to float on the surface of the liquid system and stratified with the liquid system, and the surface oil is used to recover the oil. The recovered oil amount and the amount of PBDEs collected were calculated to obtain a recovery rate of 76%.

Example 7: Treatment of phthalate-containing sediment

Weighing 12.35Kg of the bottom sediment weight into the rectification tank of the environmental remediation system of Figure 2, and 0.395ml of phthalate esters (PAEs) of di(2-ethylhexyl) phthalate (DEHP) was added to the sediment to 50 mg/Kg. The premix was obtained by adding the emulsified stock solution A to the sediment at a ratio of the dry weight of the sediment relative to the amount of the emulsified stock solution A of 1:0.84, and the mixture was stirred by a stirrer for 7 minutes. Then, 4.56 L of a 0.78 M sodium carbonate demulsifier was added, and aeration was carried out for 30 minutes while stirring, and then allowed to stand for 16 hours to wait for the demulsification to occur. The waste oil is allowed to float on the surface of the liquid system and stratified with the liquid system, and the surface oil is used to recover the oil. The recovery of the amount of oil collected and the amount of DEHP were calculated to obtain a recovery of 71%.

Example 8: Treatment of phthalate-containing sediment

Weighing 12.35Kg of the bottom sediment weight into the rectification tank of the environmental remediation system of Figure 2, and adding 0.073ml of phthalate (PAEs) of dibutyl phthalate (DBP) to the sediment. In 10mg/Kg. The premix was obtained by adding the emulsified stock solution A to the sediment at a ratio of the dry weight of the sediment relative to the amount of the emulsified stock solution A of 1:0.84, and the mixture was stirred by a stirrer for 7 minutes. Then, 4.56 L of a 0.78 M sodium carbonate demulsifier was added, and aeration was carried out for 30 minutes while stirring, and then allowed to stand for 16 hours to wait for the demulsification to occur. The waste oil is allowed to float on the surface of the liquid system and stratified with the liquid system, and the surface oil is used to recover the oil. The amount of oil collected and recovered was calculated by calculating the amount of DBP to obtain a recovery rate of 62%.

Example 9: Treatment of phthalate-containing sediment

Weighing 12.35Kg of the bottom sediment weight into the rectification tank of the environmental remediation system of Figure 2, and adding 0.068ml of phthalate (PAEs) diethyl phthalate (DEP) to the sediment. In 10mg/Kg. The premix was obtained by adding the emulsified stock solution A to the sediment at a ratio of the dry weight of the sediment relative to the amount of the emulsified stock solution A of 1:0.84, and the mixture was stirred by a stirrer for 7 minutes. Following On the other hand, 4.56 L of a 0.78 M sodium carbonate demulsifier was added, and aeration was carried out for 30 minutes while stirring, and then allowed to stand for 16 hours to wait for the demulsification to occur. The waste oil is allowed to float on the surface of the liquid system and stratified with the liquid system, and the surface oil is used to recover the oil. The recovered oil amount and the amount of DEP collected were calculated to obtain a recovery rate of 73%.

Example 10: Treatment of phthalate-containing sediment

Weighing 12.35Kg of the bottom mud into the remediation tank of the environmental remediation system of Figure 2, and adding 0.07ml of phthalate (PAEs) toluene butyl phthalate (BBP) to the bottom. The mud is made into 10mg/Kg. The premix was obtained by adding the emulsified stock solution A to the sediment at a ratio of the dry weight of the sediment relative to the amount of the emulsified stock solution A of 1:0.84, and the mixture was stirred by a stirrer for 7 minutes. Then, 4.56 L of a 0.78 M sodium carbonate demulsifier was added, and aeration was carried out for 30 minutes while stirring, and then allowed to stand for 16 hours to wait for the demulsification to occur. The waste oil is allowed to float on the surface of the liquid system and stratified with the liquid system, and the surface oil is used to recover the oil. The amount of oil recovered and the amount of BBP recovered was calculated to obtain a recovery rate of 64%.

Example 11: Biodegradation treatment of emulsified recovery sludge

The weight of the bottom sediment is 12.3Kg, which is placed in the rectification tank of the environmental remediation system of Figure 2. The emulsified stock solution A is added to the sediment with the dry weight of the sediment relative to the amount of the emulsified stock solution A of 1:0.84. A premix was obtained and the premix was stirred by a mixer for 7 minutes. Then, 4.56 L of a 0.78 M sodium carbonate demulsifier was added, and aeration was carried out for 30 minutes while stirring, and then allowed to stand for 24 hours to wait for the demulsification to occur. The waste oil is allowed to float on the surface of the liquid system and stratified with the liquid system, and the surface oil is used to recover the oil. After the oil slick is collected, 30 g of the sediment in the rectification tank is taken out and placed in a petri dish, and placed for 225 days without a lid. The concentration of benzene (a) quinone (BaP) was measured on the 25th day, the 48th day, the 65th day, the 133rd day, the 155th day, the 180th day, and the 217th day. The obtained concentration data is a graph showing the change in BaP concentration with time in Fig. 4 versus time.

Example 12: Biodegradation treatment of sediment without emulsification recovery

Weigh 30g of the sediment and place it in the culture dish. Leave it for 225 days without a lid. The concentration of BaP was measured on the 25th day, the 48th day, the 65th day, the 133rd day, the 155th day, the 180th day, and the 217th day. The obtained concentration data is a graph showing the change in BaP concentration versus time in Fig. 4 in terms of Δ.

From the results of Examples 1 to 3, it is understood that the average particle diameter of the oil particles of the emulsified stock solution in the examples of the present invention is in the range of 1 nm to 1000 nm in terms of preparation of the emulsified stock solution for environmental remediation. Preferably, the average particle size has a better oil-water layer effect in the range of 300 nm to 400 nm. Further, the emulsified stock solution A of Example 1 having a large soybean oil content has a preferable stratification effect. However, it is not limited to this in the field of the present invention.

In terms of the treatment of the contaminated environment, from the experimental results of Examples 4 to 19, the emulsified stock solution for environmental remediation according to the embodiment of the present invention is used, and the contaminated environment according to the embodiment of the present invention is used. The remediation method can rectify the contaminated sediment and achieve excellent oil recovery. Further, from the experimental results of Examples 5 to 10, nitrogen gas was introduced to disturb the oil particles, thereby accelerating the completion of the demulsification, and a better oil recovery can be achieved as compared with Example 4 without aeration. rate.

Further, in terms of the degradation of the contaminants in the sediment by the microorganisms, from the experimental results of Example 11 and Example 12, the emulsified and recovered sludge of Example 11 is under natural rejuvenation conditions. After 217 days, the concentration of BaP decreased from 2.5 mg/kg to 0.335 mg/kg (approximately 86.6% degradation). Also under the conditions of natural re-cultivation, compared with Example 11, the un-emulsified recovered sludge of Example 12 had a poor degradation rate for BaP, and after 217 days, the concentration of BaP was 2.5. The mg/kg was only reduced to 1.08 mg/kg (approximately 56.7% degradation). Moreover, Example 11 had a significant biodegradation effect on the 25th day, while Example 12 was placed on the surface for more than 60 days to have a significant biodegradation effect. Therefore, it can be inferred that the sediment containing the emulsified stock solution and being emulsified and recovered is advantageous for the microorganism to degrade BaP in the sediment, and has the effect of reducing environmental ecological pollution.

In summary, the emulsified stock solution for environmental remediation prepared by the preparation method of the present invention can be used to remediate the polluted environment, and the oil can be efficiently recovered, and the sediment in the rectified contaminated environment has excellent biological properties. Degradation ability of pollutants. River sediment pollution remediation can be completed quickly and in a short period of time, and any need for pollution concerns can be reduced. In addition, the emulsified stock solution for environmental remediation of the present invention can be directly applied to the soil or the sediment to recover the hydrophobic substance, and the hydrophobic substance in the soil can be effectively recovered or removed.

However, the above is only an embodiment of the present invention, but the scope of the present invention is of course not limited thereto. It should be understood by those skilled in the art that the present invention can be easily modified and modified without departing from the spirit and scope of the invention. Within the scope. In addition, any of the embodiments or the claims of the present invention are not required to include all of the objects or advantages or features disclosed in the specification. In addition, the abstract sections and headings are only used to assist in the search of patent documents and are not intended to limit the scope of the invention.

S10, S20, S30, S40‧‧‧ steps

Claims (8)

An emulsified liquid for environmental remediation, which is used for remediation of polybrominated diphenyl ethers (PBDEs), phthalates (PAEs), brominated diphenyl ethers (BDE209), and phthalic acid di(2-) At least one of ethylhexyl ester (DEHP), dibutyl phthalate (DBP), diethyl phthalate (DEP), tolyl phthalate (BBP), or a combination thereof Contaminated soil, sediment, natural water or groundwater, and the emulsified liquid for environmental remediation includes at least: 40 to 60 parts by weight of water, 30 to 50 parts by weight of oil solutes, and 10~ a non-nano-doped (o/w) oil-in-water emulsified stock solution composed of 30 parts by weight of a nonionic surfactant; wherein the nonionic surfactant is from polyethylene glycol, polyoxyethylene sorbitan, poly Oxyethylene sorbitan monooleate, hexahexyl laurate, sorbitan mono-9-octadecenoate, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene-poly The oxypropenol, the polyoxyethylene fatty acid ester, the trialkylamine oxide, and the mixture thereof constitute at least one selected from the group; the oil solute is from a large At least one selected from the group consisting of soybean oil, peanut oil, coconut oil, olive oil, grape seed oil, cottonseed oil, sunflower oil, palm oil, food grade oil, and mixtures thereof; and the oil solute content is greater than 40%, and the average particle diameter of the oil particles of the emulsified stock solution for environmental remediation is in the range of 300 nm to 400 nm. The emulsified stock solution for environmental remediation according to claim 1, wherein the surfactant comprises polyoxyethylene sorbitan monolaurate (Tween 20), polyoxyethylene sorbitan monooleate (Tween 80), Sorbitan monooleate (Span 80), and mixtures thereof, constitute at least one selected from the group. The emulsified stock solution for environmental remediation according to claim 1, which further comprises an oil-water fusion agent, an emulsion stabilizer, an emulsification accelerator, an antioxidant, and a combination thereof. The composition forms at least one selected from the group to enhance the emulsification between the oil solute and the water. A method for remediating a contaminated environment, comprising: injecting an emulsified liquid for environmental remediation according to any one of claims 1 to 3 into a contaminated environment and stirring it for a period of 1 to 15 minutes; At the time, the contaminated environment contains polybrominated diphenyl ethers (PBDEs), phthalates (PAEs), brominated diphenyl ethers (BDE209), di(2-ethylhexyl) phthalate. Soil of (DEHP), contaminant of at least one of dibutyl phthalate (DBP), diethyl phthalate (DEP), butyl butyl phthalate (BBP), or a combination thereof , sediment, natural water or groundwater; adding demulsifier and stirring for a period of not more than 72 hours, the demulsifier is from sodium carbonate, calcium carbonate, copper sulfate, magnesium sulfate, aluminum sulfate, sodium chloride An ionic demulsifier or a non-ionic type of at least one selected from the group consisting of calcium chloride, sodium benzoate, SP type demulsifier, AP type demulsifier, AE type demulsifier, AR type demulsifier and mixtures thereof Emulsion; and by surface floatation, stripping, mechanical oil scraping, or a group thereof The oil slick is recovered in combination; wherein the pollutant in the polluted environment has a log Kow value of 1.0 or more. The method for remediation of a polluted environment as recited in claim 4, wherein the contaminated environment is 1 ppm of brominated diphenyl ether (BDE209), or 50 mg/Kg of phthalic acid di(2-ethylhexyl) In the case of the sludge of the ester (DEHP), the ratio (X:Y) of the contaminated environment (X) to the emulsified stock solution (Y) for the environmental treatment is 1:0.84. The method for remediation of a polluted environment as recited in claim 4, wherein the contaminated environment is 10 mg/Kg of diethyl phthalate (DEP), dibutyl phthalate (DBP), or The contaminated environment when the sludge of butyl phthalate (BBP) is present The addition ratio (X:Y) of (X) to the emulsified stock solution (Y) for the environmental treatment was 1:0.84. The method for remediation of a polluted environment as recited in claim 4, wherein before the step of recovering the oil slick, the air is further introduced to sufficiently aerate. The method for remediation of a polluted environment as recited in claim 4, wherein the demulsifier is sodium carbonate.