TWI658008B - Reversible transformation emulsion suitable for remediation of contaminated sediment and treatment method for contaminated sediment - Google Patents

Abstract

The invention provides a reverse transformation emulsion suitable for remediation of contaminated sediment and a treatment method for contaminated sediment. The reverse transformation emulsion is composed of at least an oil solute and a first surfactant; the oil solute is from soybean oil, peanut oil, coconut oil, olive oil, grape seed oil, cottonseed oil, sunflower oil, palm oil, The food grade oil, and mixtures thereof, comprise at least one selected from the group consisting of: the average particle size of the oil particles in the reverse transformation emulsion is in the range of from 1 nm to 5000 nm. The method of remediating contaminated sediment includes a reverse transformation emulsification stock injection step; and a buffer push step. The reverse rotation temperature of the reverse conversion emulsified stock solution is in the range of 30 ° C to 99 ° C. The buffer is injected in an amount of at least 1.0 pore volume.

Description

Reversible transformation emulsion suitable for remediation of contaminated sediment and treatment method for contaminated sediment

The present invention relates to an emulsion and a method for using the same to remediate a polluted environment, in particular, a reverse conversion emulsion suitable for remediation of contaminated sediment, and a reverse conversion and activity capping using the reverse transformation emulsion in combination with the current site The method of remediation of contaminated sediments.

The mud pollution situation in Taiwan is quite serious. The monitoring concentrations of many hydrophobic organic pollutants and heavy metal pollution are among the best in the world. The monitoring concentration of most organic pollutants has repeatedly exceeded the regulatory limit.

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 final marine 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 addressed (Netzband, 2002), may result in sustainable river and sea pollution.

Confined aquatic disposal is to dig a groove in the sediment below the surface of the water, to put the contaminated sediment into the groove, and cover it with clean sand, stones, etc. (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 remediation 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.

The existing vitrification method must first be dredged, and then the sediment obtained by dredging is sent to the treatment site for vitrification. During the dredging process, a large amount of small particles can be suspended and lost, and the pollutants in the sediment are about 80-90% of the pollution quality is small particles below 30 μm, which often results in unrecognized or failed remediation results. About 50% of the remediation cases with dredging as a necessary means cannot be confirmed or failed. How to avoid the loss of small particles is a very important issue.

In order to solve the problems of the above conventional techniques, the inventors of the present application have developed a series of patented innovative technologies. For example, in the invention patent of the Republic of China No. I511935 "emulsion as a remediation agent for soil, groundwater, sediment and other environmental media", a method for utilizing nanoemulsification for hydrophobic organic pollution in sediments has been disclosed. The technology for the degradation of substances; the invention patent of the "Environmental Medium Remediation Method" of the Republic of China No. I478876 discloses a technique for recovering and degrading hydrophobic organic pollutants in sediments using a double emulsion; in the Republic of China The invention patent of I558671 "Emulsifying liquid for environmental remediation and treatment of contaminated environment" has disclosed a recovery and degradation of hydrophobic organic matter using a high oil emulsion.

However, in the above-mentioned three prior patent applications, the emulsion is not injected immediately after heating, and it is not directly reversed in the sediment and lacks the mechanism for simultaneous microbial thermal screening, thereby causing pollution prevention treatment. It takes a long time, so that the processing cost is high and it is still unsatisfactory. In addition, the emulsions used in the prior patent applications of the above three applications are mainly limited to the use of oil in water (O/W) type emulsion or water in oil in water (W/O/W). The double emulsion of the type, because the emulsion is stabilized by the surface of the oil particles as the surfactant, that is, the outermost layer is a polar group facing the water phase, and the non-polar group is facing inward; therefore, at normal temperature, it is often There are emulsions that are not sufficiently in contact with hydrophobic contaminants, so that the treatment effect on hydrophobic contaminants is highly uncertain, and in addition to the difficulty in achieving satisfactory treatment efficiency, it may even cause unnecessary secondary pollution.

Therefore, the environmental pollution remediation industry is not looking forward to developing a new and effective pollution remediation technology that can not only effectively overcome the uncertainty of previous pollution remediation technologies, but also reduce the possibility of secondary pollution or prevent secondary pollution.

Therefore, the present inventors carefully analyzed the defects of the prior art and thoroughly reviewed various feasible solutions capable of overcoming the above-mentioned various problems of the prior art, and finally completed a kind of excavation without the need for site excavation through hard research and development. No need to carry out dry separation, no need to transport to a specific treatment site, no final disposal, combined with heat to accelerate the transmission and reduction of oil particles is conducive to recovery, and as long as the emulsion is completed by high temperature reverse conversion, the hydrogen production bacteria and anaerobic can be effectively screened. The present invention is achieved by dechlorinating bacteria and utilizing residual oil to achieve effective biodegradation to achieve pollution remediation. In other words, the present invention provides a reverse-type emulsion that can be reverse-transferred, and a method of using the reverse-transition emulsion combined with the current reverse-transfer and active capping methods for contaminating the sediment.

Specifically, the present invention provides a reverse transformation emulsion suitable for remediation of contaminated sediment, and the use of it in combination with in situ phase-inversion emulsification and active capping (ISPIE&AC) for remediation of contaminated sediment. The method mainly comprises the following steps: (1) using high-temperature water to directly contact the hydrophobic organic pollutants in the oil into the pores, and efficiently transferring the pollutants into the oil phase by utilizing the characteristics of high temperature accelerated desorption and diffusion; The upper sediment causes the technology of cooling to complete the reverse transformation of the emulsion to form ultra-small oil particles, and quickly and effectively transports the pollutants to the top of the sediment for removal; (2) using the shallow sediment that has been initially rectified as a ready-made addition The cover material is bioactive capping; (3) after the capping is completed, the hydrogen-producing microorganisms which are dominated by the hot-sifting in the bottom sediment can be used as the dominant bacteria to ferment the residual emulsion. Hydrogen, the anaerobic reductive dehalogenating bacteria in the upper sediment uses hydrogen to carry out effective and sustained biodegradation to form an effective active biological barrier.

Further, according to the method for rectifying the reverse transformation emulsion and the contaminated sediment suitable for remediation of contaminated sediment of the present invention, it can be confirmed that at least the following effects of the invention can be achieved: (1) According to one of the technical viewpoints of the present invention, a surfactant is used. The hydrophilicity is different at different temperatures. For lower temperature, the oil is originally heated in water (O/W) emulsion, which is converted into higher temperature water in oil (W/O). The emulsion is used to make the emulsion transport path highly similar to the hydrophobic contaminant, and can effectively contact and accelerate the mass transfer efficiency. (2) According to still another technical point of view of the present invention, an oppositely transformed emulsion is injected into an environment contaminated by a hydrophobic organic pollutant such as soil, sediment, sludge, etc. at a high temperature to provide an oil phase. The storage space of the emulsion after the reverse conversion phase; in addition, as the temperature is lowered, the oil is again converted into oil of small particles in the water (O/W) type emulsion, and the contaminants confined to the oil are not easily exchanged. come out. (3) According to another technical point of view of the present invention, by injecting a clean buffer, the emulsion filled with the contaminant can be transported in a specific direction, thereby effectively removing the contamination in the environmental matrix. (4) According to still another technical point of the present invention, in the transfer process of the emulsion containing the contaminant, since the removal effect is gradually decreased as the temperature is gradually lowered, the removal rate of the contaminant in the region where the temperature is higher is better. That is, the concentration of residual pollutants in the bottom sediment will be relatively low, and the concentration of pollutants remaining in the upper sediment will be relatively high. (5) According to another technical point of view of the present invention, it is possible to use to screen different specific strains by forming a sediment at a local high temperature state. For example, as shown in FIG. 1 , when the lower sediment is formed in a state suitable for the growth of the dominant bacteria of the hydrogen-producing microflora, and the upper sediment is formed into a state suitable for the growth of the dominant bacteria of the anaerobic dehalogenating bacteria group, The hydrogen-producing bacteria in the bottom sediment can effectively utilize the residual emulsion for hydrogen production, and the hydrogen dissolved in the pore water is transported upwards into the highly polluted upper sediment, and the dominant bacteria present in the upper mud The anaerobic dehalogenating bacteria group can continue to effectively perform biodegradation, thereby achieving the purpose of sufficiently and effectively removing the dye.

That is, the present invention can provide a method for remediating contaminated sediment. The technical features of the present invention are three, one is an in-situ emulsion liquid phase reversal method which can effectively and effectively reduce the quality of hydrophobic chlorine-containing organic pollutants in the sediment; one is to effectively utilize the initially cleaned bottom mud as a barrier deep sediment. The localized bottom mud capping technology; one is to use the high temperature and sufficient residence time to screen the hydrogen-producing bacteria and the effective anaerobic reductive dechlorination bacteria that are not significantly affected by the upper layer to carry out the continuous and effective degradation of chlorine-containing organic pollutants.

The technical feature of the present invention focuses on the risk of chlorine-containing hydrophobic organic pollutants in the sediment, and if the quality of the pollutants in the surface sediment is greatly reduced in a short time, the ecological and health can be effectively reduced. risk.

The technical feature of the present invention is that the cost of the active capping material is not low, and it is often troubled by the anaerobic microbial gas production after the laying, so the effective use has removed most of the The direct recovery of the sediment of the pollutants is used as a capping material. Under slight disturbance, the particle size distribution of the sediment can be effectively reconstituted, so that the larger particle size sediment settles first, and the smaller particle size sediment particles settle slowly. Ventilation characteristics can also gradually increase the exposure of pollutants to the surface of the particles, organic matter and microorganisms, and can adsorb the pollutant flux that blocks upward diffusion from below;

The third feature of the present invention is that after the hot water is added to the high temperature water, the emulsion in the oil will cause the gas in the pore water to be heated to form bubbles, and the surface sediment will be slightly disturbed by the floating layer, and the temperature will be rapidly cooled due to the influence of the upper water column. The lower sediment is subjected to microbial thermal sieving due to the contact with high temperature for a long period of time. The spore-producing bacteria (such as the genus Clostridia) in the hydrogen production will become the dominant bacteria, and the upper layer will quickly cool down and the result will be no heat screening effect. The effect of slightly warming, and the most suitable growth temperature of most known anaerobic reductive dehalogenating bacteria are between 35-37 °C, and also become the main dominant bacteria in the upper sediment due to the warming effect.

Therefore, according to the present invention, after the recovery operation is completed, the distribution of dominant microflora in different upper and lower regions can be formed; the lower hydrogen producing bacteria can use the residual emulsion to produce hydrogen, and the upper layer of anaerobic reductive dehalogenating bacteria can be effective. Using hydrogen as an electron supplier, the hydrophobic organic compounds (HOCs) that have not been completely removed are further decomposed and removed; after a slight pressure compaction, the already fluffy bottoms can be restored to a denser condition, from below The pollutant flux that is disturbed by the sediment is blocked by the barrier of biodegradation and avoids direct contact with the upper water body and surface benthos.

One aspect of the present invention is to provide an inversely transitioning emulsion suitable for use in remediating contaminated sediments comprising a first surfactant, an oil solute.

In one embodiment, the first surfactant of the present invention comprises polyethylene glycol, polyoxyethylene sorbitan, polyoxyethylene sorbitan monooleate, hexahexyl laurate, mono-9 - sorbitan sorbitan ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene-polyoxypropylene alcohol, polyoxyethylene fatty acid ester, trialkylamine oxide, poly Selected from the group consisting of oxyethylene sorbitan monolaurate (Tween 20), polyoxyethylene sorbitan monooleate (Tween 80), sorbitan monooleate (Span 80), and mixtures thereof At least one of them.

In one embodiment, the first surfactant of the present invention is preferably hexitol laurate, sorbitan mono-9-octadecenoate, polyoxyethylene alkyl ether, polyoxyethylene alkyl Phenyl ether, polyoxyethylene-polyoxypropenol, polyoxyethylene fatty acid ester, trialkylamine oxide, polyoxyethylene sorbitan monolaurate (Tween 20), polyoxyethylene sorbitan mono oil The acid ester (Tween 80), sorbitan monooleate (Span 80), and mixtures thereof form at least one selected from the group.

In one embodiment, the first surfactant of the present invention is more preferably a trialkylamine oxide, polyoxyethylene sorbitan monolaurate (Tween 20), or polyoxyethylene sorbitan monooleate. The ester (Tween 80), sorbitan monooleate (Span 80), and mixtures thereof form at least one selected from the group consisting of.

In one embodiment, the first surfactant of the present invention is preferably composed of polyoxyethylene sorbitan monolaurate (Tween 20), polyoxyethylene sorbitan monooleate (Tween 80), and The mixture forms at least one selected from the group.

In one embodiment, the oil solute of the present invention comprises a 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. At least one selected in the middle.

In one embodiment, the reversely convertible emulsion of the present invention is a non-nano-wish (o/w) oil-in-water type.

In one embodiment, the volume ratio (v/v) of the first surfactant to the second surfactant in the emulsion is in the range of 1:25 to 25:1; preferably at 1 Range of 25~20:1; better in the range of 1:20~15:1; best in the range of 1:20~10:1

In one embodiment, the ratio of the total amount of the surfactant and the volume ratio of the oil solute (v/v) of the first surfactant to the second surfactant in the emulsion is 1:20~ The range of 20:1: preferably in the range of 1:15 to 15:1; more preferably in the range of 1:10 to 10:1; the best is in the range of 1:1 to 9:1.

In one embodiment, the reversely convertible emulsion of the present invention further comprises at least one of an oil-water fusion agent, an emulsion stabilizer, an emulsification accelerator, an antioxidant, or a combination thereof for promoting oil solute and water. Emulsification.

In one embodiment, the oil particles of the reverse transformation emulsion of the present invention have an average particle size ranging from 1 nm to 5000 nm.

In one embodiment, the reverse transformation emulsion system further comprises a second surfactant, the second surfactant comprising polyethylene glycol, polyoxyethylene sorbitan, polyoxyethylene sorbitan monooleate , hexaol laurate, mono-9-octadecenoic acid sorbitan ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene-polyoxypropylene alcohol, polyoxyethylene fat Acid esters, trialkylamine oxides, polyoxyethylene sorbitan monolaurate (Tween 20), polyoxyethylene sorbitan monooleate (Tween 80), sorbitan monooleate (Span 80) And, the mixture thereof constitutes at least one selected from the group.

In one embodiment, the second surfactant of the present invention is preferably hexitol laurate, sorbitan mono-9-octadecenoate, polyoxyethylene alkyl ether, polyoxyethylene alkyl Phenyl ether, polyoxyethylene-polyoxypropenol, polyoxyethylene fatty acid ester, trialkylamine oxide, polyoxyethylene sorbitan monolaurate (Tween 20), polyoxyethylene sorbitan mono oil The acid ester (Tween 80), sorbitan monooleate (Span 80), and mixtures thereof form at least one selected from the group.

In one embodiment, the second surfactant of the present invention is more preferably a trialkylamine oxide, polyoxyethylene sorbitan monolaurate (Tween 20), or polyoxyethylene sorbitan monooleate. The ester (Tween 80), sorbitan monooleate (Span 80), and mixtures thereof form at least one selected from the group consisting of.

In one embodiment, the second surfactant of the present invention is preferably polyoxyethylene sorbitan monolaurate (Tween 20), polyoxyethylene sorbitan monooleate (Tween 80), dehydrated sorbus The alcohol monooleate (Span 80), and mixtures thereof, constitute at least one selected from the group.

Moreover, the present invention provides a method for remediating a contaminated sediment by injecting an emulsion of the above-mentioned reverse transformation emulsion to a temperature above a reverse rotation temperature, and then performing a buffer for the suspension for a certain period of time to complete a certain volume. After the buffer solution is pushed, the hydrophobic pollutants in the sediment are separately treated, and the upper and lower layers have different dominant bacteria groups in the original sediment, and the dominant bacteria group and the upper anaerobic dehalogenating bacteria group are utilized. Perform continuous biodegradation of hydrophobic contaminants in the sediment.

In one embodiment, the reverse temperature of the present invention is between 30 ° C and 99 ° C.

In one embodiment, the reverse conversion emulsion of the present invention is injected between 0.33 and 1.0 pore volumes.

In one embodiment, after the reverse transformation emulsion of the present invention is injected into the column, the residence time in the column is at least 30 minutes.

In one embodiment, the buffer of the present invention is added in an amount of at least 1.0 pore volume, and the buffer is a carbonate buffer.

The embodiments of the present invention will be described and illustrated in detail in the detailed description of the embodiments of the invention. The scope of the present invention is not limited in any way by the following specific examples, but the scope of the present invention is not intended to be limited.

In addition, it is to be understood by those skilled in the art that the present invention is not limited to the examples, and the same or equivalent functions and steps are used to achieve the invention.

The various embodiments of the reverse transformation emulsion of the present invention, the preparation method thereof, and the method for treating the contaminated sludge contaminated with the reverse transformation emulsion are set forth below for illustration.

In accordance with one aspect of the present invention, an embodiment of an inversely transitioning emulsion is proposed which is suitable for use in remediating a contaminated environment. In this embodiment, the reverse transformation emulsion system includes at least a first surfactant, an oil solute.

The physical properties of the reverse conversion emulsion relating to this embodiment are as follows. The average particle diameter of the oil particles of the emulsified stock solution may range from 1 nm to 5000 nm; preferably from 1 nm to 2000 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 first surfactant may be a nonionic surfactant which does not dissociate in water and has a hydroxyl group (—OH) or an ether bond ( R—O—R′) as a hydrophilic group. a structural molecule having a hydrocarbon chain of 8 to 18 carbons as a lipophilic group. 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 At least one selected from the group consisting of sorbitan esters and mixtures thereof

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 emulsion 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 emulsion 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 .

In an embodiment of the present invention, the reversely transformable emulsion is preferably prepared by a "phase inversion temperature method (PIT method)" to obtain an inversely transformed emulsion. Further, the particle size of the oil particles formed by the reverse conversion emulsion is preferably analyzed by dynamic light scattering.

The "reverse temperature method" is applied to a non-ionic surfactant, which means that the physicochemical properties of the surfactant act, and the change in temperature changes the hydrophilicity and lipophilicity of the surfactant, and is water at low temperatures. Oil in water (o/w) type, in the case of high temperature, it becomes a water in oil (w/o) type. When the temperature is gradually increased, the oil-in-water (o/w) is converted into The water-in-oil (w/o) type, after being uniformly cooled, is reduced to a natural bending degree to form an oil-in-water type to achieve the effect of dispersing the oil particles and reducing the particle size.

In an embodiment of the present invention, the particle size of the reverse transformation emulsion may be performed, preferably, the laser light is injected into the sample to be tested via a dynamic light scattering instrument, and the oil particles cause the laser light to scatter, and the oil particles themselves Irregular Brownian motion changes the scattered laser light and calculates the particle size of the oil particles to measure the particle size distribution.

In an embodiment of the present invention, the oil solute is preferably based on, for example, soybean oil, peanut oil, sunflower oil, and grape seed oil. Further, in the emulsification process, other additives may be further added. The additives which can be used in the present invention are, for example, oil-water fusion agents, emulsion stabilizers, emulsion accelerators, antioxidants, deodorants, disinfectants, microbial nutritional supplements and the like.

According to the present invention, 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 lower the surface tension between the oil and the water, and enter the oil. Between the water 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 is lowered, the emulsified oil or water is gradually thinned and transmitted through the non-ion a type of surfactant is 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, thereby The oil or water is emulsified and uniformly dispersed in other liquids. However, in the preparation method of the present invention, it is not limited thereto.

Organic contaminants suitable for use in the process of the present invention, for example, may be contaminants in a contaminated environment having a log Kow value of 1.0 or greater. For example, polychlorinated biphenyls (PCBs), hexachlorobenzene (HCB), polybrominated diphenyl ethers (PBDEs), phthalates (PAEs), brominated diphenyl ethers (BDE209), ortho-benzene Di(2-ethylhexyl) dicarboxylate (DEHP), dibutyl phthalate (DBP), diethyl phthalate (DEP), tolylbutyl phthalate (BBP), and At least one of the combinations selected.

More specifically, contaminants suitable for treatment using the method of the present invention are preferably hydrophobic contaminants. For example, tetrachloroethylene, trichloroethylene, cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, 1,1-dichloroethylene, vinyl chloride, trichloroethylene Alkane, ethyl chloride, 1,1-dichloroethane, 1,2-dichloroethane, carbon tetrachloride, chloroform (chloroform), dichloromethane, methyl chloride, polychlorinated biphenyls, Brominated diphenyl ethers, dioxins, chlorobenzenes, chlorophenols, benzene, toluene, ethylbenzene, xylene, phenols, 2, 4-di (2, 4-D), Carbofuran, Diazinon, Metahamidophos, Paraquat, Parathion, Aldrin, Chlordane, Dichlorodiphenyltrichloroethane (DDT) and its derivatives, Dieldrin, Endrin, Heptachlor, Toxaphene, Endosulfan; benzoquinone, anthraquinone, anthraquinone, Diphenyl (a, h) ruthenium, iridium (1, 2, 3-cd) ruthenium, naphthalene, phenanthrene, anthracene, pyrene, decene, chrysene, benzene (a) pyrene, benzene (a) Polycyclic aromatic hydrocarbons such as hydrazine, benzene (b) benzoquinone, benzene (g, h, i) fluorene, benzene (k) benzoquinone; 1,2-dichloropropane, 1, 2-Dichlorobenzene, 1, 3-dichlorobenzene, 3, 3'-dichlorobenzidine, hexachlorobenzene, pentachlorophenol, 2, 4, 5-trichlorophenol, 2, 4, 6-trichloro Phenol, di(2-ethylhexyl) phthalate, dibutyl phthalate (DBP), diethyl phthalate (DEP), butyl benzyl phthalate (BBP) 1,1,1,2-Tetrachloroethane, 1,1,1,2-tetrachloroethane, 1,1,1-Trichloroethane, 1,1,1-trichloroethane, 1,1,2,2- Tetrachloroethane, 1,1,2,2-tetrachloroethane, 1,1,2-Trichloroethane, 1,1,2-trichloroethane, 1,1-Dichloroethane, 1,1-Dichloroethene, 1,1- Dichloropropene, 1,1-dimethyl-ethylbenzene, 1,2,3-Trichlorobenzene, 1,2,3-Trichloropropane, 1,2,3-trichloropropane, 1,2,3-trichlorobenzene, 1,2,4-Trichlorobenzene, 1,2,4-trichlorobenzene, 1,2-Dibromo-3-chloropropane, 1,2-Dibromoethane, 1,2-Dichlorobenzene, 1,2-Dichloroethane, 1,2- Dichloropropane, 1,2-dichloropropane, 1,2-dichlorobenzene, 1,2-dibromo-3-chloropropane, 1,2-dibromoethane, 1,3-Dichloropropane, 1,3-two Chloropropane, 1,4-Dichlorobenzene, 1,4-dichlorobenzene, 1-methyl-propylbenzene, 2,2-Dichloropropane, 2,2- Chloropropane, 2-Chlorotoluene, 2-chlorotoluene, 4-Chlorotoluene, 4-chlorotoluene, Bromochloromethane, Bromodichloromethane, Bromoform, Bromomethane, Carbon tetrachloride, Chlorobenzene, Chlorodibromomethane, Chloroethane, Chloroform, Chloromethane, cis-1, 2-Dichloroethene, Cis-1,3-dichloropropene, Dibromomethane, Dichlorodifluoromethane, Ethylbenzene, Hexachlorobutadiene, Isopropylbenzene, Methylene chloride, m-Xylene, trans-1, 2-Dichloroethene, trans-1,3-dichloropropene, Trichloroethene, Trichlorofluoromethane, Vinyl chloride, Chlorobromomethane, dichlorodifluoromethane, dichloromethane, trichlorofluoromethane, hexachlorobutadiene, trans-1,2-dichloroethylene, trans-1,3-dichloropropene, carbon tetrachloride , n-butylbenzene, n-propylbenzene, vinyl chloride, ethyl chloride, methyl chloride, m-xylene, cis-1,2-dichloroethylene, cis-1,3-dichloropropene, bromodichloromethane Organic matter such as methyl bromide, bromoform, bromochloromethane or o-xylene.

In an embodiment of the method for remediating the contaminated sediment of the present invention, the remediation method is: after heating the reverse transformation emulsified liquid solution to a temperature above the reverse rotation temperature, and then injecting into the contaminated sediment, and keeping the residence for at least 30 minutes. In the above time, the opposite transformation emulsion is fully reacted with the hydrophobic pollutant in the sediment; and after the foregoing reaction is completed, a certain volume of the buffer is input to recover the hydrophobic pollutant in the sediment.

In an embodiment of the method for remediating the contaminated sediment of the present invention, after the buffer solution is pushed, the sediment is pushed out from the column, and is divided into upper, middle and lower sections for accelerated solvent extraction and reduction of the sediment. After GC-ECD analysis, such as pressure concentration, purification, and concentration under reduced pressure, the concentration curve of PCB (Aroclor 1254) in the outflow as shown in Fig. 2 can be obtained. The cross-flow curve of the PCB (Aroclor 1254) is 1.0. There is a sharp rise between the PV and 2.0 PV, and there seems to be a serious tailing. It seems that adding more buffer solution can still recover a higher amount of PCB (Aroclor 1254).

In one embodiment of the method of remediating contaminated sludge of the present invention, in combination, the addition of a high heat emulsion of 0.87 PV is estimated to be effective at least about 58.2% of the PCB (Aroclor 1254) in the overall column sludge. Moreover, as shown in the bar graph of the biodegradation rate factor of the PCB of Fig. 4a, in the bottom sediment of the column, that is, the water subjected to high heat can effectively remove about 76.7% in the case of contact with the emulsion in the oil. The PCB (Aroclor 1254) removes approximately 56.4% of the PCB (Aroclor 1254) in the middle of the cooling and reverse rotation, but the bottom mud near the exit position in the uppermost section is 41.6%.

In an embodiment of the method for remediating contaminated sediment of the present invention, as shown in the variation diagram of HCB concentration in the flowing water of FIG. 3, the HCB concentration in the final outflow water is slightly higher than that of the PCB (Aroclor 1254), and the calculation is performed. The recovery rate (or removal rate) of the reverse conversion operation was 56.5%, which was quite close to the recovery rate of PCB (Aroclor 1254). Moreover, as shown in the bar graph of the biodegradation rate factor of the PCB of Fig. 4b, in the bottom sediment of the column, that is, the water subjected to high heat can effectively remove about 81.7% in the case of contact with the emulsion in the oil. Compared with the recovery rate of 50.7% of BDE-209 (log Kow about 10.0) in PBDEs with high oil emulsion at the normal temperature, it can be seen that the reverse recovery method is better than the previous high oil emulsion. The way of recycling.

According to the method of the present invention for remediating contaminated sediment, it is preferred to carry out column colony analysis to further understand the colony distribution. The so-called "column group analysis" is a cluster analysis by polymerase PCR chain reaction-electric gradient gel electrophoresis. The sediments of the above different sections are placed in an anaerobic glove box before chemical analysis. After three days of culture in a general anaerobic liquid medium (endospores need to be regenerated for 2-3 days and grow to a comparable total number of bacteria), DNA extraction is performed. After PCR amplification of the 968f /1392r universal primer pair, denaturing gradient gel electrophoresis was performed. In this embodiment, the gradient of the gradient is changed from 35% to 65% of the denaturant gradient. After the electrophoresis gel is photographed by the glue machine, the image is reversed by the Microsoft painter software to obtain a negative image. For example, the PCR-DGGE negative image of the microbiota in the lower layer of the upper layer in the upper column of the column as shown in Fig. 5; the ladder in the figure is a colony rich in a certain bacteria phase used in the laboratory of the inventor as a review every time. The positive control of DGGE effect and quality, the separation effect of Ladder shows that the quality of this DGGE program is ideal.

In an embodiment of the present invention, as shown in FIG. 5, in the lower sediment, after exposure to the emulsion in the oil of high temperature of 90 ° C, it is indeed a relatively single fungus phase, only one bright band. Appears and shows that the heat sifting effect is good. This bright band should be a hydrogen producing bacteria that can produce endospores. The middle section is the section where the opposite rotation is carried out, and the temperature should be between 40 ° C and 60 ° C (the upper outlet water temperature is measured to be about 30 ° C). If the temperature is maintained for more than 30 minutes, the endospores may not be promoted. Producing bacteria to produce endospores, can also effectively kill most of the moderate temperature bacteria (as in Pasteurization), resulting in no bacteria in any three days can be effectively cultivated successfully, in order to avoid any wrong conclusions, Further repeated tests will confirm whether the situation occurs repeatedly; while the upper outlet water temperature is between 28-30 ° C, it is estimated that the temperature of the upper sediment should be between 30 ° C and 40 ° C. The temperature is only slightly higher than room temperature, which can make most of the mesophilic bacteria survive. Therefore, after 3 days of cultivation, the results of the bacteria phase are quite rich, and at least 12 bright bands can be seen. Some of the bright bands may not be completely complete. Isolation and Purification

According to the present invention, since the bottom mud in the large pipe string is relatively fluffy after the reverse transfer operation, a part of the concentration remains in the water phase. After the recovery operation is completed, part of the water phase is also removed, and after being slightly pressed back to the upper layer of sediment, it is allowed to stand and monitored; however, the sample data may be more reliable after the second (inclusive) and thereafter. If there is not enough dehalogenated bacteria in the lower sediment in the bottom of the column, it is reasonable to continue to level, and the above-mentioned flora is only exposed to very short heat, that is, about 4.0 PV is immediately performed. The push solution of about 25 ° C can still retain most of the dehalogenated bacteria.

In addition, in an embodiment of the present invention, as shown in FIG. 6 and FIG. 7 , the concentration of the PCB (Aroclor 1254) and HCB in the upper, middle and lower layers within 35 days, the upper column It does show a gradual decrease trend. After the first reverse recovery test, the bottom sediment in the column is subjected to DNA extraction by sacrificial sampling, that is, all the upper, middle and lower layers are taken out and mixed, and then subjected to DNA extraction. The bacterial phase can be obtained by performing PCR-DGGE, but DNA extraction can also be performed if sufficient sediment cannot be obtained.

Moreover, as shown in Fig. 6 and Fig. 7, the concentration of PCB (Aroclor 1254) and HCB in the upper sediment decreased by about 26.4 and 27.9% in 35 days respectively. If the first-order degradation dynamic equation is used for preliminary simulation, the half-life period is For 62 and 15 days; the concentration of PCB (Aroclor 1254) and HCB in the upper sediment decreased by 28.4 and 31.2% in 35 days respectively. If the first-order degradation dynamic equation is used for preliminary simulation, the half-life is 58 and 48 days. .

In an embodiment of the present invention, the reverse rotation test results show that a single operation can remove 58.2% of the PCB (Aroclor 1254) and 56.5% of the hexachlorobenzene in the experimental column, and the removal rate in the lower sediment is about 80%. (The overall removal rate is about 50%), and the reverse transfer operation of the PCB (Aroclor 1254) and hexachlorobenzene can indeed achieve the purpose of screening a specific flora, and can continue to effectively degrade the target hydrophobicity within the next 35 days. Contaminants reach 30%.

Hereinafter, a representative example of preparation of an emulsion prepared by using an oil solute of soybean oil as a base oil-based material and adding a suitable surfactant is further exemplified, and the reverse transformation emulsification to which the present invention is applied is exemplified and explained in more detail. The preparation method of the liquid. "Preparation of reverse phase emulsified stock solution A1~A3"

First, the first surfactant and the second surfactant were slowly added to the container in a ratio as shown in Table 1 at room temperature and uniformly mixed to make an emulsion system. Then, the emulsified system was stirred for 30 minutes at a rotation speed of about 50 to 1000 rpm by a magnet stirrer to uniformly mix the particles. Since the surfactant was easy to foam, the generation of bubbles should be minimized during the preparation process. Then, the soybean emulsified soybean oil (Taiwan Sugar Co., Ltd.) was slowly added to the oil solute at a ratio shown in Table 1 at room temperature, and waited for stabilization to obtain a reverse transition emulsified stock solution A1 to A3 having a thick milky appearance. Further, as shown in Table 1, the surfactant contained in the reverse transformation emulsified stock solution A1 is composed only of the first surfactant; and the interface of the reverse transformation emulsification liquid A2 and the reverse transformation emulsification liquid A3 described above. The active agent is composed of a first surfactant and a second surfactant.

Further, as shown in Table 1, the volume content ratio (S1: OL) of the surfactant (S1) and the oil solute (OL) contained in the above-mentioned reverse conversion emulsified stock solution A1 was about 90.9: 9.1.

Further, as shown in Table 1, the volume content ratio (S1 + S2: OL) of the surfactant (S1 + S2) to the oil solute (OL) contained in the above-mentioned reverse conversion emulsified stock solution A2 was about 90.9: 9.1.

Further, as shown in Table 1, the volume content ratio (S1+S2:OL) of the surfactant (S1+S2) and the oil solute (OL) contained in the above-mentioned reverse conversion emulsified liquid A3 was about 50:50.

Next, the above-mentioned reverse transformation emulsified stock solutions A1 to A3 are heated from 25 ° C to 95 ° C at a fixed heating rate, and the apparent transition temperature of the oppositely transformed emulsified stock solutions A1 to A3 is observed to determine the reverse rotation temperature and the resistance value thereof is measured. . As shown in FIG. 8, when the reverse transformation emulsified stock solution is below the opposite rotation temperature, it exhibits an oil-in-water (O/W) emulsion dosage form, and its appearance is cloudy and hazy; and, as shown in FIG. On the contrary, when the transition emulsified stock solution is heated to the opposite temperature, it exhibits a water-in-oil (W/O) emulsion dosage form, and its appearance changes from a white mist to a clear liquid. Then, the observed reverse rotation temperature of each of the reverse transformation emulsified stock solutions A1 to A3 and the resistance value reaching the opposite rotation temperature are respectively shown in Table 1.

Table 1      Reverse transformation emulsified liquid A1 Reverse transformation emulsified liquid A2 Reverse transformation emulsified liquid A3 First surfactant (vt%) 90.9 67.3 2.5 Second surfactant (vt%) 0 23.6 47.5 Soybean oil (vt%) 9.1 9.1 50 Reverse Temperature (°C) 87 74 45 Resistance (Ω) 0.9775 1.0264 1.931

As shown in Table 1 above, it can be known that the reverse conversion temperatures of the reverse conversion emulsions prepared from the first surfactant, the second surfactant, and the soybean oil according to the present invention are 87 ° C and 74 ° C, respectively. And 45 ° C, between 30 ° C and 99 ° C. <<Example 1 to Example 9>>

First, in the laboratory, a pipe column experiment was carried out by filling the bottom mud of Errenxi into a column of a transparent PVC pipe having a diameter of 4 inches. The depth range of 0 to 15.00 cm from the uppermost surface of the sediment is the surface sediment, the depth range of 15.01 to 20.00 cm is the middle sediment, and the lower sediment is in the range of 20.01 to 30.00 cm. While heating the bottom of the column, the average temperature of the bottom sediment at a depth of 20.01 to 30.00 cm is maintained above 80 °C.

The physicochemical properties of the Errenxi bottom mud were measured, and the measured values were respectively reported in Table 3. In addition, the concentration of PCB and HCB (Aroclor 1254) was obtained by high pressure extraction, concentration under reduced pressure, column purification, and concentration and concentration again, and then analyzed by gas chromatography GC-ECD detector. The GC-ECD analysis conditions for PCB and HCB are shown in Table 2 below.

Table 2   Analysis conditions of the project PCB HCB analysis conditions HP-5 (length 30 m, caliber 0.32 mm, 0.25 μm behind the membrane), 12 cm/sec N2 HP-5 (length 30 m, caliber 0.32 mm, 0.25 μm behind the membrane) ), 12 cm/sec N2 injection port 225 °C, without splitting, inject 1μl 200 °C, without splitting, inject 1μl heating equation 100 °C for 2 min, 15 °C / min to 160 °C, then The temperature is raised to 270 ° C at 5 ° C / min, the final temperature is 270 ° C 100 ° C for 1 min, the temperature is raised to 140 ° C at 20 ° C / min, and then raised to 280 ° at 15 ° C / min C and keep the temperature for 15 minutes. The detector ECD detects the temperature of 300 °C. ECD detects the temperature of 300 °C.

Next, the reverse transformation emulsion obtained in the above preparation example is diluted 20 times, and then filled in an emulsion storage device capable of releasing a high temperature liquid from the lower end of the device, and released from the emulsion storage device and maintained in the opposite direction. The emulsion is transformed in the opposite direction of temperature, and while avoiding the formation of the dominant flow path, the pulse flow pump is used from the lower side of the column, and the average flow rate is converted into a quantitative flow rate of about 0.5 mL hr-1, and is avoided. In the short-flow phenomenon, the reverse transformation emulsion (reverse temperature is about 90 ° C) is injected into the sediment in the column from the bottom up.

The reverse transfer emulsion was injected in an amount of about 1 liter (i.e., a pore volume of about 0.6). In addition, while the temperature of the bottom sediment is maintained at a depth of 20-30 cm, the temperature of the sediment is maintained at 80 ° C or higher for hot screening, and then the temperature of the upper sediment is monitored in time, and the residence time of the transition emulsion is reversed (hr) ).

Then, after stopping the injection and flow for at least 30 minutes, inject 400 ml of carbonate buffer (concentration: 15%) at room temperature to avoid drastically changing the ionic strength in the sediment. It is also ensured that the microbial flora of the bottom sediment is indeed hot-sifted to obtain hydrogen-producing bacteria capable of producing endospores in extreme environments. The experiment consisted of 5 sampling points in 49 days, and the calculation of PCB and HCB concentration analysis on the outflow solution of the column on the 0th, 7th, 14th, 28th, and 49th days respectively. The PCB and HCB removal rates were obtained, and the results are shown in Fig. 10 and Fig. 11, respectively, and the removal rate of the PCB and HCB on the 49th day is shown in Table 3.

In various embodiments of the invention, the recovery of organic contaminant concentration is defined as the recovery of PCB and HCB for a concentration of 10 mg/kg. In addition, the bottom of the hot sieve will be cooled and the most easily fermented hydrogen-producing glucose will be used as the substrate for hydrogen production test and PCR-DGGE phase investigation and strain identification, and the results of the bacteria phase and the original domesticated bacteria The comparison is made to confirm whether the strains obtained by the sampling belong to the hydrogen-producing bacteria or the indigenous new bacteria which have been reported in the well-known literature.

Table 2      Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Source of the bottom mud Errenxi Errenxi Errenxi Errenxi Errenxi Errenxi Erren Xierenxi Errenxi Temperature (°C) 10 10 10 20 20 20 30 30 30 pH 5.5 7.0 8.5 5.5 7.0 8.5 5.5 7.0 8.5 Organic Matter Content (wt%) 0 0.1 1.0 0 0.1 1.0 0 0.1 1.0 Total Fill Height ( Cm) 30 30 30 30 30 30 30 30 30 Emulsion input (%) 0 1.0 10 1.0 10 0 10 1.0 0 PCB removal rate (%) on day 49 20.17 33.65 42.7 47.21 54.51 46.43 58.04 46.64 55.52 Day 49 HCB removal rate (%) 47.73 57.11 65.24 80.15 83.85 72.64 91.22 84.09 88.46

It can be seen from Table 3, Figure 10 and Figure 11 that the degradation effect of PCB (Aroclor 1254) is the best in Example 7, the removal rate is 58.04%, and the HCB is also in Example 7, the removal rate is about 91.22%, the second best. All are Example 9. The conditions of Example 7 are 30 ° C, pH 5.5, 10% high concentration emulsion and 0.10% medium soil organic matter; the conditions of Example 9 are 30 ° C, pH 8.5, 0% high concentration emulsion And 1.0% higher soil organic matter.

Next, a control factor analysis is performed. As shown in the PCBs factor reaction table shown in Table 4, in the PCBs factor reaction table, when the factor A (temperature) is at a variation level of 1 (10 ° C), the level 1 value is experimental group 1, 2, The average removal rate of 3 (32.17%); and when the variation level is 2 (20 °C), the level 2 value is the average removal rate of the experimental group 4, 5, 6 (49.39%); When it becomes 3 (30 °C), its level 3 value is the average removal rate (53.40%) of the experimental group 7, 8, and 9. The factor effect value is obtained by subtracting the average removal rate of different variation levels under the same control factor. If the factor A changes from level 1 to level 2, the level change is 17.21, and the value of E1→2 in Table 4; when the level 2 changes to 3, the level change is 4.01, and E2→3 in the table. The value. It means that when the temperature is raised from 10 °C to 20 °C, the removal rate will increase by 17.21%; and when the temperature is increased from 20 °C to 30 °C, the removal rate will increase by 4.01%. Range is the difference between the maximum and minimum values of the three fluctuation levels. For example, the Range of the A factor is the difference between the level 3 minus the level 1 (21.23). Similarly, the Range value of each factor is compared, and the A factor is ranked first according to its value, indicating that the temperature has the highest influence on the PCBs removal effect, the second is the emulsion addition amount (C factor), and the organic matter addition amount and The pH values (B and D factors) ranked 3 and 4, indicating no significant effect on the removal rate of PCBs.

Table 4   Experimental group A B C D Level 1 32.17 41.81 37.75 43.40 Level 2 49.39 44.93 45.46 46.04 Level 3 53.40 48.22 51.75 45.52 E1→2 17.21 3.13 7.71 2.64 E2→3 4.01 3.28 6.29 -0.52 Range 21.23 6.41 14.00 2.64 Rank 1 3 2 4

As shown in Table 5, in the HCB factor reaction table, when the factor A (temperature) is at a variation level of 1 (10 ° C), the level 1 value is the average removal rate of the experimental group 1, 2, and 3 (56.69). %); and when the change level is 2 (20 °C), the level 2 value is the average removal rate of the experimental group 4, 5, 6 (78.88%); when the change level becomes 3 (30 °C) When the level 3 value is the average removal rate (87.92%) of the experimental group 7, 8, and 9. The factor effect value is obtained by subtracting the average removal rate of different variation levels under the same control factor. If the factor A changes from level 1 to level 2, the level change is 22.19, and the value of E1→2 in Table 5; when the level 2 changes to 3, the level change is 9.04, and E2→3 in the table. The value. It means that when the temperature is raised from 10 °C to 20 °C, the removal rate will increase by 22.19%; and when the temperature is increased from 20 °C to 30 °C, the removal rate will increase by 9.04%. Range is the difference between the maximum and minimum values of the three fluctuation levels. For example, the Range of the A factor is the difference between the level 3 minus the level 1 (31.23). Similarly, the Range value of each factor is compared, and the first factor is ranked according to the value of the A factor, indicating that the temperature has the highest influence on the HCB removal effect, the second is the emulsion addition amount (C factor), and the pH value and organic matter. The addition amounts (D and B factors) ranked 3 and 4, indicating no significant effect on the removal rate of HCB.

table 5   Experimental group A B C D Level 1 56.69 73.03 68.15 73.35 Level 2 78.88 75.02 75.24 73.66 Level 3 87.92 75.45 80.10 76.49 E1→2 22.19 1.98 7.09 0.31 E2→3 9.04 0.43 4.87 2.83 Range 31.23 2.41 11.95 2.83 Rank 1 4 2 3

In addition, FIG. 12 and FIG. 13 are respectively a PCB control factor reaction diagram and a HCB control factor reaction diagram. As shown in Figure 12, it can be seen that the significant control factors for PCB (Aroclor 1254) are temperature and emulsion concentration, both of which increase with the control factor; that is, the higher the temperature, the degradation within the test range. The faster the rate; the higher the concentration of the emulsion, the faster the degradation rate, but the effect of the former is more significant. Again, as shown in Figure 13, the situation is very similar for HCB.

In addition, the method for remediating the contaminated sediment of the present invention can use the Taguchi method to predict the removal rate of the optimal parameter combination, and the factor effects in the Taguchi method can be superimposed on each other, and the reaction value of the optimal factor combination is calculated according to the empirical formula. Medium Y̅ represents the average removal rate of Examples 1-9, and Y̅ _A1 , Y̅ _B2 , Y̅ _C3, and Y̅ _D3 represent the A, B, and C combined D control factors at the best change levels of 1, 2, and 3, respectively. The average removal rate is calculated according to the table and the value entered into the formula to calculate the removal rate of the optimal parameter combination. The calculation process for the removal rate of the PCB (Aroclor 1254) is as follows: Y = Y̅ + ( Y̅ _{A 3} - Y̅ ) + ( Y̅ _B3 –Y̅ ) + ( Y̅ _C3 –Y̅ ) + ( Y̅ _D2 – Y̅ ) = 44.98 + ( 53.40 – 44.98 ) + ( 48.22 – 44.98 ) + ( 51.75 – 44.98 ) + ( 46.04 – 44.98 ) = 64.47%

In addition, the calculation process for the removal rate of HCB is as follows: Y = Y̅ + ( Y̅ _{A 3} - Y̅ ) + ( Y̅ _B3 –Y̅ ) + ( Y̅ _C3 –Y̅ ) + ( Y̅ _D3 – Y̅ ) = 74.50 + ( 87.92 – 74.50 ) + ( 75.45 – 74.50 ) + ( 80.10 – 74.50 ) + ( 76.49 – 74.50 ) = 96.46%

It can be seen from the results that the removal rate of PCBs under the optimal condition level (temperature 30 ° C, organic matter 1%, emulsion 10%, pH 7.0) can reach 64.47%; while HCB is under the optimal combination of conditions ( The removal rate is up to 96.46% at a temperature of 30 ° C, organic matter 1%, emulsion 10%, pH 8.5. However, the empirical formula is based on the assumption that the effects of each control factor are independent, and there is no interaction between the factors. For example, two factors with greater influence are selected in the HCB batch experiment. A (temperature) and C (emulsion addition), respectively, assuming that when the factor C is at the level 1, 2, and 3, when the factor A changes from the level 1 to 2, the removal rate increases by 39%, but in actual conditions. The amount of variation in the factor A below may vary depending on the setting parameters of C.

Figure 14 is a graph showing the interaction between the two significant factor temperatures of the PCB (Aroclor 1254) and the concentration of the emulsion. If the two lines are completely parallel, the two factors are completely independent. If there is an interlacing, there is an interaction, which should be further tested. In an embodiment of the method for remediating contaminated sediment of the present invention, as shown in FIG. 14, when the concentration of the emulsion is between 1.0 and 10.0%, the influence of the temperature and the concentration of the emulsion on the degradation efficiency is almost completely independent. Since this technology is applied to the site, its concentration is easily controlled between 1.0-10.0%. From this interaction, it is also known that in the absence of an emulsion, the temperature is raised from 10 ° C to 20 ° C, and the effect is remarkably increased, but the effect is limited from 20 ° C to 30 ° C.

In addition, Figure 15 shows the interaction between the two significant factor temperatures of HCB and the concentration of the emulsion. As shown in Figure 15, the three segments are almost completely parallel, indicating the temperature at the current test (10 ° C -30 ° C) and the emulsion. Within the concentration range (0-10.0%), the two control factors are almost completely independent, and it is easy to estimate the temperature at which temperature and which emulsion concentration can be obtained (pH and organic matter can be almost completely ignored) . <<Example 10 to Example 13>>

Using the reverse transformation emulsion obtained in the above preparation example, the local mode field test was carried out in Errenxi. As shown in Table 6, nutrients were separately added in different sampling areas (for example, containing nitrogen, phosphorus, potassium, calcium, magnesium). , inorganic salts such as sulfur, manganese, iron, boron, zinc, or copper), performing the reverse conversion step or biodegrading step, and detecting the residues of PCB and HCB in the upper, middle, and lower layers of the sampling area after 70 days. The amount, and then the total removal rate of PCB and HCB, was calculated and recorded in Table 6.

Table 6      Example 10 Example 11 Example 12 Example 13 Contaminated land Errenxi local underground sediment Errenxi local underground sediment Errenxi local underground sediment Errenxi local sediment sampling area ABCD nutrient points XX ○ ○ Local reverse steps X ○ ○ ○ Biodegradation step XXX ○ Total removal rate of PCB 38±0.8% 98.3±0.4% 86.5±16.4% 98.0±0.1% Total removal rate of HCB 87.7±17.4% >97%* >97%* >97% * * The final residual amount of HCB is less than the machine detection limit and cannot be detected, so the removal rate is greater than 97%.  

16 and 17 are schematic views showing the total removal rates of the PCB and HCB in the sampling areas A to D, respectively. It can be seen from the above Table 6 and FIG. 16 that the use of the reverse transformation emulsion of the present invention for the in situ reverse rotation step can increase the total removal rate of the PCB from 38% to 98.3%; in addition, it can be seen from Table 6 and FIG. 18 above that: The reverse transformation of the emulsion of the present invention to carry out the in situ reverse rotation step can increase the total removal rate of HCB from 87.7% to greater than 97%. In other words, the reverse-transformed emulsion prepared by the preparation method of the present invention can be used to rectify the contaminated environment, and the oil can be efficiently recovered, and the sediment in the treated contaminated environment has an excellent biological pair. The ability to degrade 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.

In summary, according to the reverse transformation emulsion of the present invention and the contaminated sludge treatment method using the same, it can be confirmed that at least the following effects of the invention can be achieved: (1) According to one of the technical viewpoints of the present invention, the surfactant is used differently. The hydrophilicity at the temperature is not the same. For the lower temperature, the oil is originally heated in the water (O/W) emulsion, which is converted into higher temperature water in the oil (W/O) type. The emulsion is used to make the emulsion transport path highly similar to the hydrophobic contaminant, and can effectively contact and accelerate the mass transfer efficiency. (2) According to still another technical point of view of the present invention, an oppositely transformed emulsion is injected into an environment contaminated by a hydrophobic organic pollutant such as soil, sediment, sludge, etc. at a high temperature to provide an oil phase. The storage space of the emulsion after the reverse conversion phase; in addition, as the temperature is lowered, the oil is again converted into oil of small particles in the water (O/W) type emulsion, and the contaminants confined to the oil are not easily exchanged. come out. (3) According to another technical point of view of the present invention, by injecting a clean buffer, the emulsion filled with the contaminant can be transported in a specific direction, thereby effectively removing the contamination in the environmental matrix. (4) According to still another technical point of the present invention, in the transfer process of the emulsion containing the contaminant, since the removal effect is gradually decreased as the temperature is gradually lowered, the removal rate of the contaminant in the region where the temperature is higher is better. That is, the concentration of residual pollutants in the bottom sediment will be relatively low, and the concentration of pollutants remaining in the upper sediment will be relatively high. (5) According to another technical point of view of the present invention, it is possible to use to screen different specific strains by forming a sediment at a local high temperature state. For example, as shown in FIG. 1 , when the lower sediment is formed in a state suitable for the growth of the dominant bacteria of the hydrogen-producing microflora, and the upper sediment is formed into a state suitable for the growth of the dominant bacteria of the anaerobic dehalogenating bacteria group, The hydrogen-producing bacteria in the bottom sediment can effectively utilize the residual emulsion for hydrogen production, and the hydrogen dissolved in the pore water is transported upwards into the highly polluted upper sediment, and the dominant bacteria present in the upper mud The anaerobic dehalogenating bacteria group can continue to effectively perform biodegradation, thereby achieving the purpose of sufficiently and effectively removing the dye.

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.

no.

1 is a diagram showing the step of biodegrading residual contaminants according to an embodiment of the present invention, by using the dominant bacteria of the hydrogen-producing bacteria in the bottom sediment and the anaerobic dehalogenating bacteria in the upper sediment to continue the residue Schematic diagram of the ISPIE&AC operating concept for biodegradation of hydrophobic contaminants in the sediment. Figure 2 is a graph showing changes in PCB concentration in the outflow water in an embodiment of the present invention. Fig. 3 is a graph showing changes in HCB concentration in the outflow water according to an embodiment of the present invention. 4a and 4b are graphs showing changes in concentration of PCB and HCB retained in the tube after reverse conversion according to an embodiment of the present invention. A PCB biodegradation rate factor reaction diagram showing an embodiment of the present invention is shown. Fig. 5 is a view showing the PCR-DGGE result image of the flora in the upper middle and lower sediments in the column of one embodiment of the present invention. Fig. 6 is a graph showing degradation results of PCB (Arochlor 1254) and HCB in the middle and lower sediments above the column of one embodiment of the present invention. Fig. 7 is a graph showing the results of HCB degradation in the middle and lower sediments above the column of one embodiment of the present invention. Figure 8 is a diagram showing the appearance of an inversely transformed emulsion of one embodiment of the present invention below the reverse rotation temperature. Figure 9 is a diagram showing the appearance of the reversely transformed emulsion of one embodiment of the present invention after reaching the opposite temperature. Fig. 10 is a graph showing the results of batch experiments of the PCBs of Examples 1 to 9 of the present invention. Fig. 11 is a graph showing the results of batch experiments of HCBs of Examples 1 to 9 of the present invention. Figure 12 is a graph showing the PCB biodegradation rate factor reaction of Examples 1 to 9 in the present invention. Figure 13 is a graph showing the HCB biodegradation rate factor reaction of Examples 1 to 9 in the present invention. Figure 14 is a graph showing the PCB biodegradation rate factor interaction diagrams of Examples 1 to 9 in the present invention. Figure 15 is a graph showing the HCB biodegradation rate factor interaction diagrams of Examples 1 to 9 in the present invention. Fig. 16 is a graph showing the result of PCB removal rate in Examples 10 to 13 in the present invention. Fig. 17 is a graph showing the result of HCB removal rate in Examples 10 to 13 in the present invention.

Claims (7)

A method for remediating a contaminated sediment comprises the steps of: inverting a transition emulsification stock solution: heating the oppositely transformed emulsified stock solution to a temperature above the opposite temperature, and then injecting into the contaminated sediment, and staying at least for more than 30 minutes, In order to fully react the reverse transformation emulsion with the hydrophobic pollutant in the sediment, wherein the reverse conversion emulsification stock solution has a reverse rotation temperature ranging from 30 ° C to 99 ° C; and a buffer input step: after the completion of the above reaction, Loading a volume of the buffer to recover the hydrophobic contaminants in the sediment, wherein the buffer is added in an amount of at least 1.0 pore volume or more; wherein the reverse conversion emulsified stock solution is an oil solute, and the first surfactant Constructed, and the reverse rotation temperature is between 30 ° C and 99 ° C; the first surfactant is from polyethylene glycol, polyoxyethylene sorbitan, polyoxyethylene sorbitan monooleate, hexa Alcohol laurate, sorbitan mono-9-octadecenoate, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene-polyoxypropylene alcohol, polyoxyethylene fatty acid , trialkylamine oxide, polyoxyethylene sorbitan monolaurate (Tween 20), polyoxyethylene sorbitan monooleate (Tween 80), sorbitan monooleate (Span 80), And the mixture thereof comprises 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 The mixture constitutes at least one selected from the group; and the average particle size of the oil particles in the reverse transformation emulsion is in the range of 1 nm to 5000 nm. The method for remediating contaminated sediment according to claim 1, wherein the reverse conversion emulsified liquid system further comprises a second surfactant; the second surfactant is from polyethylene glycol, polyoxyethylene sorbitan, poly Oxyethylene sorbitan monooleate, hexaol laurate, mono-9-octadecenoic acid sorbitan ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, Polyoxyethylene-polyoxypropylene alcohol, polyoxyethylene fatty acid ester, trialkylamine oxide, polyoxyethylene sorbitan monolaurate (Tween 20), polyoxyethylene sorbitan monooleate (Tween) 80), sorbitan monooleate (Span 80), and mixtures thereof, comprising at least one selected from the group consisting of. The method for remediating a contaminated sediment according to claim 1 or 2, wherein the reverse conversion emulsified liquid further comprises an emulsification accelerator for promoting an emulsification between the oil solute and the water; the emulsification accelerator is an oil-water fusion agent, and an emulsion is stabilized. The agent, and combinations thereof, form at least one selected from the group. The method for remediating contaminated sediment as recited in claim 1 or 2, wherein the contaminated sediment is derived from at least polychlorinated biphenyl (PCB), hexachlorobenzene (HCB), polybrominated diphenyl ethers (PBDEs), Phthalates (PAEs), brominated diphenyl ethers (BDE209), di(2-ethylhexyl) phthalate (DEHP), dibutyl phthalate (DBP), phthalic acid At least one component of diethyl formate (DEP), tolyl phthalate (BBP), or a combination thereof. The method for remediating contaminated sediment as recited in claim 1 or 2, further comprising the step of biodegrading residual contaminants: by utilizing the dominant flora of the hydrogen producing bacteria in the bottom sediment, and the anaerobic desorption in the upper sediment The halobacteria continue to biodegrade the hydrophobic contaminants remaining in the sediment. The method for remediating contaminated sediment as claimed in claim 1 or 2, wherein the amount of the reverse conversion emulsion is in the range of 0.33 to 1.0 pore volume. The method for remediating contaminated sediment according to claim 1 or 2, wherein the buffer is a carbonate buffer solution.