TWI411585B - Gel material for treating chloric pollution and the application thereof - Google Patents

Description

Colloidal matrix for remediation of chlorine-containing contaminants and application thereof

The present invention relates to a colloidal matrix and its use, and more particularly to a colloidal matrix capable of sustained release of a carbon source, a hydrogen source and a nutrient substrate for a long period of time and its use for rectifying chlorine-containing contaminants.

Chlorinated organic solvents are used in a large number of industrial processes such as degreasing, electronic parts cleaning and dry cleaning. However, due to improper management and disposal of human beings, the leakage of chlorine-containing organic solvents makes chlorine-containing pollutants one of the main sources of soil and water pollution at home and abroad. Taking groundwater pollution as an example, the most common chlorine-containing pollutants are dense non-aqueous phase liquids (DNAPL) pollutants, including vinyl chloride (VC), dichloroethylene (dichloroethylene, DCE). ], trichloroethylene (TCE), perchloroethylene (PCE), methylene chloride or chloroform. Among them, since the density of the heavy non-aqueous phase solution is heavier than water and incompatible with water or only slightly soluble in water, a heavy non-aqueous phase solution forms a separate liquid phase after entering the groundwater layer.

The conventional method for remediation of chlorine-containing contaminants is the extraction treatment. The method is mainly for placing at least one injection well above the contaminated area of the chlorine-containing pollutant, and at least one extraction well is disposed above the opposite downstream of the contaminated area. A surfactant is then added to the contaminated area from the injection well. Since the surfactant is a polymer having a hydrophilic group and a hydrophobic group structure, when the surfactant is added to the contaminated region, the hydrophobic group of the surfactant can be The chlorine-containing contaminant forms an organic phase for increasing the solubility of the chlorine-containing contaminant; and the hydrophilic group of the surfactant can be combined with one water to make the chlorine-containing contaminant soluble in the aqueous phase, To enhance the solubility of the chlorine-containing contaminant in the aqueous phase. Finally, a liquid [such as: groundwater] is injected into the contaminated area from the injection well to push the chlorine-containing pollutant to the bottom of the extraction well, and then the chlorine-containing pollutant is extracted through the extraction well to ground. Conventional methods for remediating chlorine-containing contaminants utilize the surfactant to increase the solubility of the chlorine-containing contaminant relative to water, thereby reducing the concentration of the chlorine-containing contaminant in the contaminated area.

However, the conventional method for remediating chlorine-containing contaminants requires continuous injection of a surfactant into the injection well as a matrix for participating in the reaction. Therefore, it is necessary to continuously inject a surfactant through a mechanical facility, so that the treatment cost cannot be reduced. In addition, since it is difficult to control the amount of the surfactant to be used, it is easy to cause a decrease in the efficiency of the treatment, or excessive waste of the surfactant due to an excessive injection amount or a too fast addition rate. In addition, the conventional method of remediating chlorine-containing contaminants only removes the chlorine-containing contaminants from the contaminated area, and subsequent treatment problems will still result in additional costs and more remediation procedures.

Another conventional method for remediating chlorine-containing contaminants is to place a permeable reactive wall on site. The method is to establish a ditch or a remediation wall perpendicular to the groundwater flow direction downstream of the pollution source, a row of vertical or horizontal remediation wells, or a funnel-type collection system (funnel-and- Gate system). Then, reactive materials are disposed in the water-permeable reaction wall, and when the contaminated groundwater flows through the water-permeable reaction wall, the chlorine-containing pollutants and the reaction substances in the water-permeable reaction wall are physically, chemically or The biological reaction mechanism is used to remove the chlorine-containing pollutants and make the groundwater flowing through the water-permeable reaction wall a rectified groundwater. Broadly speaking, any method that can reduce the concentration of pollutants in the passive way in the field can be called the in-situ remediation wall technology.

In the case of a biological reaction mechanism, a microorganism (for example, a bacterium) is used as a reaction substance to decompose the chlorine-containing contaminant by biodegradation. In addition, if the microorganism-carbon source is provided, the microorganism is co-metabolized to enhance the efficiency of the microorganism to decompose and remove the chlorine-containing pollutant. Among them, biodegradation can be distinguished into aerobic biodegradation and anaerobic biodegradation. Aerobic biodegradation is the use of dissolved oxygen as an electron acceptor by subsurface microorganisms. The anaerobic procedure uses different biodegradation mechanisms, such as the use of nitrates, ferric iron, sulfate or carbon dioxide as the ultimate electron acceptor.

(1) Aerobic biodegradation (aerobic biodegradation)

Aerobic biodegradation often occurs near the edge of the contaminated mass and near the water surface. When groundwater is contaminated, existing microbes use dissolved oxygen as an electron acceptor to perform aerobic biodegradation, which removes contaminants by aerobic co-metabolism. Dissolved oxygen is first used by microorganisms as an electron acceptor because the microorganisms can obtain the maximum energy after aerobic respiration, which is beneficial to the synthesis of more microbial cells.

(2) Anaerobic biodegradation

Anaerobic biodegradation mainly occurs inside the contaminated mass. Generally, anaerobic biological remediation technology is adopted to solve the problem that the above-mentioned conventional extraction treatment method cannot decompose chlorine-containing pollutants in situ. Among them, anaerobic biodegradation uses hydrogen as an electron supplier in anaerobic reductive dechlorination, so it is necessary to generate hydrogen by fermentation substrate. It is widely used in the field of anaerobic biodegradation technology because the contaminated area is injected into the substrate, such as sugar (molasses), vegetable oil, organic acid (lactate, formate, butyrate, propionate or benzoate). Acid salts), alcohols (methanol or ethanol) or yeast extracts, etc., to promote the growth of microorganisms in the contaminated area, and to generate hydrogen through the microbial fermentation substrate to promote the reductive dechlorination of chlorine-containing pollutants. .

Generally speaking, in the anaerobic reduction dechlorination reaction, vegetable oil or molasses is mostly used as a nutrient substrate for microorganisms, so that the existing microorganisms form a biologically permeable reaction wall to treat chlorine-containing pollutants in the local environment. Vegetable oils are hydrolyzed to form long-chain fatty acids and glycerol. Glycerin is easily soluble in water and can be rapidly broken down by microorganisms. Long-chain fatty acids are poorly water-soluble and are decomposed by microorganisms to form H ₂ and acetic acid. Among them, the hydrogen production reaction of vegetable oil is as follows: C ₁₈ H ₃₂ O ₂ +16 H ₂ O→9CO ₂ +9H ₂ CO ₃ +50 H ₂ . In addition, if molasses is used as a matrix source, a microbial carbon source can be provided to promote aerobic co-metabolism.

Since microorganisms cannot directly obtain the energy required for the reaction by metabolizing chlorine-containing contaminants, it is necessary to additionally add a matrix to the microbial metabolism to obtain energy, so that the microorganism can be made through the aforementioned aerobic co-metabolism or anaerobic reductive dechlorination reaction. Degradation of chlorine-containing pollutants.

However, if the microorganism cannot continuously obtain a sufficient carbon source, hydrogen source or nutrient, it is impossible to increase the number of microbial bacteria and maintain a certain amount of hydrogen production for the reductive dechlorination reaction of the chlorine-containing contaminant. Therefore, the above-mentioned substrate must be frequently added, for example, by continuously injecting a substrate into the water-permeable reaction wall by a mechanical device to promote microbial growth.

In addition, the transport of the matrix between the soils, that is, the mobility of the matrix, is also one of the main factors affecting the reductive dechlorination reaction. If vegetable oil is used as the nutrient substrate alone, the direct injection of the vegetable oil will not easily move the soil pores due to the poor ductility of the vegetable oil, which may cause the vegetable oil to easily become agglomerated and not fully dispersed in the soil. The use of microorganisms, resulting in low efficiency of overall remediation; if molasses is used as a nutrient substrate, molasses and the soil in the contaminated area have low adsorption capacity, so it is easily affected by groundwater flow and the matrix is washed away by groundwater. The matrix is not fully utilized by microorganisms, resulting in inefficient overall remediation. It can be seen from the above-mentioned two substrates that the vegetable oil which is too low in mobility causes uneven dispersion, and the molasses which is too mobile is caused to be lost too quickly. Therefore, in order to maintain the efficiency of remediation, it is necessary to continuously replenish the injection by mechanical force, so that the processing cost cannot be further reduced.

For the above reasons, the above-mentioned conventional methods for remediating chlorine-containing contaminants do still have to be improved.

The present invention provides a colloidal matrix for rectifying chlorine-containing contaminants for improving the efficiency of remediation for the purpose of the present invention.

A second object of the present invention is to provide a colloidal matrix for remediating chlorine-containing contaminants to reduce the cost of remediation.

Still another object of the present invention is to provide a colloidal matrix which can stably and continuously supply a microbial carbon source, a hydrogen source and a nutrient for remediating chlorine-containing contaminants.

In order to achieve the foregoing object, the technical means and the achievable effects of the present invention include: a colloidal matrix for remediating chlorine-containing contaminants, comprising: a microbial nutrient mixture and a polymeric colloid The polymeric colloid is dispersed in the microbial nutrient mixture, the polymeric gum system is composed of a vegetable oil and a surfactant, and the surfactant coats the vegetable oil.

A method for remediating a chlorine-containing contaminant, comprising: an injecting step of injecting the aforementioned colloidal matrix for remediating chlorine-containing contaminants into a contaminated area contaminated with chlorine contaminants, and the contaminated area contaminated with chlorine contaminants There is a microorganism; and a biological decomposition step, the carbon matrix, the hydrogen source and the nutrient required by the microorganism are provided by the colloidal matrix to promote the microorganism to continuously ferment the substrate and generate hydrogen to reduce and dechlorinate the chlorine-containing pollutant.

The above and other objects, features and advantages of the present invention will become more <RTIgt; The colloidal matrix for remediating chlorine-containing contaminants uniformly disperses and suspends a polymeric colloid in a microbial nutrient mixture to form a colloidal matrix of the present invention to form a sustainable and stable carbon source and hydrogen required for supplying microorganisms. The source and the colloidal matrix of nutrients promote the growth of microorganisms already present in the soil.

The polymeric gum system is composed of a vegetable oil and a surfactant, and the surfactant is coated on the surface of the vegetable oil to form the polymeric colloid. The vegetable oil belongs to a fixed continuous decomposition matrix, preferably a vegetable oil refined from vegetable oil, soybean oil and sesame oil. The colloidal matrix of the present invention for remediating chlorine-containing contaminants can induce more growth of microorganisms which are favorable for decomposing chlorine-containing contaminants by the vegetable oil coated in the colloidal matrix. Among them, the contact of vegetable oil with groundwater will produce a hydrolysis reaction, which will continue to release glycerol (alcohols) and long-chain fatty acids (LCFAs). When glycerin is present in the system, it can stimulate microbial growth and be rapidly decomposed. The multi-chain fatty acid is adsorbed between the pores of the soil, and is slowly oxidized by the oxidative decomposition of microorganisms and continuously generates hydrogen and acetate. Hydrogen is the electron acceptor of the microbial reduction and dechlorination reaction. Under redox conditions, the chlorine-containing contaminant gradually replaces the chlorine atom in the chlorine-containing contaminant by a hydrogen atom to complete the reductive dechlorination reaction. Furthermore, the vegetable oil has strong enrichment characteristics for the chlorine-containing pollutants, and the high concentration of chlorine-containing pollutants can be concentrated in the emulsified oil droplets formed by mixing the vegetable oil and the surfactant, and the local aquifer environment is not yet annoying. When oxygen production occurs, vegetable oil can effectively block chlorine-containing pollutants dissolved in water. After the growth of microorganisms, vegetable oil can enhance chlorine-containing pollutants by simultaneous physical blockage and microbial anaerobic hydrogen production and dechlorination. Processing efficiency.

The surfactant is a biodegradable surfactant. The polymer colloid is coated on the surface of the vegetable oil to form agglomerated clogging of the vegetable oil, and is not sufficiently uniformly dispersed in the soil to be utilized by the microorganism. The surfactant has a hydrophilic group and a hydrophobic group. When the hydrophilic moiety is stronger than the lipophilic moiety, the entire molecule is hydrophilic, soluble in water but insoluble in oil. On the other hand, if the strength of the lipophilic moiety is stronger than that of the hydrophilic moiety, the molecule is lipophilic, soluble in oil but insoluble in water. Among them, the hydrophilic-lipophilic balance is used to indicate the ratio between the molecular weight of the hydrophilic group of the surfactant and the molecular weight of the hydrophobic group. The larger the HLB value, the stronger the hydrophilicity of the surfactant; on the contrary, the smaller the HLB value, the stronger the lipophilicity. The lipophilic surfactant HLB has a maximum of 0, while the hydrophilic surfactant HLB has a maximum of 20 and an equilibrium value between 0 and 20. Preferably, the surfactant of the present invention comprises a lipophilic surfactant and a hydrophilic surfactant, and the surfactant is combined with the lipophilic surfactant and the hydrophilic surfactant. After the vegetable oil is mixed and emulsified, a high-encapsulation mixed protective film can be generated on the surface of the vegetable oil to form the polymeric colloid, so that the vegetable oil droplets collide with each other and are not easily broken due to coating of the protective film, thereby increasing the polymerization colloid. The emulsion stability and the coating of the mixed protective film achieve the effect of increasing the moving force of the polymeric colloid between the soil pores, so that the polymeric colloid can be sufficiently uniformly dispersed in the soil and fully utilized by the microorganism.

Further, since the surfactant is a biodegradable surfactant which can be decomposed by microorganisms in the environment, the mixed protective film does not hinder the ability of the microorganism to come into contact with the vegetable oil in the polymeric gel. Furthermore, the remaining surfactant can be smoothly decomposed by the microorganisms, so that the environment is not affected, so that secondary pollution to the environment can be further avoided. Wherein, in the mixed surfactant of the present invention, the preferred volume ratio of the lipophilic surfactant to the hydrophilic surfactant (the lipophilic surfactant volume/hydrophilic surfactant volume) is preferably between 0.4 and 1.7. between. When the volume ratio is less than 0.4, the emulsification effect is not good, and the emulsion stability is affected. When the volume ratio is more than 1.7, the particle size of the polymer colloid is too large, which affects the dispersibility of the polymer colloid, affecting the ability of the polymer colloid to contact with microorganisms, and the colloidal matrix of the present invention cannot be sufficiently utilized by microorganisms.

A preferred lipophilic surfactant for use in the present invention is lecithin having an HLB between 2 and 4. Lecithin is a natural compound surfactant. The main components are phosphatidtlcholine, phosphatidyl ethanolamine (PE), phospholipidyl inostitol (PI), phosphatidic acid (PA). And other unnamed phosphorus-containing compounds. A preferred hydrophilic surfactant for use in the present invention is butyl cellosolve (Simple Green, SG). SG is a nonionic surfactant with an HLB of about 11. Among them, SG can also be called 2-Butoxyethanol, and the chemical formula is HOCH ₂ H ₂ O-(CH ₂ ) ₃ CH ₃ . In the present invention, the lipophilic surfactant is first mixed with the vegetable oil so that the lipophilic surfactant can be completely coated on the surface of the vegetable oil, and then the hydrophilic surfactant is added to the lipophilic surfactant and the vegetable oil mixed solution. The present invention combines the lipophilic group of the hydrophilic surfactant with the chlorine-containing contaminant, and combines the hydrophilic group of the hydrophilic surfactant with one water to increase the chlorine-containing contaminant relative to water. The solubility helps to dissolve the chlorine-containing contaminants, thereby preventing the chlorine-containing contaminants from staying in the environment.

For example, a preferred embodiment of the colloidal matrix of the present invention for remediating chlorine-containing contaminants is to mix 1 ml of vegetable oil with 0.2 to 0.4 ml of surfactant and 0.5 to 2 per 1 ml of vegetable oil. Mix the milliliters of the microbial nutrient mixture. Wherein, if the surfactant mixed with less than 0.2 ml per 1 ml of vegetable oil will make the colloidal matrix have insufficient emulsion stability; when the surfactant is greater than 0.4 ml, the vegetable oil in the colloidal matrix and the surfactant are produced. The liquid discharge phenomenon causes the surfactant to not completely coat the vegetable oil, thereby affecting the mobility of the colloidal matrix. If the microbial nutrient mixture mixed per 1 ml of vegetable oil is less than 0.5 ml, the colloidal matrix of the present invention cannot provide sufficient carbon source for microbial growth, and if it is higher than 2 ml, the polluted environment is acidic, but instead Inhibition of microbial growth, resulting in insufficient microorganisms, can not fully decompose the chlorine-containing pollutants.

In addition, the microbial nutrient mixture of the present invention is a substrate for rapid decomposition of microorganisms, mainly comprising water and microbial nutrients, mainly utilizing the microbial nutrient to provide a carbon source required for the initial stage of microbial growth, promoting microbial growth and growth, and In the contaminated area, sufficient microorganisms can be generated to perform aerobic co-metabolism or anaerobic reduction dechlorination reaction, thereby increasing the degradation efficiency of the chlorine-containing pollutants, thereby improving the remediation efficiency of the chlorine-containing pollutants. Among them, the microbial nutrient of the preferred embodiment of the present invention comprises a group consisting of a combination of vitamins, vitamin B, molasses and sodium lactate. Among them, the comprehensive vitamin contains many trace elements to promote microbial growth. Vitamin B12 in the vitamin B group promotes the growth of microbial flora that is beneficial for reductive dechlorination, such as the growth of dehalorespiring, Anaeromyxobacter, Desulfitobacterium, Trichlorobacter and Dehalobacter. In addition, molasses and sodium lactate are primarily sources of carbon that are required for microbial growth. Preferably, the present invention comprises, as per micromolecular nutrient mixture, 0.005 to 0.03 g of molasses, 0.05 to 0.5 g of sodium lactate, 0.02 to 0.12 g of a combination of vitamins and 0.02 to 0.12 g of a vitamin B group as the microorganism. Nutrients. Molasses can promote the growth of microorganisms, and can effectively induce aerobic co-metabolism of TCE by microorganisms with co-metabolism potential in soil and groundwater. If the molasses is higher than 0.03 g, the microbial metabolism will produce too much organic acid, causing the pH to drop, which in turn will inhibit the growth of the microorganisms. If it is less than 0.005 ml, the colloidal matrix of the present invention cannot quickly obtain a sufficient carbon source, thereby prolonging the curing time. If the combined vitamin or vitamin B group is less than 0.02 grams, it will cause insufficient trace elements and affect microbial growth.

Evaluation of emulsion stability of vegetable oils by surfactants

(1) Effect of single surfactant on emulsification of vegetable oil

To understand the effect of a single surfactant (SG or lecithin) on vegetable oil emulsification, the present invention utilizes 20, 40, 60, 80 and 100 mg/L lecithin and 20, 40, 60, 80, 100 and 120 mg/L, respectively. The SG synthesizes 50 wt% emulsified oil. Please refer to Table 1 below. When the single surfactant is lecithin and the concentration is 20, 40, 60, 80 and 100 mg/L, the proportion of the emulsion layer is about 62%, 94%, 100%, 100%. And 100%. In addition, please refer to Table 1 below. When the single surfactant is SG and the added concentrations are 20, 40, 60, 80, 100 and 120 mg/L, the proportion of the emulsion layer is 55.6% and 57.1%, respectively. 56.4%, 58.2%, 57.9 and 57.9%. From the results, it was found that when a single surfactant was used, a stable emulsified oil could be synthesized only when 60 mg/L or more of lecithin was added. However, increasing the SG concentration could not increase the ratio of the emulsified layer. The main reason is that lecithin is a lipophilic surfactant, and SG is a hydrophilic surfactant.

(2) Effect of emulsification of mixed surfactant (SG and lecithin) on vegetable oil emulsification

In order to understand the effect of mixed surfactant (SG and lecithin) on vegetable oil emulsification, the present invention divides the experiment into two parts. The first part fixes the lecithin concentration, and the lecithin concentration is fixed at 60 mg/L and 80 mg/L, respectively. And mixed with SG of concentration 20, 40, 60, 80, 100, 150mg / L and 200mg / L, the second part is the fixed SG concentration, so that the SG concentration is fixed at 50mg / L and 100mg / L, respectively The concentrations of 20, 40, 60, 80 and 100 mg/L of lecithin were mixed to synthesize 50% by weight of emulsified oil.

Please refer to Table 2 below. Group A has a fixed lecithin concentration of 60 mg/L and SG concentrations of 20, 40, 60, 80, 100, 150 mg/L and 200 mg/L, respectively. 72.7%, 61.8%, 91.2%, 86.2%, 85%, 70.5% and 62.9%. Group B has a fixed lecithin concentration of 80 mg/L, and SG concentrations of 20, 40, 60, 80, 100, 150 mg/L and 200 mg/L, respectively, and the ratio of the obtained emulsion layers is 90.9%, 76.8%, and 57.1%, respectively. 73.7%, 86.7%, 72.9% and 69.8%.

Please refer to Table 3 below. Group C has a fixed SG concentration of 50 mg/L and lecithin concentrations of 20, 40, 60, 80 and 100 mg/L, respectively. The obtained emulsified stratification ratios are 76.4% and 84.2%, respectively. 57%, 57.2% and 79.3%. In group D, the fixed SG concentration was 100 mg/L, and the lecithin concentrations were 20, 40, 60, 80, and 100 mg/L, respectively. The proportions of the obtained emulsion layers were 60.3%, 67.2%, 77.6%, 90.0%, and 83.6%, respectively. . From the above results, the lecithin concentration of 60 mg / L mixed SG concentration of 60 mg / L, lecithin concentration of 80 mg / L mixed SG concentration of 20 mg / L, SG concentration of 50 mg / L mixed lecithin 40 mg / L and SG concentration of 100 mg / L mixed The emulsification effect and stability of lecithin 80mg/L are the best. Therefore, if a vegetable oil stable emulsion is prepared using a mixed surfactant, the higher the concentration of lecithin added, the lower the concentration of SG required to be added. The reason why the excessive concentration of SG does not contribute to the emulsion stability is that the excess SG easily causes the lipophilic group of the surfactant to push to form a space barrier, so that too much SG combines with water and precipitates under the emulsion, causing the row to be discharged. Liquid phenomenon, so the subsequent use of surfactants in lecithin and SG should be carefully considered to achieve a more stable emulsified oil.

The present invention preferably finds the optimal emulsification formula by the central combination method, and the lecithin and SG concentrations are preferably 72 mg/L and 71 mg/L, respectively, and the emulsion stability can be greater than 90%, and the present invention is based on 50 wt% emulsified oil. When the emulsification test is actually carried out in this ratio, the degree of emulsification can reach 100%, indicating that the ratio of the surfactant is the optimum emulsification ratio. The stability of the emulsified oil must be based on the external force and the surfactant. The external force can control the particle size of the small oil droplets in the dispersed phase. The surfactant can form a protective film on the oil droplets and reduce the surface tension of the oil and water. Both the size of the particle size and the physical and chemical properties of the protective film affect the emulsion stability. Generally, the most important factor affecting the emulsified oil droplets is the size of the oil droplets. The larger the particle size, the larger the consolidation rate. When the particle diameter is larger than 7 μm, the moment generated by the collision of the large particle diameters tends to cause the protective film to disintegrate or fall off, so that the surfactant cannot completely cover the vegetable oil.

The preparation method of the colloidal matrix for remediating chlorine-containing pollutants according to the preferred embodiment of the present invention is: firstly mixing 5 mL of vegetable oil with 0.75 g of lecithin, then adding 0.7 mL of SG to mix uniformly, and then adding 5 mL of microbial nutrient mixture. liquid. The microbial nutrient mixture is prepared by dissolving 0.5 g of sodium lactate, 0.05 g of molasses, and 1 part of the integrated vitamin and vitamin B group in 5 mL of water, and then mixing the mixture at 12,000 rpm for 30 min in a homogenizer to prepare the colloidal matrix of the present invention. The colloidal matrix had an oil droplet diameter D ₅₀ of 2.33 μm and a D ₁₀ of 0.99 μm.

Evaluation of the best emulsification synthesis method of the invention

Please refer to Annexes 1 to 8 and Table 4 below for the evaluation of the mixed emulsification conditions of vegetable oil, surfactant and microbial nutrient mixture by means of emulsifier homogenizer and mixer. Among them, the speed of the mixer is medium speed, and the stirring speed of the homogenizer is preferably 12,000 rpm, the stirring time is 10 and 30 minutes respectively, and the surfactant is selected from a single surfactant (80 mg/L lecithin) and Mixed surfactant (72 mg/L lecithin and 71 mg/L SG). After mixed emulsification, the particle size of the oil droplets after emulsification was measured by a laser particle size analyzer and an optical microscope, and the surface potential of the oil droplets was measured by an exponential potential analyzer.

Among them, the attachments 1 to 4 respectively indicate the particle size distribution of the groups H1 to H4. Annexes 5 to 8 indicate the particle size distribution of groups K1 to K4, respectively. In addition, please refer to Table 4 below for the detailed conditions of Annexes I to 8. Wherein, the mixing principle is: dispersing the two liquids which are incompatible with each other by a mechanical force or the like to disperse the dispersed phase in the continuous phase to form an emulsion, and the process is called emulsification, wherein The small droplets of the emulsion are oil dispersed in an aqueous solution, referred to as an oil phase (O/W) emulsion in the water, and vice versa as an aqueous phase (W/O) emulsion in the oil. Reasons for affecting the stability of the emulsion In addition to the surfactant concentration, the stirring mode and rate also affect the oil droplet size and emulsion stability after emulsification. Stirring provides energy and increases the efficiency and emulsification reaction of the two mutually incompatible liquids. When the rotation speed is increased, the energy becomes larger, and the shearing force also increases, and the droplet diameter of the emulsion is cut smaller, so that the overall average particle diameter of the emulsion is lowered to become a more stable state.

Please refer to the second part of the figure. It can be seen from the figure that the H2 group can produce the emulsified oil droplets with the smallest particle size. Among them, the mixing condition of the H2 group was that the vegetable oil was mixed with 72 mg/L of lecithin and 71 mg/L of SG by an emulsification homogenizer for 30 minutes to obtain an average particle diameter of 2.10 μm. Wherein D ₁₀ (10% of the emulsified oil droplet average particle diameter) was 0.93 μm, and D ₉₀ (90% of the emulsified oil droplet average particle diameter) was only 4.56 μm. In addition, regardless of the single lecithin emulsified oil or lecithin and SG mixed emulsified oil, the Zeta potential is negative, and the boundary potential of the lecithin and SG mixed emulsified oil is smaller than the single lecithin emulsified oil. Among them, the lower the boundary potential, the stronger the repulsive force and the better the emulsion stability, so the emulsion stability of the lecithin and SG mixed emulsified oil is better than that of the single lecithin emulsified oil. By increasing the boundary potential of the surfactant to form a protective film on the oil droplets, the mutual repulsive force between the oil droplets can be increased, thereby reducing the chance of emulsification oil coagulation, and increasing the colloid of the present invention for rectifying chlorine-containing pollutants. The uniformity of dispersion of the matrix in the soil enables the colloidal matrix of the present invention to be fully utilized by microorganisms to enhance the efficiency of decomposition and removal of the chlorine-containing contaminants, thereby improving the overall efficiency of remediation. In addition, although the particle size of the oil droplets of the emulsified oil contains large particles (D ₉₀ is 4.56 μm), since the potentials at the boundary between the surface of the oil droplets and the surface of the soil particles are negative, the oil droplets only adsorb to the boundary potential. On some soil particles, the remaining oil droplets continue to cross the soil pores through the water flow, while the pure vegetable oil has no surfactant as a protective film on the surface of the oil droplets, making the oil droplets easily accumulate on the surface of the soil particles, resulting in an increase in organic matter content. Therefore, the uniformity of the adhesion of the emulsified oil is better than that of the pure vegetable oil.

From the above results, the present invention is preferably an emulsifier homogenizer which is emulsified and mixed at a rotation speed of 12,000 rpm, and preferably has a mixing time of 30 minutes. The colloidal matrix for treating chlorine-containing contaminants of the present invention is formed by mixing vegetable oil with a surfactant to form an emulsified form, thereby improving the colloidal matrix of the present invention for remediating chlorine-containing contaminants. The mobility between the regional soil pores makes the colloidal matrix of the present invention for remediating chlorine-containing contaminants easier to transport between the pores of the soil particles.

Please refer to Figure 1 for a comparison of the outflow rates of different substrates in the soil column. It can be seen from the results that the flow rate of pure vegetable oil (labeled as A1 in the figure) is 0.231 mL/sec, which is faster than the emulsified oil of the present invention (labeled as A2 in the figure) and sodium chloride (labeled as A3 in the figure). The reason is that the flow rate of the pure vegetable oil increases due to the short flow condition caused by the blockage between the soil pores. Compared with the pure vegetable oil, the present invention uses the emulsified oil type to uniformly move the colloidal matrix of the chlorine-containing contaminant to move between the soil pores, and the pure vegetable oil is agglomerated in the middle of the soil column to make the oil layer and the soil. The layer pushes each other to cause delamination, indicating that the emulsified oil droplets of the present invention are more likely to move between the soil pores than the unemulsified vegetable oil. The average particle diameter of the oil droplets after emulsification of the present invention is 2.10 μm, and the formation of pure vegetable oil droplets is mainly caused by the surface tension and the extrusion between the pores of the soil particles, and the oil droplets formed by the pure vegetable oil have no surfactant. The coating forms a protective film, so that it is easy to agglomerate and cause clogging. Therefore, in the present invention, the vegetable oil and the surfactant are mixed and emulsified, so that the emulsified oil droplets are easier to move between the soil media than the pure vegetable oil.

In practical applications, the colloidal matrix of the present invention for rectifying chlorine-containing contaminants can be used to bond a water-permeable reaction wall to form a passive bioreactor wall. The water permeable reaction wall is selected from the group consisting of a remediation wall, a ditches, a remediation well and a funnel-type water collection system.

In addition, the colloidal matrix of the present invention can be applied to the remediation of chlorine-containing contaminants, thereby providing a colloidal matrix for continuously releasing carbon sources, hydrogen sources and nutrients for use by microorganisms for improving the conventional rectification of chlorine-containing contaminants. The method requires continuous injection of a substrate into the permeable reaction wall by a mechanical facility to promote microbial growth, resulting in the disadvantage that the processing cost cannot be reduced.

Referring to FIG. 2, the method for rectifying chlorine-containing contaminants comprises: an injecting step S1 and a biodegrading step S2.

The injecting step S1 injects the aforementioned colloidal matrix of the present invention into a contaminated area containing chlorine contaminants having microorganisms. The colloidal matrix of the present invention is preferably combined with a water permeable reaction wall to form a passive bioreactor wall. Wherein, the water permeable reaction wall is disposed in the contaminated area of the chlorine-containing pollutant. The water permeable reaction wall is selected from the group consisting of a remediation wall, a ditches, a remediation well and a funnel-type water collection system. The polymeric colloidal matrix of the present invention can be initially used as a substrate for the growth of ex situ microorganisms by using the microbial nutrient mixture to mass-produce a flora suitable for degrading chlorine-containing contaminants in the water-permeable reaction wall. In the present invention, when the colloidal matrix is injected into the underground aquifer by coating the vegetable oil as a protective film with the surfactant, the colloidal matrix can be uniformly dispersed and adhered to the soil particles in the contaminated site. And the vegetable oil in the inner layer of the colloidal matrix induces more growth of microorganisms which are beneficial to decompose the chlorine-containing pollutants, and the hydrogen is continuously fermented by the microorganism to promote the reductive dechlorination of the chlorine-containing pollutants.

The biodegradation step S2 utilizes microorganisms for biodegradation. The colloidal matrix promotes microbial growth and continuously supplies carbon sources, hydrogen sources and nutrients required by the microorganisms, promotes the continuous fermentation of the microorganisms to produce hydrogen and acetate, and the acetate further generates hydrogen, which is promoted by the continuously generated hydrogen. Reductive dechlorination of chlorine-containing contaminants contributes to the decomposition of the chlorine-containing contaminants. The vegetable oil of the inner layer of the colloidal matrix enables the vegetable oil droplets to continuously release fatty acids and glycerol from the vegetable oil by hydrolysis, thereby stably and continuously providing the carbon source required by the microorganism to achieve long-lasting continuous treatment. The purpose of chlorine pollutants. Therefore, the present invention does not require continuous injection of mechanical equipment, and the cost of the remediation equipment can be reduced.

Furthermore, since trichloroethylene (hereinafter referred to as TCE) is the most common chlorine-containing contaminant in sites contaminated by dense non-aqueous phase liquids (DNAPL), this embodiment Chlorine-containing contaminants were selected for further analysis with trichloroethylene. Wherein, if the groundwater layer contains oxygen, the biodegradation step S2 performs biodegradation, and the microorganism first performs aerobic biodegradation, that is, aerobic co-metabolism. After the oxygen in the groundwater layer is consumed, the anaerobic biodegradation is carried out, that is, the dechlorination reaction is carried out.

Effects of different substrates on microbial aerobic co-metabolism of trichloroethylene (TCE)

In the aerobic biodegradation of trichloroethylene, the decomposition of trichloroethylene produces HCl and oxidase, which consumes hydrogen atoms, and cannot produce reducing energy (NADH), which causes microbes to use trichloroethylene as a growth substrate. Can take the form of co-metabolism. When performing aerobic co-metabolism, microorganisms use oxygen as the electron acceptor. Since trichloroethylene cannot be used as the main substrate, another additional carbon source must be provided to cause the enzyme to decompose trichloroethylene when the microorganism decomposes the carbon source. To achieve the purpose of biological treatment. The following is a comparison of the feasibility and decomposition rate of trichloroethylene aerobic co-metabolism under aerobic conditions for a single substrate, such as a combination of vitamins and a colloidal matrix of the present invention. The present invention co-configures three sets of solutions as microbial decomposition tests [microcosms] to further verify that the colloidal matrix of the present invention for remediating chlorine-containing contaminants does have microorganisms as a carbon source, a hydrogen source, and a nutrient. The effect is to use the clean aquifer soil collected from the contaminated site as a source of microorganisms.

The first group is the local groundwater group (control group); the second group is the integrated vitamin co-metabolism group; the third group is the colloidal matrix group of the present invention. In each group, the existing aquifer soil, the trichloroethylene solution and the buffer solution were placed in a 160 mL culture flask. In the second to third groups, a combination of a multivitamin and a colloidal matrix was added as a matrix. Among them, the headspace of the culture bottle is 10 mL, and the headspace is filled with air as a source of oxygen. The feasibility of microbial aerobic co-metabolism of trichloroethylene was compared by adding different matrices.

Please refer to Figure 3 and Table 5 below. The first group is the groundwater group without substrate. The initial concentration of trichloroethylene is 1.01mg/L. After 17 days of reaction, the residual concentration of trichloroethylene is 0.92mg/L, the degradation efficiency of trichloroethylene is about 0.47%, and the total bacterial count (TBC) is 2.05×10 ⁶ CFU/ The mL increased to 1.82 × 10 ⁸ CFU/mL, and the total number of bacteria did not increase significantly after the first day. The dissolved oxygen (DO) decreased from a starting concentration of 5.2 mg/L to 1.35 mg/L, the oxidation-reduction potential (ORP) decreased from 223 mV to 130 mV, and the pH value was neutral (7.6-6.68). It is speculated that in the absence of matrix, the microbial system uses the local natural organic matter as a carbon source to increase the number of microbial bacteria, but the natural organic matter cannot induce the microbial growth of the co-metabolism effect of the microorganism on trichloroethylene, so the concentration of trichloroethylene decreases only Due to the adsorption of natural organic matter, the chlorine-containing pollutants cannot be decomposed.

Please refer to Figure 4 and Table 5 below. The second group is a comprehensive vitamin co-metabolism group. The initial concentration of trichloroethylene was 0.4 mg/L, and the concentration of trichloroethylene was 0.37 mg/L after the 20th day of the reaction. The total number of bacteria increased from 2.05×10 ⁶ CFU/mL to 8.10×10 ⁷ CFU/mL. The dissolved oxygen decreased from 5.1 mg/L to 3.35 mg/L. The pH is still neutral (6.79-6.5). The initial oxidation-reduction potential decreased from 209 mV to 4 mV, still in the oxidation state. The results show that although synthetic vitamins can promote microbial growth, but can not effectively enhance microbial activity, it can not be used alone as a carbon source for aerobic co-metabolism of trichloroethylene.

Referring to Figure 5 and Table 5 below, the third group is the colloidal matrix set of the present invention. As can be seen from the figure, the colloidal matrix of the present invention rapidly consumes dissolved oxygen in groundwater and creates an anaerobic reducing environment. Therefore, in order to maintain the aerobic reaction of the microorganisms, 40 mL of 100% pure oxygen was separately injected on the first day and the 10th day, respectively. On the 17th day of the reaction, the residual trichloroethylene concentration decreased from the initial concentration of 0.8 mg/L to 0.41 mg/L, the dissolved oxygen decreased from 5.4 mg/L to 0.39 mg/L, and the redox potential decreased from 223 mV to -124 mV. The pH is slightly acidic (6.26). It is known from the results that the colloidal matrix for rectifying chlorine-containing contaminants of the present invention can effectively consume dissolved oxygen in water and stimulate microbial growth.

in conclusion

The present invention compares the aerobic co-metabolism degradation ratio of trichloroethylene of each matrix with a degradation ratio, and the results are shown in Table 5 below. From the results, it can be seen that the first to third groups, the groundwater (without matrix), the integrated vitamin and the aerobic degradation ratio of the colloidal matrix of the present invention for remediating chlorine-containing contaminants are 0.47, 0.5 and 2.29 μg/day/g, respectively. The aerobic degradation ratio is arranged according to the size to obtain the colloidal matrix of the present invention> comprehensive vitamin> groundwater (no matrix). From the results, it was found that the aerobic degradation ratio of the added matrix was higher than that of the unadded matrix. The final dissolved oxygen of the present invention is less than 1, thereby demonstrating that the degradation of trichloroethylene does aerobic co-metabolism for the microbial utilization of the substrate as a carbon source. Furthermore, the redox potential is an important reference for subsequent anaerobic reductive dechlorination. The redox potential of the colloidal matrix of the present invention can be converted from an oxidized state (223 mV) to a reduced state (-124 mV), which is advantageous for subsequent reductive dechlorination.

Effect of microbial reduction of dechlorinated trichloroethylene (TCE) under different groundwater conditions

For different groundwater conditions (single groundwater, nitrate-rich and sulphate-rich), whether it is beneficial to the existing microorganisms to carry out anaerobic reduction and dechlorination of trichlorochloride in the soil and groundwater environment if it contains nitrate or sulfate in the groundwater environment. Ethylene reaction.

The first group is the local groundwater group (without matrix); the second group is the nitrate-rich group of the present invention; the third group is the sulfate-rich group of the present invention; and the fourth group is the colloidal matrix group of the present invention. In each group, the existing aquifer soil, the trichloroethylene solution and the buffer solution were placed in a 160 mL culture flask. Groups 2 to 4 use the colloidal matrix of the present invention as a microbial growth substrate. In addition, 0.5 g/L of sodium nitrate (NaNO ₃ ) was added to the second group to provide nitrate as an electron acceptor; and in the third group, 0.7 g/L of potassium sulfate (K ₂ SO ₄ ) was additionally added to provide sulfuric acid. Salt as an electron acceptor. The headspace of the culture bottle is 10 mL, and the headspace is filled with nitrogen and carbon dioxide.

Please refer to Figure 6 and Table 6 below for the local groundwater group (anaerobic group). The anaerobic degradation ratio was 0.37 μg/day/g. Groundwater without matrix can only use natural organic matter as an electron supplier to increase the number of microbial bacteria. It can be seen from the results that no trichloroethylene by-products are produced, indicating that natural organic matter cannot induce reductive dechlorination of trichloroethylene by anaerobic microorganisms, and the decrease in trichloroethylene concentration is only caused by the adsorption of natural organic matter. Therefore, in a substrate-free environment, microorganisms cannot decompose chlorine-containing contaminants.

Please refer to Figures 7 and 8 and Table 6 below for the nitrate electron supplier group (Group 2) and the sulfate electron supplier group (Group 3). The anaerobic degradation ratios are 0.92 and 1.74, respectively. Gg/day/g. When the concentration of nitrate in the environment is too high, the hydrogen production of the colloidal matrix of the present invention may be delayed, thereby delaying the reductive dechlorination of trichloroethylene. When the reaction environment is in a sulfate-rich state, although the cis-DCE concentration is accumulated in the initial stage, due to the continuous hydrogen production of the colloidal matrix of the present invention, after the sulfate concentration is lowered, the hydrogen production can be continued to stimulate the dechlorination bacteria for reduction. Dechlorination, so the trichloroethylene by-products can continue to degrade in the late stage of the reaction. Therefore, it can be seen from Groups 2 and 3 that the colloidal matrix of the present invention, in the environment rich in sulfate or sulfate, although the degradation time is increased, the chlorine-containing contaminant can still be effectively carried out by continuously producing hydrogen. Degradation.

Referring to Figure 9 and Table 6 below, Group 4 is added to the colloidal matrix of the present invention under normal circumstances. The results show that the colloidal matrix of the present invention can effectively promote the reduction and dechlorination reaction of anaerobic microorganisms, and degrade the trichloroethylene to ethylene (ethene). Acetate increased with increasing number of days of reaction, and the acetate concentration was determined to be 3,489 mg/L after the 52nd day of the reaction. The total number of bacteria increased from 1.48 × 10 ⁵ CFU/mL to 1.96 × 10 ⁸ CFU/mL. According to the total number of bacteria and the tendency of acetate formation, when acetate is formed, hydrogen is also produced in an anaerobic environment to promote the anaerobic reduction and dechlorination of microorganisms. Among them, the formation of acetate represents that the vegetable oil of the inner layer of the colloidal matrix of the present invention is decomposed by microorganisms. However, since the vegetable oil has the property of adsorbing the chlorine-containing contaminant, it is necessary to additionally test whether the inner layer vegetable oil decomposes to cause more release of the chlorine-containing contaminant, resulting in incomplete decomposition. As a result, it is known that there is no accumulation or increase in the concentration of trichloroethylene, because in the environment, a sufficient amount of dechlorination species (such as Dehalococcoides, etc.) has been previously induced by the microbial nutrient mixture and the surfactant of the present invention, thereby avoiding When the vegetable oil is decomposed, it additionally causes accumulation of trichloroethylene and other degradation by-products.

Referring to Table 6 below, Groups 1 to 4 are sequentially the groundwater group (without matrix), the nitrate-rich group, the sulfate-rich group, and the colloidal matrix group of the present invention. The anaerobic degradation ratios of the groups are respectively determined. It is 0.37, 0.92, 1.74 and 2.46 μg/day/g. If the anaerobic degradation ratio is arranged, the colloidal matrix group of the present invention is > sulfate-rich group > nitrate-rich group > groundwater (without matrix). It can be seen from the results that the colloidal matrix group of the present invention can effectively promote the anaerobic biological reduction dechlorination reaction and degrade the trichloroethylene to ethylene. At the beginning, through the consumption of dissolved oxygen, the reaction environment is in a reduced state, and the growth of the anaerobic dechlorination group is promoted. Later in the anaerobic environment, hydrogen and acetate are slowly released, which promotes anaerobic reduction and dechlorination to decompose chlorine-containing pollutants. By using the colloidal matrix of the present invention as a substrate for anaerobic bioremediation, continuous perfusion can be avoided, and the effect of reducing the cost of rectification can be achieved.

The colloidal matrix for remediating chlorine-containing contaminants of the present invention is prepared by mixing the vegetable oil (slow decomposition matrix) with the mixed surfactant (biodegradable surfactant) to coat the surfactant The vegetable oil surface is combined with the vegetable oil to form the polymeric colloid, and then the microbial nutrient mixture (quick decomposition matrix) is added to the polymeric colloid, and homogeneously emulsified to form the colloidal matrix, thereby emulsifying the vegetable oil into a more easily diffused emulsion. The type of hydrogen release matrix is used for long-term supply of carbon source, hydrogen source and nutrient matrix required for microbial co-metabolism aerobic or anaerobic reduction dechlorination, so that the colloidal matrix can be fully and uniformly dispersed in the soil and fully utilized by microorganisms. In order to achieve the effect of improving the efficiency of remediation.

The colloidal matrix for remediating chlorine-containing contaminants of the present invention rapidly stimulates the growth of the existing microorganisms by the microbial nutrient mixture (rapid decomposition matrix), and coats the surface of the vegetable oil via the surfactant to make the surface of the colloidal matrix The potential is negatively charged to facilitate the transfer of movement between the pores of the soil, and because the surfactant is biodegradable, the microorganism can easily further decompose the vegetable oil (slow decomposition matrix) in the inner layer of the colloidal matrix to continuously generate hydrogen, and effectively degrade. The chlorine-containing contaminant, the carbon source, the hydrogen source and the nutrient substrate required for the long-term supply of aerobic or anaerobic reductive dechlorination of the microorganisms, so that the colloidal matrix can be sufficiently uniformly dispersed in the soil and fully occupied by the microorganisms Use, to achieve the effect of improving the efficiency of remediation.

The colloidal matrix for remediating chlorine-containing contaminants of the present invention, by increasing the moving force of the polymeric colloid between the pores of the soil, allows the matrix to be continuously utilized by the microorganisms, so that the colloidal matrix of the present invention does not need to be continued by mechanical facilities. It is continuously injected into the water-permeable reaction wall to achieve the effect of reducing the cost of remediation.

While the invention has been described in connection with the preferred embodiments described above, it is not intended to limit the scope of the invention. The technical scope of the invention is protected, and therefore the scope of the invention is defined by the scope of the appended claims.

Fig. 1 is a graph showing the relationship between the outflow rate of a colloidal matrix according to a preferred embodiment of the present invention.

Figure 2: Flow chart of a method for treating chlorine-containing contaminants by a colloidal matrix of a preferred embodiment of the invention.

Figure 3: Test chart for decomposing chlorine-containing contaminants in the local groundwater group (without matrix).

Figure 4: Test chart for the decomposition of chlorine-containing contaminants by the integrated vitamin co-metabolism of the present invention.

Figure 5: Test chart for the decomposition of chlorine-containing contaminants by the colloidal matrix set of the present invention.

Figure 6: Test chart for decomposing chlorine-containing pollutants by reductive dechlorination in the groundwater group (anaerobic group).

Figure 7: Test chart for the decomposition of chlorine-containing contaminants by the reductive dechlorination reaction of the nitrate electron supplier group of the present invention.

Figure 8: Test chart for the decomposition of chlorine-containing contaminants by the reductive dechlorination reaction of the sulfate electron supplier group of the present invention.

Figure 9: Test chart for the decomposition of chlorine-containing contaminants by the reductive dechlorination reaction of the colloidal matrix of the present invention.

Annex I: Particle size distribution map of Group H1 of the present invention.

Annex 2: Particle size distribution diagram of a preferred embodiment (Group H2) of the present invention.

Annex III: Particle size distribution map of Group H3 of the present invention.

Annex IV: Particle size distribution map of Group H4 of the present invention.

Annex 5: Particle size distribution of Group K1 of the present invention.

Annex VI: Particle size distribution of Group K2 of the present invention.

Annex VII: Particle size distribution of Group K3 of the present invention.

Annex VIII: Particle size distribution of Group K4 of the present invention.

Claims (8)

A colloidal matrix for smelting chlorine-containing contaminants, comprising: a microbial nutrient mixture; and a polymeric colloid dispersed in the microbial nutrient mixture, the polymer gum system comprising a vegetable oil and a surfactant The surfactant is coated with the vegetable oil, wherein the surfactant comprises a lipophilic surfactant and a hydrophilic surfactant, and the volume of the lipophilic surfactant and the hydrophilic surfactant The ratio is between 0.4 and 1.7, and the lipophilic surfactant and the hydrophilic surfactant both coat the vegetable oil. The colloidal matrix for rectifying a chlorine-containing contaminant according to claim 1, wherein the lipophilic surfactant is lecithin. The colloidal matrix for rectifying a chlorine-containing contaminant according to claim 1, wherein the hydrophilic surfactant is butyl cellosolve. The colloidal matrix for remediating chlorine-containing contaminants according to the scope of claim 1, wherein each 1 ml of vegetable oil is mixed with 0.2 ml to 0.4 ml of a surfactant to form the polymeric colloid, and dispersed in 0.5 ml to 2 ml of the microbial nutrient mixture. The colloidal matrix for remediating chlorine-containing contaminants according to the scope of claim 1, wherein the microbial nutrient mixture comprises water and microbial nutrients, and is selected from the group consisting of a combination of vitamins, vitamin B, molasses and sodium lactate. The group acts as a nutrient for the microorganism. a colloidal matrix for remediation of chlorine-containing contaminants according to item 5 of the scope of the patent application, wherein each 1 ml of the microbial nutrient mixture is packaged 0.005 to 0.03 g of molasses, 0.05 to 0.5 g of sodium lactate, 0.02 to 0.12 g of a combination of vitamins and 0.02 to 0.12 g of a vitamin B group are used as the microbial nutrient. A method for remediating a chlorine-containing contaminant, comprising: an injecting step of injecting a colloidal matrix for remediating a chlorine-containing contaminant as described in claim 1 into a contaminated area contaminated with chlorine-containing contaminants, and The microorganism contaminated with the chlorine-containing contaminant has a microorganism; and a biodegrading step, the colloidal matrix provides the carbon source, the hydrogen source and the nutrient required by the microorganism to promote the microbial continuous fermentation of the substrate and generate hydrogen to make chlorine Contaminants are reduced and dechlorinated. The method for rectifying a chlorine-containing contaminant according to the seventh aspect of the patent application, wherein in the injecting step, the colloidal matrix is injected into a water-permeable reaction wall in the contaminated area containing the chlorine contaminant, Together to form a passive bioreactor wall.