TWI478877B - Degradation of chlorinated hydrocarbon compounds and methods for their preparation - Google Patents

Description

Composition for degrading chlorine-containing hydrocarbon and preparation method thereof

The present invention relates to a composition for degrading a chlorine-containing hydrocarbon and a preparation method thereof, and particularly to a composition for degrading a chlorine-containing hydrocarbon containing calcium peroxide nanoparticle coated with vegetable oil and a preparation method thereof .

Bioremediation has the advantages of reducing or eliminating the toxicity of pollutants, better economic benefits and not destroying the original use of contaminated sites. In recent years, it has been widely used to remediate pollution fields contaminated by chlorinated hydrocarbons. At the site, the chlorinated hydrocarbons can be further divided into high chlorine number chlorine-containing hydrocarbons (for example: tetrachloroethylene, trichloroethylene, etc.) and low chlorine number chlorine-containing hydrocarbons (for example: 1, 1-Dichloroethylene, cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, vinyl chloride, etc.).

The principle of bioremediation technology is to use microorganisms to dechlorinate chlorinated hydrocarbons to achieve the purpose of degrading chlorinated hydrocarbons, and can be divided into anaerobic treatment and aerobic treatment. In anaerobic treatment, vegetable oil or emulsion made of vegetable oil can be used as a growth substrate and electron supplier for anaerobic reductive dechlorination reaction of microorganisms, and microorganisms with anaerobic fermentation ability can be used as an electron supplier first. Fermentation to form hydrogen After the gas, hydrogen is supplied to the anaerobic halophilic bacteria by inter-species hydrogen transfer, so that the high chlorine number chlorocarbon is subjected to reductive dechlorination reaction. Degradation of chlorine-containing hydrocarbons. In aerobic treatment, oxygen release compounds (ORC), such as hydrogen peroxide, sodium percarbonate, metal peroxides (magnesium peroxide and calcium peroxide), release oxygen for aerobic microorganisms. Aerobic treatment to oxidize and dechlorinate low chlorine number chlorine-containing hydrocarbons to achieve the purpose of degrading all chlorine-containing hydrocarbons.

In the past, when a pollution site contaminated with chlorinated hydrocarbons was rectified, a two-stage injection method was used. The first stage of the method was to inject the electron supplier into the pollution site to allow high chlorine content. The hydrocarbon undergoes a reductive dechlorination reaction. If the dechlorination is incomplete, a less toxic chlorine-containing hydrocarbon is formed, so that the oxygen release compound is injected into the contaminated site in the second stage. In order to carry out oxidative dechlorination of low chlorine number chlorine-containing hydrocarbons. However, the disadvantage of this method is that the low chlorine number chlorine-containing hydrocarbon is formed in the first stage, but the oxygen release compound injected in the second stage does not necessarily move to the area containing the low chlorine number chlorine-containing hydrocarbon, and It is impossible to completely oxidize and dechlorinate low-chlorinated chlorine-containing hydrocarbons.

From the above, it can be seen that if a material capable of supplying an electron donor and an oxygen-releasing compound simultaneously in the same region can be developed, it is ensured that the oxygen-releasing compound reaches a region containing a low chlorine number chlorine-containing hydrocarbon so that the chlorine content is low. Oxidative dechlorination of hydrocarbons immediately upon formation The reaction is very helpful in remediating contaminated sites that are contaminated with chlorinated hydrocarbons.

Accordingly, a first object of the present invention is to provide a process for preparing a composition for degrading a chlorine-containing hydrocarbon. The method can prepare a material capable of providing an electron donor and an oxygen releasing compound simultaneously in the same region, ensuring that the oxygen releasing compound reaches a region containing a low chlorine number chlorine-containing hydrocarbon to make a low chlorine number chlorine-containing hydrocarbon The oxidative dechlorination reaction can be carried out immediately at the time of formation.

Thus, the method for preparing a composition for degrading a chlorocarbon-containing compound of the present invention comprises the steps of: providing an oil phase solution comprising calcium peroxide nanoparticles, a vegetable oil component and a lipophilic surfactant; providing a water containing And an aqueous phase solution of a hydrophilic surfactant; and emulsification treatment of the oil phase solution and the aqueous phase solution to obtain a composition for degrading a chlorine-containing hydrocarbon, the composition for degrading the chlorine-containing hydrocarbon The material comprises calcium peroxide nano particles, an emulsion and calcium peroxide nanoparticles coated with vegetable oil.

Accordingly, a second object of the present invention is to provide a composition for degrading a chlorine-containing hydrocarbon.

Thus, the composition for degrading a chlorocarbon-containing compound of the present invention is obtained by the above-described preparation method, and the composition for degrading the chlorocarbon-containing compound comprises calcium peroxide nanoparticles, an emulsion, and a vegetable oil-coated product. Calcium oxide nanoparticle.

The composition for degrading a chlorine-containing hydrocarbon prepared by the preparation method of the present invention can provide an electron supplier in the same region at the same time by containing calcium peroxide nano particles, an emulsion and a calcium peroxide nanoparticle coated with vegetable oil. And the material of the oxygen-releasing compound ensures that the oxygen-releasing compound will reach the region containing the low-chlorinated chlorine-containing hydrocarbon, so that the low-chlorinated chlorine-containing hydrocarbon can be immediately oxidatively dechlorinated when it is formed, which is helpful. Degradation of chlorinated hydrocarbons.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph of oxygen release rate, illustrating the oxygen release rates of the compositions of the degraded chlorine-containing hydrocarbons of Examples 2 and 3 at various seawater ionic strengths in a buffer solution of pH = 5.8; The oxygen rate diagram illustrates the oxygen release rate of the composition for degrading the chlorocarbon compound of Examples 2 and 3 at various seawater ionic strengths when the buffer solution is pH=8.0; FIG. 3 is a diagram of the oxygen release rate, illustrating The deoxidation chlorinated hydrocarbon compositions of Examples 2 and 3 have an oxygen release rate at various seawater ionic strengths when the buffer solution is pH=7.0; FIG. 4 is a graph showing the relationship between the K value and the seawater ion intensity, indicating the implementation. The oxygen release rates of the compositions of the chlorinated hydrocarbons of Examples 2 and 3 at various seawater ionic strengths; Figure 5 is a plot of K values versus pH values illustrating the degradation of chlorinated hydrocarbons of Examples 2 and 3. The stability of the composition at various pH values; Figure 6 is a particle size distribution diagram illustrating the degradation of the chlorine-containing carbon of Example 1. The particle size distribution of the oil particles of the composition for a hydrogen compound.

"Preparation method for components for degrading chlorine-containing hydrocarbons"

The preparation method of the composition for degrading a chlorine-containing hydrocarbon of the present invention comprises the steps of: providing an oil phase solution comprising calcium peroxide nano particles, a vegetable oil component and a lipophilic surfactant; providing a water and a water An aqueous phase solution of a hydrophilic surfactant; and an emulsification treatment of the oil phase solution and the aqueous phase solution to obtain a composition for degrading a chlorine-containing hydrocarbon, the composition for degrading the chlorocarbon-containing compound Calcium peroxide nanoparticle, emulsion and calcium peroxide nanoparticle coated with vegetable oil.

Preferably, the volume ratio of the aqueous phase solution to the oil phase solution amount (aqueous phase solution/oil phase solution) ranges from 0.2 to 4. More preferably, the volume ratio of the aqueous phase solution to the oil phase solution (aqueous phase solution/oil phase solution) ranges from 0.5 to 3.

The method for preparing the oil phase solution is not particularly limited, and for example, (Process 1): the calcium peroxide nanoparticle is first mixed with the vegetable oil component to obtain a mixed solution, and the mixture is mixed with the lipophilic interface. The active agent is mixed to obtain the oil phase solution; and (Process 2): the calcium peroxide nanoparticle is first mixed with the lipophilic surfactant to obtain a mixed solution, and then the mixed solution and the vegetable oil component are mixed Mix Combine to obtain the oil phase solution. The mixing process can be carried out by means of stirring of the spoon, stirring of the stirrer, oscillation of the vortex oscillating machine (Vortex), and oscillation of the ultrasonic probe. Preferably, the volume ratio of the vegetable oil component to the lipophilic surfactant is from 1:25 to 125:25.

Preferably, the calcium peroxide nanoparticle is used in an amount ranging from 0.1 to 0.5 g when the total volume of the vegetable oil component and the lipophilic surfactant is in the range of 5 to 150 ml.

Preferably, the volume ratio of the aqueous phase solution to the total amount of the vegetable oil component and the lipophilic surfactant (aqueous phase solution/vegetable oil component + lipophilic surfactant) ranges from 0.5 to 3.

The apparatus used for the preparation and mixing of the aqueous phase solution is not particularly limited, and for example, water and the hydrophilic surfactant may be placed in a stirrer to be stirred and uniformly mixed. Preferably, the total volume of the aqueous phase solution is 100 vol%, the amount of water is in the range of 90 to 99 vol%, and the hydrophilic surfactant is used in an amount ranging from 1 to 10 vol%. More preferably, the total volume of the aqueous phase solution is 100 vol%, the amount of water used is 98 vol%, and the amount of the hydrophilic surfactant is 2 vol%.

The method of the emulsification treatment is not particularly limited, and examples thereof include, but are not limited to, a reverse temperature method, an injection method, a microfluid method, a homogenization stirring method, and a supersonic method (Sonication). Preferably, the emulsification treatment is an ultrasonic method. In a specific example of the present invention, the oil phase solution and the aqueous phase solution are first uniformly mixed, and then an ultrasonic emulsification method is performed using an ultrasonic probe having a power of 100 watts.

The respective components used in the preparation method of the composition for degrading a chlorine-containing hydrocarbon of the present invention are further explained below:

[Calcium peroxide nanoparticle]

The calcium peroxide nanoparticle is not particularly limited, and a general commercial product can be used.

Preferably, the calcium peroxide nanoparticle has a particle size ranging from 5 to 100 nm.

Preferably, the calcium peroxide nanoparticle is modified by polyethylene glycol modified calcium peroxide nanoparticles or modified by polyoxyethylene (20) sorbitan monooleate (Tween 80). A fine calcium peroxide nanoparticle, wherein the polyethylene glycol has a weight average molecular weight ranging from 190 to 210. In a specific embodiment of the present invention, the polyethylene glycol-modified calcium peroxide nanoparticle is prepared according to the Journal of Hazardous Materials, 192 (2011), 1437-1440, and the polyethylene glycol used. It is a polyethylene glycol of the German company Merck which is called PEG200. In another embodiment of the invention, the calcium oxysorbate nanoparticles modified with polyoxyethylene sorbitan monooleate are used.

[Vegetable Oil Components]

Preferably, the vegetable oil component has a melting point in the range of 50 to 40 ° C. The use of the vegetable oil component of the melting point range avoids premature contact of the calcium peroxide with groundwater and early initiation of oxygen release inhibits anaerobic of the chlorocarbon-containing compound. Reduce dechlorination.

Preferably, the vegetable oil component comprises coconut oil, palm Oil, soybean oil, sunflower oil, rapeseed oil, peanut oil, cottonseed oil, palm kernel oil, corn oil, olive oil. In one embodiment of the invention, the vegetable oil comprises coconut oil and palm oil, and the volume ratio of coconut oil to palm oil is 1:1.

[Lipophilic surfactant]

Preferably, the lipophilic surfactant is a lipophilic nonionic surfactant.

Preferably, the lipophilic surfactant is selected from the group consisting of sorbitan monolaurate (Span 20), sorbitan monooleate (Span 80) or a combination thereof.

[hydrophilic surfactant]

Preferably, the hydrophilic surfactant is a hydrophilic nonionic surfactant.

Preferably, the hydrophilic surfactant is selected from the group consisting of polyoxyethylene (20) sorbitan monolaurate (Tween 20), polyoxyethylene sorbitan monopalmitate [Polyoxyethylene (20). )sorbitan monopalmitate, Tween 40], polyoxyethylene (20) sorbitan monostearate, Tween 60], polyoxyethylene sorbitan monooleate [Polyoxyethylene (20) sorbitan monooleate, Tween 80] or a combination of these.

"Degradation of Chlorocarbon Hydrocarbon Compositions"

The composition for degrading a chlorine-containing hydrocarbon of the present invention is obtained by the above-described method for preparing a composition for degrading a chlorine-containing hydrocarbon, and the composition for degrading a chlorine-containing hydrocarbon comprises calcium peroxide nanoparticles, an emulsion And calcium peroxide nanoparticles coated with vegetable oil.

Preferably, the composition for degrading the chlorocarbon-containing compound has an average particle diameter ranging from 10 to 5000 nm.

The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.

<Example> [Preparation Example 1] Preparation of calcium peroxide nanoparticle

3 g (0.027 mol) calcium chloride (CaCl ₂ , manufacturer: JTBaker, USA), 30 ml deionized water, 15 ml aqueous ammonia solution (concentration 1 M, 0.0428 mol), and 120 ml (0.675 mol) polyethylene Alcohol 200 (polyethylene glycol 200, PEG 200 for short, Vendor: Merck) was uniformly mixed, and then 15 ml (0.1323 mol) of an aqueous hydrogen peroxide solution (manufacturer: Sigma-aldrich, concentration: 30 wt%) was added to form a mixed solution, and the mixture was mixed. The solution was placed in a supersonic cleaning shaker (manufacturer: Delta New Instrument Co., Ltd., model: DC600H) controlled at 40 ° C for 2 hours, and the color of the mixed solution gradually changed from colorless to yellow. The mixed solution has a pH of about 9, and then a sodium hydroxide solution (concentration 1 N) is added to the mixed solution to raise the pH of the mixed solution to 11.5 to produce a calcium hydroxide precipitate, and then sodium hydroxide. After the calcium hydroxide precipitate was washed three times with a solution (concentration: 1 N), the calcium hydroxide precipitate was washed three times with deionized water to obtain a calcium peroxide nanoparticle of Preparation Example 1 (particle diameter: 11.88 ± 1.737 nm). The reaction equation is as follows: CaCl ₂ + H ₂ O ₂ → CaO _{2 (hydrate)} + ₂ HCl

2 HCl+2NH ₃ → 2NH ₄ Cl

NH ₄ Cl+NaOH → NH ₃ (g) + NaCl + H ₂ O

[Preparation Example 2] Preparation of calcium peroxide nanoparticle

Dissolve 3 g (0.027 mol) of calcium chloride in 30 ml of deionized water, followed by 15 ml of aqueous ammonia (concentration 1 M, 0.0428 mol) and 2 ml of polyoxyethylene sorbitan monooleate (Tween 80) After mixing, a mixed solution is uniformly formed, and then 45 ml of an aqueous hydrogen peroxide solution (concentration: 30 wt%) is taken, and it is slowly dropped into the mixed solution at a rate of 1 drop per second, and then stirred at room temperature. The reaction was carried out for 2 hours to give a slightly yellow solution. Then, a sodium hydroxide solution (concentration: 1 N) was added to the slightly yellow solution to adjust the pH of the slightly yellow solution to 11.5 to obtain a white suspension. After filtering the white suspension to obtain a white precipitate, the white precipitate was obtained. The solution was washed 3 times with sodium hydroxide solution, and then added with 100 ml of phosphate buffered saline (concentration 0.01 M, pH=5.8), and vacuum-dried at 80 ° C for 2 hours to obtain preparation example 2 peroxidation. Calcium nanoparticles.

[Example 1] Preparation of a composition for degrading a chlorine-containing hydrocarbon

0.1 g of the calcium peroxide nanoparticle of Preparation Example 1 was placed in an anaerobic tank 1 ml vegetable oil component (composed of coconut oil and palm oil in a volume ratio of 1:1; coconut oil and palm oil supplier: German and Italian chemical, food grade) in vortex oscillating machine (VORTEX-GENIE2, USA, model number G650) is uniformly mixed to form a mixed solution. Then, 1 ml of this mixture and 5 ml of Span 80 (supplier: Sigma-aldrich) were added to a 50 ml centrifuge bottle to form an oil phase solution. 0.2 ml of Tween 20 (supplier: Sigma-aldrich) was mixed with 9.8 ml of deionized water to form an aqueous phase solution containing 2 vol% Tween 20, and 10 ml of the aqueous phase solution was added to the centrifuge bottle to The vortex oscillating machine (manufacturer: Scientific Industries, model: Vortex-Genue 2 G650) was uniformly mixed, and the degradation was prepared using an ultrasonic probe (manufacturer: Virtis company, model: Virsonic 100, power: 100 watts, time: 20 seconds). A composition for a chlorine-containing hydrocarbon comprising calcium peroxide nanoparticle, an emulsion, and calcium peroxide nanoparticles coated with vegetable oil.

[Examples 2 to 3]

Examples 2 to 3 were prepared in the same manner as in Example 1, except that Examples 2 to 3 used commercially available calcium peroxide (99%, particle size less than 75 μm), and the vegetable oil components used contained different ratios. Coconut oil and palm oil.

[Examples 4 to 19]

Except for changing the type and amount of the components according to Table 1, Examples 4 to 19 were carried out using the calcium peroxide nanoparticles of Preparation Example 2, different preparation methods and mixing methods, wherein Examples 4 to 6 were Preparations 2 of calcium peroxide. Nai The rice granules and the vegetable oil component are first stirred uniformly with a spatula to obtain a mixed solution, followed by the lipophilic surfactant Span 80 to obtain an oil phase solution; and then the oil phase solution and the water containing 2 vol% Tween 20 For the phase solution, a composition for degrading a chlorine-containing hydrocarbon was prepared using an ultrasonic probe (manufacturer: Virtis company, model: Virsonic 100, power: maximum power, time: 20-30 seconds). In Examples 7 to 9, the calcium peroxide nanoparticle of Preparation Example 2 and the vegetable oil component were first shaken by an ultrasonic probe (power: 3 watts, time: 20-30 seconds) to obtain a mixed solution, and then added to the parent. The oily surfactant Span 80 is oscillated with an ultrasonic probe (power of 3 watts, time: 20-30 seconds) to obtain an oil phase solution; then the oil phase solution is contained with 2 vol% Tween 20 The aqueous phase solution was prepared by using an ultrasonic probe (power: maximum power, time: 20-30 seconds) to decompose a composition containing a chlorine-containing hydrocarbon. In Examples 10 to 13, the calcium peroxide nanoparticles of Preparation Example 2 and the lipophilic surfactant Span 80 were first vortexed with an ultrasonic probe (power: 3 watts, time: 20-30 seconds) to obtain a mixed solution. Then add the vegetable oil component and oscillate with an ultrasonic probe (power is 3 watts, time: 20-30 seconds) to obtain an oil phase solution; then the oil phase solution and the water phase containing 2 vol% Tween 20 For the solution, a composition for degrading a chlorine-containing hydrocarbon was prepared using an ultrasonic probe (power: maximum power, time: 20-30 seconds). In Examples 14 to 19, the calcium peroxide nanoparticles of Preparation Example 2 and the lipophilic surfactant Span 80 were first vortexed by a vortex oscillating machine to obtain a mixed liquid, and then the vegetable oil component was added and vortexed to obtain a mixture. An oil phase solution; then oil A phase solution and an aqueous phase solution containing 2 vol% of Tween 20 were used to prepare a composition for degrading a chlorine-containing hydrocarbon using an ultrasonic probe (power: maximum power, time: 20-30 seconds).

The kinds and amounts of the components used in the compositions for degrading chlorine-containing hydrocarbons of Preparation Examples 1 to 19 are shown in Table 1.

[Oxygen release rate test]

A sodium phosphate buffer solution of pH = 5.8, 7.0 and 8.0 was prepared. The preparation method is to prepare a stock solution of Na ₂ HPO ₄ (concentration 1.0 M) and a stock solution of NaH ₂ PO ₄ (concentration 1.0 M), and then take the reserve of Na ₂ HPO ₄ according to the amount shown in Table 2. The solution and the stock solution of NaH ₂ PO ₄ , and the two were mixed, and then 900 ml of deionized water was added to obtain a sodium phosphate buffer solution of pH=5.8, 7.0 and 8.0.

Then, in the sodium phosphate buffer solution of pH=5.8, 7.0 and 8.0, three seawater ionic strengths (or seawater salinity) were added according to the seawater ion master table, and the chloride ion was 19.36 g/L, the sodium ion was 10.78 g/L, and the magnesium ion was obtained. 1.283 g/L, sulfate ion 1.807 g/L, calcium ion 0.413 g/L, potassium ion 0.399 g/L as 100% seawater ionic strength; 10% seawater ionic strength diluted 10 times for each ion concentration; % of the seawater ionic strength was added without any ions, and nine buffer solutions were prepared. The environment simulated by pH and seawater ion intensity is shown as follows: the intersection of river and seawater (100% seawater ionic strength), the tidal reaches (10% seawater ionic strength), and no contact with seawater. River (sea water Ionic strength 0%), high-chlorinated hydrocarbons that have not been decomposed by microorganisms (pH ≒ 8.0), groundwater contaminated with chlorinated hydrocarbons (pH ≒ 7.0), and high chlorinated hydrocarbons have been microbial Decomposes to low chlorine hydrocarbons (pH ≒ 5.8).

Hereinafter, the composition for degrading the chlorine-containing hydrocarbon of Example 2 will be described in order to facilitate the description of the measurement method, and Example 3 is measured in the same manner.

First, 200 ml of each of the above 9 kinds of buffer solutions were placed in nine 500 ml anaerobic bottles, and then 5 ml of the composition for degrading the chlorocarbon-containing compound of Example 2 was added to the anaerobic bottles. After mixing, 9 liquids to be tested were obtained. Then, using the syringe to take 5 ml of the test solution to the dissolved oxygen at 0 minutes, 30 minutes, 60 minutes, 2 hours, 4 hours, 4 hours, 4 hours, 8 hours, 24 hours, 3 days, 7 days and 28 days. meter The oxygen release rate was measured in a test tube (manufacturer: Taiwan Lutron, model: DO-5510). The results of the oxygen release rate of the compositions of Examples 2 and 3 are shown in Figures 1 to 3.

[column experiment]

A column column experiment was carried out using the composition for degrading a chlorine-containing hydrocarbon of Example 1.

In order to understand the effect of degrading the composition of chlorine-containing hydrocarbons to remove trichloroethylene from the groundwater layer, four types of groundwater layers (high concentrations of trichloroethylene, high concentrations of trichloroethylene and humic acid, The low concentration of trichloroethylene, containing a low concentration of trichloroethylene and humic acid, was passed through the column of Example 1 to degrade the chlorinated hydrocarbon composition. The following is a further explanation of the column experiment steps:

(1) Column packing: firstly, the glass sands of five particle sizes (75 μm, 130 μm, 200 μm, 300 μm, 600 μm) are first subjected to a pickling step with a concentration of 20% nitric acid, followed by deionization. Wash with water for later use when filling the column.

The bottom end of a glass column (1.7 cm inner diameter, 12 cm long) was plugged with a No. 5 silicone plug with a 7 mm hole, and five stainless steel spacers with small pores were placed in the column to avoid Subsequent filled glass sand flows out. Next, a Teflon line is inserted into the hole of the glue plug, and the Teflon line is connected by a copper valve. The cleaned glass sand is then filled to the column according to the general soil distribution ratio. Inside, the length of the glass sand in the post-filled column was 9.5 cm, and the uniformity coefficient D60/D10 was 1.74 (D60 represents a cumulative weight percentage of 60% of the particle size; D10 represents a cumulative weight percentage of 10% of the particle size). Next, five stainless steel shims with fine pores were placed first, and then the top of the column was stoppered with a No. 5 silicone plug having a hole of 7 mm, and then the Teflon line and the copper valve were also connected. In order to avoid the presence of air bubbles in the column during the filling process, the above assembly and filling operations are carried out in water, and the filled column is visually inspected. If there are no bubbles in the column, the subsequent column experiment can be performed. The filled column is labeled as the column (I). The columns (II) to (IV) are then filled in the same manner.

Then measure the hydraulic conductivity (K value of the column (I) to (IV) by the Falling head measurement (K value, which represents the difficulty of groundwater flowing in the aquifer. The larger the value, the easier the water flow) To confirm that the filled column has similar sand layer characteristics. The formula for calculating the K value is as follows:

Where a = the area of the water pipe at the water head; A = the area of the column filled with sand; L = the length of the sand column; H ₀ = the height of the head before the experiment; H ₁ = experiment The head after the water is high; t = H ₀ to H ₁ elapsed time. The hydraulic conductivity coefficients of the columns (I) to (IV) are shown in Table 4. It can be seen from the results of Table 4 that the sand layers of the columns (I) to (IV) have similar properties and can be used to prepare the column for simulating the groundwater layer.

(2) Preparation of the column for simulating the groundwater layer:

(I) Column with high concentration of trichloroethylene and humic acid [column (I)]: Take the above column (I), and inject humic acid and trichloroethylene into the column, respectively. The detailed process is as follows: i) Injecting humic acid---washing the column with deionized water for at least 24 hours. After the completion of the rinsing, dissolve 210 mg of humic acid in 0.42 ml of deionized water and then inject into the column. After at least 24 hours, the flow sample was collected at a sampling point of 1 PV [10 ml, PV is the Pore volume], and analyzed by a liquid total carbon analyzer (manufacturer: OI-Analytical model: 1020A). The amount of humic acid per PV outflow sample [analytical method refers to the total organic carbon detection in the water announced by the Taiwan Environmental Protection Institute - combustion / infrared measurement method (NIEA W530.51C)] until the humic acid output flow approaches zero, after After 52 PV (520 ml), the total amount of humic acid was subtracted from the initial amount of humic acid, that is, the residual amount of humic acid in the column was 0.244 mg (0.116%); (ii) the injection of trichloroethylene --- Then inject 0.25 mg (25 ppm) of trichloroethylene into the column, and after a closed reflow for at least 24 hours, use a closed Empty Vial headspace extraction automatic sampling instrument (Manufacturer: TurboMatrix 40: Perkin Elmer, model), each sample point 1 PV (10 ml), the headspace vial was placed in an environment of 85 ° C for 30 minutes to volatilize trichloroethylene to the top of the headspace vial, and then the trichloroethylene was introduced into a gas chromatograph [GC- ECD, PerkinElmer Clarus 580, the column used is Agilent J&W HP-5 (30 m × 0.32 mm, film 0.25 μm), the analytical method is based on the NIEA M700.01C method announced by the Taiwan Environmental Protection Institute, until the output of trichloroethylene The flow rate is close to zero. After 35 PV, the total amount of trichloroethylene is subtracted from the initial amount of trichloroethylene, and the residual amount of trichloroethylene in the column is 0.1851 mg.

(II) Column with high concentration of trichloroethylene [column (II)]: except for the uninjected humic acid and the analysis of trichloroethylene through 70 PV, the other processes with the above-mentioned high concentration of trichloroethylene and containing humic acid The process of the column was the same, and finally the residual amount of trichloroethylene in the column was 0.218 mg.

(III) Columns containing low concentrations of trichloroethylene and humic acid [column (III)]: In addition to the analysis of humic acid, a total of 60 PV, trichloroethylene analysis, a total of 35 PV, and the injection of trichloroethylene The amount of 0.025 mg (2.5 ppm) was the same as that of the high-concentration trichloroethylene and humic acid-containing column. The residual amount of humic acid in the column was 0.289 mg (0.138%). The residual amount of ethylene was 0.0153 mg.

(IV) Columns containing low concentrations of trichloroethylene [column (IV)]: Except that humic acid was not injected, the amount of trichloroethylene injected was 0.025 mg (2.5 ppm), and the analysis of trichloroethylene passed through 23 PV, the other procedures were the same as those of the above-mentioned high-concentration trichloroethylene and containing humic acid. The process was the same, and finally the residual amount of trichloroethylene in the column was 0.0234 mg.

(3) Trichloroethylene removal rate test: In order to facilitate the description of the test process, the following is a description of the column (I).

4 ml of the degraded chlorocarbon-containing composition of Example 1 was injected into the above-mentioned column (I), and a flow sample was collected by using a headspace vial at a sampling point of 1 PV (10 ml). The PV outflow sample is the amount of trichloroethylene contained in the analysis by the automatic headspace extractor and GC-ECD, and the degradation of the sample contained in Example 1 is analyzed by a solid organic carbon analyzer (manufacturer: OI-Analytical, model: 1020A). The amount of the composition of the chlorocarbon hydrocarbon, after 25 PV, the amount of removal of trichloroethylene and the flow rate of the composition can be obtained, and the removal rate of trichloroethylene and the composition per unit volume of the column (I) can be further calculated. The amount of trichloroethylene adsorbed. The columns (II) to (IV) are tested in a similar manner to the column (I), except that the columns (III) and (IV) are obtained after 23 PV respectively to obtain the amount of trichloroethylene removed and the composition flow. The experimental results are shown in Table 5.

[particle size measurement]

In the particle size measuring instrument (Manufacturer: Malvern Instruments, Worcestershire, Model: Zetasizer ^® Nano ZS) of 4-19 for the degradation of chlorinated hydrocarbon oil with a particle size analysis of Example 1 and composition Example, water and fat The refractive indices were set to 1.330 and 1.460, respectively, and the results are shown in Table 6. The particle size distribution chart of the composition for degrading the chlorine-containing hydrocarbon of Example 1 is shown in Fig. 6.

a: Trichloroethylene removal rate = (trichloroethylene removal amount) ÷ (trichloroethylene residual amount)

[Oxygen release rate test results]

In Figures 1 to 3, it can be found that the compositions of Examples 2 and 3 have started to release oxygen in the first three hours regardless of the environment, because the calcium peroxide nanoparticles and the buffer solution in the composition Direct contact and release of oxygen. In Figure 1 (pH = 5.8), the compositions of Examples 2 and 3 reduced oxygen release after about 4 hours at different seawater ionic strengths, and the oxygen release amount began to increase again after about 312 hours, indicating composition. The calcium peroxide nanoparticles coated with vegetable oil begin to release oxygen. The results of Figures 2 and 3 are substantially the same as Figure 1.

In order to better understand the relationship between the compositions of Examples 2 and 3 and the pH and seawater ionic strength, the number of experiments by the rate of oxygen release rate test According to the analysis, a first-order reaction equation is obtained, and then the K value under various conditions is obtained by the equation. The larger the K value, the faster the oxygen release rate (that is, the vegetable oil coating) The vegetable oil of the calcium oxide nanoparticle is destroyed, so that the calcium peroxide is contacted with the buffer solution to start oxygen release, and the smaller the K value, the slower the oxygen release rate (that is, the vegetable oil can stably coat the calcium peroxide nanoparticle, Calcium peroxide is slowly released to oxygen). The obtained K values were plotted against pH and seawater ion intensity, respectively, and the results are shown in Figures 4 and 5, respectively.

In Fig. 4 (the relationship between the K value and the seawater ion intensity), it is apparent that the K value of the composition of Example 3 (only coconut oil) is greatly increased as the seawater ion intensity increases, indicating that the seawater ion intensity is higher. Strong, the more destructive to vegetable oil. In contrast, the composition of Example 2 (using a mixture of palm oil and coconut oil) has no difference in K value regardless of the seawater ionic strength, indicating that the vegetable oil in the composition of Example 2 can stably exist in any seawater ion. In the strong environment, the main reason for this phenomenon is that palm oil contains 39% oleic acid and 10.5% linoleic acid, while coconut oil contains 6.0% oleic acid and 2.5% linseed oil. Acid, oleic acid contains a double bond and carboxylic acid, linoleic acid contains two double bonds, so palm oil is more resistant to ion damage, so the vegetable oil mixed with palm oil and coconut oil is more stable than pure coconut oil alone. The coated calcium peroxide nanoparticle, that is, the composition of Example 2, can be applied to various seawater ion intensity environments.

In Figure 5 (K value versus pH value), Example 3 The composition does not exist stably in a lower pH environment, but can be stably present in medium and high pH environments. The composition of Example 2 can be stably present in a low pH environment, and the overall trend shows that the higher the pH, the better the vegetable oil stability.

[column experiment results]

The composition for degrading the chlorocarbon-containing compound of Example 1 can remove trichloroethylene by more than 82% in the column of the low-concentration trichloroethylene, whether or not it contains humic acid, and the trichlorochloride per unit volume of the composition The amount of ethylene adsorbed can reach above 0.00357 mg/ml; in the column of high concentration of trichloroethylene, whether or not it contains humic acid, the efficiency of removing trichloroethylene can reach more than 14%, and the composition per unit volume of trichloroethylene The adsorption amount can reach above 0.00802 mg/ml, so it can be proved that the composition for degrading the chlorocarbon compound of Example 1 can effectively adsorb chlorine-containing hydrocarbons regardless of the groundwater layer, thereby contributing to the improvement of biological treatment efficiency. And achieve good removal efficiency.

[particle size measurement result]

It can be found in Fig. 6 that the particle diameters of the oil particles of the three main peaks of the composition for degrading the chlorocarbon-containing compound of Example 1 are 4391 nm, 1821 nm and 447.8 nm, and the distribution percentages thereof are 23.3% and 41.6%, respectively. 35.1%, the average particle size is 936.9 nm. It is also known from Table 6 that the compositions for degrading chlorine-containing hydrocarbons of Examples 4 to 19 can be efficiently transported in the soil groundwater layer because the particle size is smaller than the soil voids.

In summary, the degradation produced by the preparation method of the present invention The chlorinated hydrocarbon composition can provide electron donors and oxygen releasing compounds simultaneously in the same site in the contaminated site, and the average particle size is smaller than the soil voids and can be effectively transported in the soil groundwater layer, and can be different The continuous release of oxygen in the groundwater environment of the soil can effectively adsorb chlorine-containing hydrocarbons, which is beneficial to improve biological treatment efficiency and achieve good removal efficiency.

The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the patent application scope and patent specification content of the present invention, All remain within the scope of the invention patent.

Claims (10)

A method for preparing a composition for degrading a chlorinated hydrocarbon, comprising the steps of: providing an oil phase solution comprising calcium peroxide nanoparticles, a vegetable oil component and a lipophilic surfactant; providing a water and a An aqueous phase solution of a hydrophilic surfactant; and an emulsification treatment of the oil phase solution and the aqueous phase solution to obtain a composition for degrading a chlorine-containing hydrocarbon, the composition for degrading the chlorocarbon-containing compound Calcium peroxide nanoparticle, emulsion and calcium peroxide nanoparticle coated with vegetable oil. The production method according to claim 1, wherein the calcium peroxide nanoparticle has a particle diameter ranging from 5 to 100 nm. The preparation method according to claim 1, wherein the vegetable oil component has a melting point ranging from 50 to 40 °C. The preparation method according to claim 3, wherein the vegetable oil component comprises coconut oil, palm oil, soybean oil, sunflower oil, rapeseed oil, peanut oil, cottonseed oil, palm kernel oil, corn oil, olive oil . The preparation method according to claim 4, wherein the vegetable oil component comprises coconut oil and palm oil, and the volume ratio of the amount of coconut oil to the amount of palm oil is 1:1. The preparation method according to claim 1, wherein the lipophilic surfactant is a lipophilic nonionic surfactant. The preparation method according to claim 1, wherein the hydrophilic interface activity The agent is a hydrophilic nonionic surfactant. The preparation method according to claim 1, wherein the lipophilic surfactant is selected from the group consisting of sorbitan monolaurate, sorbitan monooleate or a combination thereof, and the hydrophilic interface activity. The agent is selected from the group consisting of polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate or One of these combinations. A composition for degrading a chlorocarbon-containing compound, which is produced by the production method according to any one of claims 1 to 8, wherein the composition for degrading the chlorocarbon-containing compound comprises calcium peroxide nanoparticles, Emulsion and calcium peroxide nanoparticles coated with vegetable oil. The composition for degrading a chlorocarbon-containing compound according to claim 9, wherein the oil particles have an average particle diameter ranging from 348.15 to 936.9 nm.