CN113275037A - Method for treating organic solvent by heterogeneous Fenton-like method - Google Patents
Method for treating organic solvent by heterogeneous Fenton-like method Download PDFInfo
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- CN113275037A CN113275037A CN202110597786.XA CN202110597786A CN113275037A CN 113275037 A CN113275037 A CN 113275037A CN 202110597786 A CN202110597786 A CN 202110597786A CN 113275037 A CN113275037 A CN 113275037A
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- organic solvent
- amino acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a method for treating an organic solvent by a heterogeneous Fenton-like method, belonging to the technical field of environment and nuclear energy intersection. Mixing an amino acid modified nano zero-valent iron material with an organic solvent, then dropwise adding hydrogen peroxide and an acidifier, and carrying out catalytic activity and interfacial reaction performance of the amino acid modified nano zero-valent iron and H2O2The reaction generates hydroxyl radicals, thereby oxidatively degrading the organic solvent. Because the amino acid modified nano zero-valent iron not only has the high-efficiency catalytic activity of the zero-valent iron, but also has better dispersibility and interface interaction brought by the surface modification of the amino acid, the amino acid modified nano zero-valent iron is beneficial to the direct attack of OH generated by the catalysis of hydrogen peroxide on organic solvent molecules and promotes the organic reactionOxidative degradation of the substance. The invention has the advantages of high volume reduction rate of radioactive waste organic solvent, good oxidation efficiency of organic matters, low COD value of reaction residual liquid and no generation of iron-containing sludge after reaction.
Description
Technical Field
The invention belongs to the technical field of environment and nuclear energy intersection, and particularly relates to a method for treating an organic solvent by a heterogeneous Fenton-like method, in particular to a method for treating a radioactive waste organic solvent in the field of nuclear industry by a Fenton-like method.
Background
Nuclear energy is used as a new energy source with abundant resources, cleanness and environmental protection, becomes an effective method for solving the energy crisis, and in the production and scientific research process of the nuclear industry, solid, liquid and gaseous wastes with different degrees of radioactivity can be generated, and the post-treatment of spent fuel is always a problem needing careful treatment. Through research and development for many years, the post-processing technology of spent fuel is gradually mature, and the PUREX process is generally adopted by countries in the world, wherein uranium, plutonium, other actinides and most products are dissolved in nitric acid solution, and then a mixed solvent of TBP and diluent n-dodecane is used as an extractant to separate and purify uranium and plutonium. In the post-treatment of spent fuels, it is necessary to recover and dispose of the used nitric acid, extractant, and solvent. Furthermore, during extraction of actinides and fibre products, TBP can be irradiated to form radiolytic products, namely dibutyl phosphate (DBP), monobutyl phosphate, organic acids and butanol, and secondary liquid waste can contain residual TBP and DBP, which can lead to emulsification and act as actinide complexing agents. Therefore, the solvent quality is gradually degraded and replaced after a certain period of use, and the used solvent becomes radioactive organic waste containing radioactive substances such as uranium, plutonium, iodine, and the like, and if the solvent is not properly disposed and disposed, the solvent is harmful to the environment and human body.
The radioactive waste organic solvent treatment process can be roughly divided into methods such as incineration, pyrolysis, absorption, solidification, wet oxidation and the like. The incineration method for treating the radioactive waste organic solvent has the advantages of good volume reduction effect, high decontamination coefficient, waste oil inorganization and the like, but the process flow is complex, the smoke generated by incineration is difficult to treat, and the requirements on the performance and material of equipment, the air tightness of a device, radiation protection safety and the like are high. Because the incineration and cracking process belongs to a high-temperature treatment method, the method has the problems of high required reaction temperature, non-normal operating conditions, tail gas purification treatment, high requirements on equipment material and corrosion resistance and the like, and has the characteristic of good volume reduction effect, but some practical problems cannot be ignored. The absorption treatment method is that the radioactive waste organic solvent is absorbed and fixed in the inside of the absorbent molecules by using the high molecular absorbent to form a stable absorption solidified body so as to be convenient for transportation and further treatment, and has the defect of causing certain capacity increase. The cement solidification method, which is a common method for radioactive waste treatment, has the advantages of waste harmlessness and stabilization, and can use the original cement solidification line of nuclear facilities, but has the problems of small packing capacity, large capacity-increasing ratio, leaching of organic waste liquid and the like. In contrast, the wet catalytic oxidation process is operated under the conditions of low temperature and normal pressure, so that not only is energy consumption saved, but also the operating cost is low, meanwhile, almost all radioactive nuclides are left in the reaction residual liquid, the radioactive nuclides cannot be carried in the gas phase, the radioactive nuclides can be directly discharged, the secondary pollution problems such as waste gas treatment and the like do not exist, the technology is reliable, and therefore, the wide attention and research are obtained.
Advanced oxidation technologies (AOPs) can generate hydroxyl radicals (& OH) with strong oxidation activity, and can nonselectively remove and degrade organic pollutants which cannot be removed by conventional water treatment methods, wherein the fenton oxidation method has the advantages of low temperature, easy operation, high efficiency and the like, so that the fenton oxidation method is widely concerned and researched by scholars in various fields and is gradually applied to engineering practice. The traditional homogeneous Fenton reaction is Fe2+And H2O2Has some advantages but H2O2Low utilization rate, narrow pH range required by reaction, generation of a large amount of iron-containing sludge after reaction and the like. To solve these problems, the development of heterogeneous fenton-like systems and their catalysts is becoming a research focus. The nano material has the advantages of large specific surface area, high adsorbability, high reactivity and the like, is widely researched and developed in recent years, and has attracted attention and made certain progress in the aspects of environmental protection, waste treatment and the like. The main objectives of fenton-like system modifications are focused on improving the reaction kinetics, increasing the catalyst reactivity and reducing the residual organics. The modified nano metal material is used as a heterogeneous Fenton-like reaction catalyst to perform a Fenton-like reaction with hydrogen peroxide, and the optimal reaction conditions are determined by experimental exploration of various influencing factors, so that the radioactive waste organic solvent is efficiently treated.
Disclosure of Invention
The invention provides a method for treating radioactive waste organic solvent by a heterogeneous Fenton-like method by using amino acid modified nano zero-valent iron as a catalyst, aiming at the problems of slow reaction kinetics, low catalyst reaction activity, more residual organic matters and the like in the technical field of treatment of radioactive waste organic solvent. The method has the advantages of simple process, mild reaction conditions, low requirements on instruments and equipment and high degradation and removal efficiency on organic matters.
According to the purpose of the invention, the method for treating the organic solvent by the heterogeneous Fenton-like method is provided, the amino acid modified nano zero-valent iron material is mixed with the organic solvent, then the aqueous hydrogen peroxide solution and the acidifier are added dropwise, and the catalytic activity and the interfacial reaction performance of the amino acid modified nano zero-valent iron and H are realized2O2The reaction generates hydroxyl radicals, thereby oxidatively degrading the organic solvent.
Preferably, the amino acid modified nano zero-valent iron material specifically comprises: amino acid in the material is adsorbed on the surface of the nano zero-valent iron to realize the modification of the nano zero-valent iron, so that the dispersion and the interface interaction of the nano zero-valent iron are enhanced; and the carbon atom on the carboxyl connected with the central carbon atom of the amino acid, the oxygen atom on the carboxyl connected with the central carbon atom and the hydrogen atom on the amino connected with the central carbon atom are respectively connected with the nano zero-valent iron through electrostatic interaction to form a stable structure.
Preferably, the oxygen atom and/or the sulfur atom on the side chain of the amino acid is connected with the nano zero-valent iron through electrostatic interaction.
Preferably, the amino acid modified nano zero-valent iron material is prepared by the following steps:
(1) under the condition of introducing non-oxidative protective atmosphere, dropwise adding potassium borohydride or sodium borohydride aqueous solution into the ferrous salt aqueous solution, wherein the potassium borohydride or the sodium borohydride is used for reducing ferrous ions and generating a precipitate nano zero-valent iron simple substance;
(2) and (2) adding an amino acid aqueous solution into the precipitate nano zero-valent iron simple substance obtained in the step (1) to perform a grafting reaction, thereby obtaining the amino acid modified nano zero-valent iron material.
Preferably, the ferrous salt is ferrous sulfate heptahydrate, ferrous chloride tetrahydrate or ferrous gluconate; the amino acid is an alpha-amino acid.
Preferably, the organic solvent is the organic solvent remaining after separation and purification of the radioactive actinides;
preferably, the actinide is uranium and/or plutonium;
preferably, the organic solvent contains tributyl phosphate and n-dodecane; the volume ratio of tributyl phosphate to n-dodecane is 1: (1-4).
Preferably, the mass ratio of the amino acid modified nano zero-valent iron to the organic solvent is (0.2-0.6): 10.
Preferably, H in the aqueous hydrogen peroxide solution2O2The volume fraction of (2) is 30%, and the volume ratio of the aqueous hydrogen peroxide solution to the organic solvent is (100-250): 10.
Preferably, the acidifying agent is sulfuric acid or nitric acid;
preferably, the initial concentration of the acidifying agent is 0.5-2.5M, and the volume ratio of the acidifying agent to the organic solvent is (30-60): 10.
Preferably, the reaction temperature is 85 ℃ to 95 ℃.
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) the invention mixes amino acid modified nano zero-valent iron powder with organic solvent, then dropwise adds hydrogen peroxide aqueous solution and acidifier to form water phase and oil phase, and utilizes the catalytic activity and interfacial reaction property of amino acid modified nano zero-valent iron and H2O2The reaction generates hydroxyl radicals, thereby oxidatively degrading the organic solvent. The invention belongs to a multiphase reaction system, and benefits from the good dispersibility of a solid catalyst and the better interface interaction between a water phase, an oil phase and a solid phase brought by the surface modification of amino acid, OH generated by the catalysis of hydrogen peroxide can directly attack organic solvent molecules, and the oxidative degradation of organic matters is promoted. At the beginning of the reaction, multiple phases exist, namely an organic phase, a water phase and a solid phase; iron ions in a solid phase can be gradually dissolved out into a water phase in the reaction process, the structure of an organic solvent can be changed, and part of an organic phase can be dissolved into the water phase(ii) a After the reaction is complete, the system is mainly aqueous, and a small amount of organic phase remains which is not completely degraded.
(2) The amino acid modified nano zero-valent iron has the high-efficiency catalytic activity of the zero-valent iron and also has better dispersibility and interface interaction brought by the surface modification of the amino acid, so that the amino acid modified nano zero-valent iron is beneficial to directly attacking organic solvent molecules by OH generated by hydrogen peroxide catalysis and promoting the oxidative degradation of organic matters.
(3) The Chemical Oxygen Demand (COD) degradation trend of the reaction system is obvious, the COD of the reaction residual liquid is low, and the COD of the solution system can be reduced from 10000mg/L to about 100mg/L within 2 h. The volume reduction rate of organic matter can be up to above 90%, and the oxidation efficiency can be up to above 60%, in which the volume reduction rate (V) is equal to (V)Initial organic phase of reaction-VOrganic phase of reaction raffinate)/VInitial organic phase of reactionX 100%, oxidation efficiency (%) - (V)Initial organic phase of reaction-VOrganic phase of reaction raffinate-VOrganic phase of condensate)/VInitial organic phase of reactionX 100 percent, the dosage of the needed catalyst is only 0.03g/mL, the reaction condition is mild, high temperature and high pressure are not needed, the instruments and equipment are simple, and no iron-containing sludge is generated.
Drawings
FIG. 1 is a view of a reaction apparatus for degrading radioactive waste organic solvent.
FIG. 2 shows the COD removal effect of radioactive spent organic solvent using different types of catalysts.
FIG. 3 is a graph of the volume reduction of radioactive spent organic solvent using different types of catalysts.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The amino acid modified nano zero-valent iron material is powdery, the amino acid is adsorbed on the surface of the nano zero-valent iron through electrostatic interaction, the surface functionalization of nano particles is realized, the dispersion and interface interaction of the nano particles are enhanced, and the modified material contains polar groups such as amino groups, carboxyl groups and the like, so that the nano zero-valent iron material has better hydrophilicity, and the branched chain with the specificity of the amino acid can generate interaction force with organic molecules, thereby having higher catalytic reaction activity and adsorption performance. The amino acid can be glycine, alanine, valine, isoleucine, proline, phenylalanine, methionine, cysteine, asparagine, serine, glutamic acid, lysine, or arginine.
The amino acid modified nano zero-valent iron material has the following structural characteristics and properties: the amino group and carboxyl group of the amino acid are the main sites for interaction with iron atoms, the side chain is hardly involved in the interaction between the amino acid and metal, and the interaction with iron occurs when the side chain contains an oxygen-containing functional group. After the amino acid reacts with iron, the shape structure and charge distribution of the amino acid are changed. The iron atom tends to transfer electrons to the carboxyl group of the amino acid, and thus the carboxyl group is the most effective adsorption site. Under the action of the adsorption force of the iron atom, the amino nitrogen atom and the carboxyl oxygen atom tend to form a stable tridentate structure with the iron atom.
The invention relates to an amino acid modified nano zero-valent iron material, wherein amino acid is adsorbed on the surface of nano zero-valent iron to realize nano zero-valent iron modification, so that the dispersion and interface interaction of the nano zero-valent iron are enhanced; and the carbon atom on the carboxyl connected with the central carbon atom of the amino acid, the oxygen atom on the carboxyl connected with the central carbon atom and the hydrogen atom on the amino connected with the central carbon atom are respectively connected with the nano zero-valent iron through electrostatic interaction to form a stable structure.
In some embodiments, the oxygen and/or sulfur atoms on the amino acid side chain are attached to the nano zero valent iron by electrostatic interaction.
In some embodiments, the amino acid is an alpha-amino acid.
In some embodiments, the a-amino acid is glycine, alanine, valine, leucine, isoleucine, proline, phenylalanine, tryptophan, methionine, cysteine, asparagine, serine, aspartic acid, glutamic acid, lysine, or arginine.
In some embodiments, the oxygen atom on the amino acid side chain is an oxygen atom on a hydroxyl group, a carboxyl group, or a carbonyl group.
The preparation method of the amino acid modified nano zero-valent iron material comprises the following steps:
(1) under the condition of introducing non-oxidative protective atmosphere, dropwise adding potassium borohydride or sodium borohydride aqueous solution into the ferrous salt aqueous solution, wherein the potassium borohydride or the sodium borohydride is used for reducing ferrous ions and generating a precipitate nano zero-valent iron simple substance;
(2) and (2) adding an amino acid aqueous solution into the precipitate nano zero-valent iron simple substance obtained in the step (1) to perform a grafting reaction, thereby obtaining the amino acid modified nano zero-valent iron material.
In some embodiments, the ferrous salt is ferrous sulfate heptahydrate, ferrous chloride tetrahydrate, or ferrous gluconate; the amino acid is an alpha-amino acid.
In some embodiments, the initial concentration of the aqueous solution of the ferrous salt is 0.02mol/L to 0.08 mol/L; the ratio of the initial concentration of the potassium borohydride aqueous solution or the sodium borohydride aqueous solution to the initial concentration of the ferrous salt aqueous solution is (4-6): 1.
In some embodiments, the mass ratio of the amino acid to the nano zero-valent iron simple substance is (1-3): 1.
The preparation process of the amino acid modified nano zero-valent iron material specifically comprises the following steps: the preparation method adopts a liquid phase reduction method and a grafting method, and comprises the following steps: at room temperature, under the conditions of nitrogen protection and electric stirring, dropwise adding a potassium borohydride aqueous solution into a ferrous salt aqueous solution at the speed of 2mL/min, carrying out reduction reaction for 2h, and standing for precipitation; washing the precipitate with oxygen-free deionized water for three times, adding an amino acid aqueous solution with a certain concentration into the precipitate for a grafting reaction, stirring the mixed solution at a low speed for 1h, standing the precipitate, then putting the precipitate into a vacuum freeze drying oven for drying for 1-2 days, and avoiding the contact of the material and oxygen in the whole process. The stirring speed of the reduction reaction is 300-500 r/min; the stirring speed of the grafting reaction is 100-200 r/min.
Example 1
FIG. 1 is a view of a reaction apparatus for degrading radioactive waste organic solvent. The temperature of the water bath was set to 95 ℃ and 3mL of tributyl phosphate and 7mL of n-dodecane were added to a 500mL four-necked flask. To examine the degradation effect of radioactive waste organic solvent when different kinds of catalysts are used, a set of experiments was carried out by dropping 50mL of 0.4mol/L ferrous sulfate solution (containing 2mol/L sulfuric acid) and 150mL of H at a dropping rate of 2mL/min into a flask2O2(30%); in one set of experiments, 0.3g of nano zero-valent iron powder is weighed and added into a flask, and 150mL of H is respectively dripped into the flask at the dripping speed of 2mL/min2O2(30%) and 50mL of a 2mol/L sulfuric acid solution; in one group of experiments, 0.3g of alanine modified nano zero-valent iron powder is weighed and added into a flask, and 150mL of H is respectively dripped into the flask at the dripping speed of 2mL/min2O2(30%) and 50mL of a 2mol/L sulfuric acid solution. The reaction is started and timed at the stirring speed of 350r/min, the sampling time is respectively 5, 10, 15, 20, 25, 30, 40, 50, 60, 90 and 120min, 11 samples are taken in total, the flask is connected with a condensing device to receive condensate generated in the reaction process, and concentrated sulfuric acid is used in a tail gas absorption device to absorb tail gas.
After the reaction is finished for 2 hours, pouring the residual liquid in the flask into a separating funnel, standing and layering, wherein the upper layer is colorless transparent oil phase, the lower layer is yellow water phase, then measuring the volume of the residual oil phase at the upper layer, and similarly, standing and layering the condensate, and measuring the volume of the oil phase in the condensate, wherein the volume reduction rate (%) is (V)Initial organic phase of reaction-VOrganic phase of reaction raffinate)/VInitial organic phase of reactionX 100%, oxidation efficiency (%) - (V)Initial organic phase of reaction-VOrganic phase of reaction raffinate-VOrganic phase of condensate)/VInitial organic phase of reactionX 100%. Diluting a part of the sample, digesting, and measuring COD value of the diluted sample at 440nm with ultraviolet-visible spectrophotometer, the COD removal effect and volume reduction rate of different catalyst types on radioactive waste organic solvent are shown in FIG. 2 and FIG. 3, and as can be seen from FIG. 2, the COD removal effect and volume reduction rate of different catalyst types on radioactive waste organic solvent are shown in FIG. 2When the alanine modified nano zero-valent iron is used as the catalyst of the system, the COD of the solution begins to decrease after 15min, the final COD of the system is the lowest, when the ferrous sulfate and the nano zero-valent iron are used as the catalyst of the system, the COD of the solution begins to decrease after 20min, and the final COD of the system is slightly higher, thereby showing that the alanine modified nano zero-valent iron has better catalytic performance and can accelerate the rate of the oxidative degradation reaction of the organic solvent. As can be seen from fig. 3, compared with ferrous sulfate and nano zero-valent iron, alanine modified nano zero-valent iron can make the organic solvent reach the highest volume reduction rate, and the volume of the oil phase of fenton oxidation and the volume of the oil phase of the condensate are both the highest, and the volume of the oil phase of the raffinate is the smallest, which indicates that when alanine modified nano zero-valent iron is used as the catalyst of the system, the oxidation efficiency of the fenton-like reaction system is the highest, the organic solvent has a better degradation effect, and the treatment requirement is more easily met.
The results of the comparison after the end of the reaction are shown in Table 1:
TABLE 1 degradation Effect of different catalyst types on radioactive spent organic solvents
| Catalyst type | Volume reduction ratio (%) | Oxidation efficiency (%) | COD(mg/L) |
| |
80％ | 51％ | 240 |
| Nano zero- |
89％ | 55％ | 420 |
| Alanine modified nano zero- |
96％ | 61％ | 75 |
As can be seen from Table 1, the amino acid modified nano zero-valent iron used as the catalyst for the Fenton-like degradation of the organic solvent has the optimal catalytic performance, when the alanine modified nano zero-valent iron is used as the catalyst, the volume reduction rate of an organic matter (oil phase) can reach more than 90%, the oxidation efficiency can reach more than 60%, the required catalyst dosage is small, the Chemical Oxygen Demand (COD) of reaction residual liquid is low, the reaction conditions are mild, the raw materials are easily available, and the method is environment-friendly.
Example 2
FIG. 1 is a view of a reaction apparatus for degrading radioactive waste organic solvent. The temperature of the water bath was set to 95 ℃ and 3mL of tributyl phosphate and 7mL of n-dodecane were added to a 500mL four-necked flask. In order to examine the degradation effect of different amino acid modified catalyst materials on radioactive waste organic solvents, 0.3g of alanine modified nano zero-valent iron powder, phenylalanine modified nano zero-valent iron powder and serine modified nano zero-valent iron powder are respectively weighed in three groups of experiments and added into a flask, and 150mL of H is respectively dripped into the flask at the dripping speed of 2mL/min2O2(30%) and 50mL of 2mol/L sulfuric acid solution, starting the reaction at a stirring speed of 350r/min and timing, wherein the sampling time is respectively 5, 10, 15, 20, 25, 30, 40, 50, 60, 90 and 120min, taking 11 samples in total, the flask is connected with a condensing device to receive condensate generated in the reaction process, and concentrated sulfuric acid is used in a tail gas absorption device to absorb tail gas.
After the reaction is finished for 2 hours, pouring the residual liquid in the flask into a separating funnel, standing for layering, wherein the upper layer is a colorless transparent oil phase, the lower layer is a yellow water phase, measuring the volume of the residual oil phase at the upper layer, and measuring the volume of the residual oil phase at the same timeStanding the condensate for layering, and measuring the volume of an oil phase in the condensate, wherein the volume reduction rate (%) is (V)Initial organic phase of reaction-VOrganic phase of reaction raffinate)/VInitial organic phase of reactionX 100%, oxidation efficiency (%) - (V)Initial organic phase of reaction-VOrganic phase of reaction raffinate-VOrganic phase of condensate)/VInitial organic phase of reactionX 100%. A portion of the sample was diluted and digested and the COD value of the diluted sample was measured at 440nm using a uv-vis spectrophotometer, the results are shown in table 2:
TABLE 2 degradation effect of different amino acid modified catalyst materials on radioactive waste organic solvent
| Catalyst type | Volume reduction ratio (%) | Oxidation efficiency (%) | COD(mg/L) |
| Alanine modified nano zero-valent iron | 97％ | 64％ | 104 |
| Phenylalanine modified nano zero-valent iron | 98％ | 98％ | 255 |
| Serine modified nano zero-valent iron | 98％ | 58％ | 148 |
As can be seen from Table 2, the amino acid modified nano zero-valent iron used as the catalyst for the Fenton-like degradation of the organic solvent has good catalytic performance, the volume reduction rate of the organic matter (oil phase) is over 95 percent, the oxidation efficiency can reach over 60 percent, even when the phenylalanine modified nano zero-valent iron is used, the oxidation efficiency can reach over 90 percent, the catalyst consumption required by the reaction is small, the COD (chemical oxygen demand) of the reaction residual liquid is low, the reaction condition is mild, the raw materials are easily available, and the method is environment-friendly.
Example 3
FIG. 1 is a view of a reaction apparatus for degrading radioactive waste organic solvent. The temperature of the water bath was set to 95 ℃ and 3mL of tributyl phosphate and 7mL of n-dodecane were added to a 500mL four-necked flask. In order to investigate the degradation effect on radioactive waste organic solvent when catalysts with different qualities are added, 0.2g, 0.3g and 0.4g of alanine modified nano zero-valent iron powder are respectively weighed in three groups of experiments and added into a flask, and 150mL of H is respectively dripped into the flask at the dripping speed of 2mL/min2O2(30%) and 50mL of 2mol/L sulfuric acid solution, starting the reaction at a stirring speed of 350r/min and timing, wherein the sampling time is respectively 5, 10, 15, 20, 25, 30, 40, 50, 60, 90 and 120min, taking 11 samples in total, the flask is connected with a condensing device to receive condensate generated in the reaction process, and concentrated sulfuric acid is used in a tail gas absorption device to absorb tail gas.
After the reaction is finished for 2 hours, pouring the residual liquid in the flask into a separating funnel, standing and layering, wherein the upper layer is colorless transparent oil phase, the lower layer is yellow water phase, then measuring the volume of the residual oil phase at the upper layer, and similarly, standing and layering the condensate, and measuring the volume of the oil phase in the condensate, wherein the volume reduction rate (%) is (V)Initial organic phase of reaction-VOrganic phase of reaction raffinate)/VInitial organic phase of reactionX 100%, oxidation efficiency (%) - (V)Initial organic phase of reaction-VOrganic phase of reaction raffinate-VOrganic phase of condensate)/VInitial organic phase of reactionX 100%. Will get the resultA portion of the sample was diluted and digested and the COD value of the diluted sample was measured at 440nm using a uv-vis spectrophotometer, with the results shown in table 3:
TABLE 3 degradation effect of different catalyst dosages on radioactive waste organic solvent
| Mass of catalyst (g) | Volume reduction ratio (%) | Oxidation efficiency (%) | COD(mg/L) |
| 0.2 | 81％ | 54％ | 95 |
| 0.3 | 96％ | 61％ | 75 |
| 0.4 | 93％ | 65％ | 88 |
It can be seen from table 3 that amino acid modified nanoscale zero-valent iron with different mass added as a catalyst has good catalytic performance when used for the Fenton-like degradation of organic solvents, and increasing the usage amount of the catalyst can improve the volume reduction rate and the oxidation efficiency of radioactive waste organic solvents, but the efficiency is slightly reduced when the catalyst is excessive, which indicates that the addition amount of the catalyst should be proper to achieve the optimal treatment effect.
Example 4
FIG. 1 is a view of a reaction apparatus for degrading radioactive waste organic solvent. The temperature of the water bath was set to 95 ℃ and 3mL of tributyl phosphate and 7mL of n-dodecane were added to a 500mL four-necked flask. In order to investigate the degradation effect of radioactive waste organic solvents when acidulants with different concentrations are used, 0.3g of alanine modified nano zero-valent iron powder is weighed and added into a flask, and 150mL of H is respectively dripped into the flask at the dripping speed of 2mL/min2O2(30%) and 50mL of sulfuric acid solution, wherein the concentration of the sulfuric acid is 1mol/L, 2mol/L and 2.5mol/L respectively, the reaction is started and timed at the stirring speed of 350r/min, the sampling time is 5, 10, 15, 20, 25, 30, 40, 50, 60, 90 and 120min respectively, 11 samples are taken in total, the flask is connected with a condensing device to receive condensate generated in the reaction process, and concentrated sulfuric acid is used in a tail gas absorption device to absorb tail gas.
After the reaction is finished for 2 hours, pouring the residual liquid in the flask into a separating funnel, standing and layering, wherein the upper layer is colorless transparent oil phase, the lower layer is yellow water phase, then measuring the volume of the residual oil phase at the upper layer, and similarly, standing and layering the condensate, and measuring the volume of the oil phase in the condensate, wherein the volume reduction rate (%) is (V)Initial organic phase of reaction-VOrganic phase of reaction raffinate)/VInitial organic phase of reactionX 100%, oxidation efficiency (%) - (V)Initial organic phase of reaction-VOrganic phase of reaction raffinate-VOrganic phase of condensate)/VInitial organic phase of reactionX 100%. A portion of the sample was diluted and digested and the COD value of the diluted sample was measured at 440nm using a uv-vis spectrophotometer, the results are shown in table 4:
TABLE 4 degradation Effect of different sulfuric acid concentrations on radioactive spent organic solvents
| H2SO4Concentration (mol/L) | Volume reduction ratio (%) | Oxidation efficiency (%) | COD(mg/L) |
| 1 | 87％ | 71％ | 206 |
| 2 | 96％ | 61％ | 75 |
| 2.5 | 82％ | 52％ | 83 |
As can be seen from Table 4, H+The concentration has certain influence on the volume reduction rate and the oxidation efficiency of the radioactive waste organic solvent, and H is increased+The concentration can increase the volume reduction rate, but the volume reduction rate is reduced after the concentration is excessive, H+The oxidation efficiency of the organic solvent can reach more than 70% when the concentration is proper, which shows that the concentration of the acidifying agent added into the system has certain influence on the treatment effect, and the proper H is used+Can achieve better treatment effect under the concentration.
Example 5
FIG. 1 is a diagram of an organic solvent degradation reaction apparatus. Setting the temperature of a water bath kettle to be 95 ℃, respectively adding 10mL of styrene and 10mL of normal octane into a 500mL four-neck flask, and weighing 0.3g of alanine modified sodium bicarbonate to examine the degradation effect of different waste organic solventsAdding the rice zero-valent iron powder into a flask, and respectively dropwise adding 150mL of H into the flask at a dropping speed of 2mL/min2O2(30%) and 2 mol/L50 mL sulfuric acid solution, starting the reaction at a stirring speed of 350r/min and timing, wherein the sampling time is respectively 5, 10, 15, 20, 25, 30, 40, 50, 60, 90 and 120min, totally 11 samples are taken, the flask is connected with a condensing device to receive condensate generated in the reaction process, and concentrated sulfuric acid is used in a tail gas absorption device to absorb tail gas.
After the reaction is finished for 2 hours, pouring the residual liquid in the flask into a separating funnel, standing and layering, wherein the upper layer is colorless transparent oil phase, the lower layer is yellow water phase, then measuring the volume of the residual oil phase at the upper layer, and similarly, standing and layering the condensate, and measuring the volume of the oil phase in the condensate, wherein the volume reduction rate (%) is (V)Initial organic phase of reaction-VOrganic phase of reaction raffinate)/VInitial organic phase of reactionX 100%, oxidation efficiency (%) - (V)Initial organic phase of reaction-VOrganic phase of reaction raffinate-VOrganic phase of condensate)/VInitial organic phase of reactionX 100%. A portion of the sampled sample was diluted and digested and the COD value of the diluted sample was measured at 440nm using a uv-vis spectrophotometer, the results are shown in table 5:
TABLE 5 degradation Effect of different kinds of organic solvents
| Organic solvent component | Volume reduction ratio (%) | Oxidation efficiency (%) | COD(mg/L) |
| Styrene (meth) acrylic acid ester | 92％ | 54％ | 329 |
| N-octane | 91％ | 48％ | 241 |
As can be seen from Table 5, the degradation effects of the organic solvents with different components are different, and the difference of the composition and the proportion of the organic solvents can cause the difference of the difficulty degree of degradation, but because the method has stronger oxidative degradation capability and OH generated in the system has no selectivity to organic matters, organic molecules can be attacked and degraded without difference, better volume reduction rate and oxidation efficiency can be obtained under proper treatment conditions, and the COD value of the final reaction residual liquid is lower.
Example 6
FIG. 1 is a diagram of an organic solvent degradation reaction apparatus. Setting the temperature of a water bath kettle to be 95 ℃, and respectively adding 10mL of pure organic solvent and 10mL of extracted Co into a 500mL four-neck flask to examine the influence of the existence of radioactive elements on the degradation effect of the organic solvent2+0.3g of alanine modified nano zero-valent iron powder is weighed and added into a flask, and 150mL of H is respectively dripped into the flask at the dripping speed of 2mL/min2O2(30%) and 2 mol/L50 mL sulfuric acid solution, starting the reaction at a stirring speed of 350r/min and timing, wherein the sampling time is respectively 5, 10, 15, 20, 25, 30, 40, 50, 60, 90 and 120min, totally 11 samples are taken, the flask is connected with a condensing device to receive condensate generated in the reaction process, and concentrated sulfuric acid is used in a tail gas absorption device to absorb tail gas.
After the reaction is finished for 2 hours, pouring the residual liquid in the flask into a separating funnel, standing and layering, wherein the upper layer is colorless transparent oil phase, the lower layer is yellow water phase, then measuring the volume of the residual oil phase at the upper layer, and similarly, standing and layering the condensate, and measuring the volume of the oil phase in the condensate, wherein the volume reduction rate (%) is (V)Initiation of the reactionOrganic phase-VOrganic phase of reaction raffinate)/VInitial organic phase of reactionX 100%, oxidation efficiency (%) - (V)Initial organic phase of reaction-VOrganic phase of reaction raffinate-VOrganic phase of condensate)/VInitial organic phase of reactionX 100%. A portion of the sampled sample was diluted and digested and the COD value of the diluted sample was measured at 440nm using a uv-vis spectrophotometer, the results are shown in table 6:
TABLE 6 influence of radioactive elements on the degradation effect of the waste organic solvent
| Organic solvent component | Volume reduction ratio (%) | Oxidation efficiency (%) | COD(mg/L) |
| Without containing radionuclides | 94％ | 56％ | 726 |
| Containing radioactive nuclide | 95％ | 50％ | 235 |
As can be seen from Table 6, the presence of radioactive elements does not hinder the degradation of the waste organic solvent, even has a certain promotion effect on the degradation, and the organic solvent and nuclide form an extraction complex to be more beneficial to be degraded by OH generated by the system, so the method has a better treatment effect on the radioactive waste organic solvent.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for treating an organic solvent by a heterogeneous Fenton-like method is characterized in that an amino acid modified nano zero-valent iron material is mixed with the organic solvent, then a hydrogen peroxide aqueous solution and an acidifier are added dropwise, and the catalytic activity and the interfacial reaction performance of the amino acid modified nano zero-valent iron and H are utilized2O2The reaction generates hydroxyl radicals, thereby oxidatively degrading the organic solvent.
2. The method for treating the organic solvent according to claim 1, wherein the amino acid-modified nanoscale zero-valent iron material is specifically: amino acid in the material is adsorbed on the surface of the nano zero-valent iron to realize the modification of the nano zero-valent iron, so that the dispersion and the interface interaction of the nano zero-valent iron are enhanced; and the carbon atom on the carboxyl connected with the central carbon atom of the amino acid, the oxygen atom on the carboxyl connected with the central carbon atom and the hydrogen atom on the amino connected with the central carbon atom are respectively connected with the nano zero-valent iron through electrostatic interaction to form a stable structure.
3. The method for treating an organic solvent according to claim 2, wherein the oxygen atom and/or the sulfur atom on the side chain of the amino acid is bonded to the nanoscale zero-valent iron by electrostatic interaction.
4. The method for treating the organic solvent by the heterogeneous Fenton-like process according to claim 2, wherein the amino acid modified nano zero-valent iron material is prepared by the following steps:
(1) under the condition of introducing non-oxidative protective atmosphere, dropwise adding potassium borohydride or sodium borohydride aqueous solution into the ferrous salt aqueous solution, wherein the potassium borohydride or the sodium borohydride is used for reducing ferrous ions and generating a precipitate nano zero-valent iron simple substance;
(2) and (2) adding an amino acid aqueous solution into the precipitate nano zero-valent iron simple substance obtained in the step (1) to perform a grafting reaction, thereby obtaining the amino acid modified nano zero-valent iron material.
5. The method of claim 4, wherein the ferrous salt is ferrous sulfate heptahydrate, ferrous chloride tetrahydrate, or ferrous gluconate; the amino acid is an alpha-amino acid.
6. The method for treating an organic solvent according to claim 1, wherein the organic solvent is an organic solvent remaining after separation and purification of radioactive actinides;
preferably, the actinide is uranium and/or plutonium;
preferably, the organic solvent contains tributyl phosphate and n-dodecane; the volume ratio of tributyl phosphate to n-dodecane is 1: (1-4).
7. The method for treating the organic solvent by the heterogeneous Fenton-like method according to claim 1, wherein the mass ratio of the amino acid modified nano zero-valent iron to the organic solvent is (0.2-0.6): 10.
8. The method for treating an organic solvent according to claim 1, wherein H is contained in the aqueous hydrogen peroxide solution2O2The volume fraction of (2) is 30%, and the volume ratio of the aqueous hydrogen peroxide solution to the organic solvent is (100-250): 10.
9. The method for treating an organic solvent according to claim 1, wherein the acidifying agent is sulfuric acid or nitric acid;
preferably, the initial concentration of the acidifying agent is 0.5-2.5M, and the volume ratio of the acidifying agent to the organic solvent is (30-60): 10.
10. The method for treating an organic solvent according to claim 1, wherein the reaction temperature is 85 ℃ to 95 ℃.
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