CN114307980A - Composite material and composition for treating unsymmetrical dimethylhydrazine pollutants, and treatment method and experimental method thereof - Google Patents
Composite material and composition for treating unsymmetrical dimethylhydrazine pollutants, and treatment method and experimental method thereof Download PDFInfo
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Abstract
The invention relates to the field of pollutant treatment, in particular to a composite material, a composition and a treatment method for treating unsymmetrical dimethylhydrazine pollutants. The composite material is prepared from graphene oxide and carboxymethyl chitosan by a solution blending method, wherein the weight ratio of the graphene oxide to the carboxymethyl chitosan is (1-25): 100. the composite adsorbing material disclosed by the invention has the characteristics of no toxicity, no harm, no spontaneous combustion, good adsorption performance and the like, and can be used for effectively removing leaked low-concentration unsymmetrical dimethylhydrazine wastewater and high-concentration unsymmetrical dimethylhydrazine waste liquid.
Description
Technical Field
The invention relates to the field of pollutant treatment, in particular to a composite material and a composition for treating unsymmetrical dimethylhydrazine pollutants, a treatment method and an experimental method.
Background
Unsym-dimethylhydrazine (UDMH, (CH)3)2NNH3) The high-energy liquid rocket propellant has high combustion heat, high density impulse, high specific impulse and other properties, so that the high-energy liquid rocket propellant is widely applied to power systems of carrier rockets and liquid missiles. The unsymmetrical dimethylhydrazine can be accidentally leaked in the production, transportation, transfer filling and use processes, a large amount of waste liquid generated by the leakage and emergency disposal of the unsymmetrical dimethylhydrazine poses great threats to the environment and the human health, and has harmful effects on human bodies such as carcinogenesis, mutagenicity, convulsion, teratogenesis, embryotoxicity and the like. When unsymmetrical dimethylhydrazine is exposed to natural conditions such as water or soil, the unsymmetrical dimethylhydrazine is spontaneously oxidized into a carcinogen N-dimethylnitrosamine (NDMA) which is more toxic than the unsymmetrical dimethylhydrazine. Therefore, before the unsymmetrical dimethylhydrazine waste liquid is discharged to the environment, the unsymmetrical dimethylhydrazine waste liquid is necessary to be reasonably treated.
The unsymmetrical dimethylhydrazine wastewater treatment method mainly comprises ozone oxidation, catalytic oxidation and various advanced oxidation technologies (AOPs), such as Fenton oxidation, photocatalytic oxidation, hydrodynamic cavitation and low-temperature plasma degradation. These methods all achieve satisfactory degradation results, but have the problems of long treatment time, high energy consumption, high cost, difficult thorough degradation and the like. Particularly, unsymmetrical dimethylhydrazine inevitably produces a series of toxic intermediates including NDMA in the treatment process, which can cause potential threats to environmental ecology and human health. In recent years, adsorption methods have been used to remove organic pollutants from wastewater with high efficiency due to their advantages of simple process, relatively low cost, and no generation of toxic intermediates. At present, few research reports on treatment of unsymmetrical dimethylhydrazine wastewater by an adsorption method exist, and efficient and applicable adsorption material research needs to be developed aiming at the adsorption treatment of unsymmetrical dimethylhydrazine.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The primary object of the present invention is to provide a composite material for treating unsymmetrical dimethylhydrazine contaminants.
The second purpose of the invention is to provide a composition for treating unsymmetrical dimethylhydrazine pollutant.
The third invention aims to provide a method for treating unsymmetrical dimethylhydrazine pollutants.
The fourth invention aims to provide an experimental method for unsymmetrical dimethylhydrazine pollutant treatment.
In order to achieve the purpose of the invention, the technical scheme is as follows:
the invention provides a composite material for treating unsymmetrical dimethylhydrazine pollutants, which is prepared from graphene oxide and carboxymethyl chitosan by a solution blending method, wherein the weight ratio of the graphene oxide to the carboxymethyl chitosan is (1-25): 100, preferably 5 to 20: 100.
optionally, the preparation method of the composite material comprises the following steps:
s1, respectively preparing carboxymethyl chitosan dispersion liquid and graphene oxide dispersion liquid;
s2, mixing the graphene oxide dispersion liquid and the carboxymethyl chitosan dispersion liquid, and performing magnetic stirring and ultrasonic dispersion;
s3, adding absolute ethyl alcohol to terminate the reaction, and adjusting the pH value to be neutral;
s4, washing, drying, grinding and sieving to obtain the composite material.
Optionally, in S1, the content of carboxymethyl chitosan in the carboxymethyl chitosan dispersion liquid is 0.01 to 0.05g/L, preferably 0.02 g/L;
preferably, the preparation method of the carboxymethyl chitosan dispersion comprises the following steps:
s11, preparing an isopropanol solution of chitosan, adding a NaOH solution with the mass fraction of 40%, and stirring at 55-65 ℃ for 1 h; the weight-volume ratio of chitosan to isopropanol is 5-8 g: 100mL, wherein the weight-volume ratio of the chitosan to the NaOH solution is 5-8 g: 120 mL;
s12, adding an isopropanol solution dissolved with chloroacetic acid, wherein the weight ratio of chitosan to chloroacetic acid is 1: 4-6; the adding speed is 1-2 mL/min;
s13, reacting for 4-6 h at 55-65 ℃ to obtain the carboxymethyl chitosan dispersion liquid.
Optionally, in S1, the concentration of graphene oxide in the graphene oxide dispersion liquid is 3-10 g/L, preferably 5 g/L; preferably prepared by ultrasonic dispersion;
preferably, in S2, the magnetic stirring is performed for 0.5 to 2 hours, and the ultrasonic dispersion is performed for 0.5 to 2 hours.
Optionally, in S4, the washing is performed with an organic solvent, preferably an alcoholic organic solvent, more preferably ethanol;
the drying is drying at 50-55 ℃, and the sieving is preferably a 100-mesh sieve.
The invention further provides a treatment method of unsymmetrical dimethylhydrazine pollutants, wherein the composite material is adopted for treatment, and the unsymmetrical dimethylhydrazine pollutants are wastewater containing 10-40 mg/L unsymmetrical dimethylhydrazine.
Optionally, the pH of the unsymmetrical dimethylhydrazine contaminant is greater than 7, more preferably greater than or equal to 12;
the treatment temperature is 20-40 ℃;
the adding amount of the composite material is 4-16 g/L, and preferably 8-12 g/L;
the treatment time is 30-720 min.
The invention provides a composition for treating unsymmetrical dimethylhydrazine pollutants, which contains the composite material, and also contains an oxidant, wherein the oxidant is preferably Ca (ClO)2；
Preferably, the weight ratio of the composite material to the oxidant is 1: 4-6, preferably 1: 5.
more preferably, the composition further comprises an inorganic phase change material, and the inorganic phase change material is preferably Na2SO4·10H2O and Na2B4O7·10H2At least one of O;
further preferably, the weight ratio of the composite material to the inorganic phase change material is 1: 5-10, preferably 1: 6.
the invention provides a treatment method of unsymmetrical dimethylhydrazine pollutants, which adopts the composite material or the composition to cover the pollutants, wherein the mass percent concentration of unsymmetrical dimethylhydrazine in the unsymmetrical dimethylhydrazine pollutants is 10-100%;
the treatment temperature is 15-25 ℃;
the treatment time is 30-60 min;
the dosage of the composite material or the composition is 1-10 g/mL, preferably 2-5 g/mL.
The invention provides an experimental method for unsymmetrical dimethylhydrazine pollutant treatment, which comprises the following steps:
s1, arranging an electric fan in the closed experiment box, connecting the unsymmetrical dimethylhydrazine gas detector to the experiment device, and turning on the electric fan in the device;
s2, removing unsymmetrical dimethylhydrazine pollutants in a watch glass, and covering the pollutants with the composite material of any one of claims 1 to 5 or the composition of claim 8;
s3, placing the cuvette into the closed experiment box, and detecting the concentration of unsymmetrical dimethylhydrazine in the air by using an unsymmetrical dimethylhydrazine gas detector;
preferably, the mass percentage concentration of the unsymmetrical dimethylhydrazine in the unsymmetrical dimethylhydrazine pollutant is 10-100%;
the unsymmetrical dimethylhydrazine gas detector is an unsymmetrical dimethylhydrazine electrochemical gas detector.
The invention has at least the following beneficial effects:
the composite adsorbing material and the composition have the characteristics of no toxicity, no harm, no spontaneous combustion, combustion supporting, good adsorption performance and the like, and can effectively remove leaked low-concentration unsymmetrical dimethylhydrazine wastewater and high-concentration unsymmetrical dimethylhydrazine waste liquid.
Drawings
FIG. 1 is a diagram of an experimental apparatus for unsymmetrical dimethylhydrazine pollutant treatment in an embodiment of the present invention;
wherein: 1-a closed experimental box, 2-an electric fan and 3-a watch glass;
FIG. 2 is a FT-IR plot of GO, CMC, and GO/CMC;
FIG. 3 is a Raman analysis plot of GO, CMC, and GO/CMC;
FIG. 4 is SEM images of GO, CMC, and GO/CMC: (a) scanning electron micrographs of GO, (b) CMC, (c) 1% GO/CMC, (d) 10% GO/CMC, and (e) 20% GO/CMC; (f) transmission electron micrograph of 10% GO/CMC;
FIG. 5 is a graph showing the effect of different initial pH values on unsymmetrical dimethylhydrazine adsorption;
FIG. 6 is a graph showing the effect of adsorption temperature on the adsorption of unsymmetrical dimethylhydrazine by the composite material;
FIG. 7 is a graph showing the effect of the amount of added adsorbent on the adsorption of unsymmetrical dimethylhydrazine by the composite material;
FIG. 8 is a graph showing the effect of contact time on unsymmetrical dimethylhydrazine adsorption by the composite material;
FIG. 9 is a graph showing the effect of composite material on the performance of treating high concentration waste liquid;
FIG. 10 is a graph of the effect of composite material plus oxidant on the performance of high concentration waste liquid treatment;
FIG. 11 is a graph showing the effect of composite materials with oxidants and inorganic phase change materials on the performance of high concentration waste liquid treatment;
FIG. 12 is a graph showing the effect of composite materials with oxidants and inorganic phase change materials on the performance of high concentration waste liquid treatment;
FIG. 13 is a graph showing the effect of deionized water, tap water and lake water on adsorbing unsymmetrical dimethylhydrazine on a composite material;
fig. 14 is a graph showing the results of an adsorption experiment performed after ultrasonic regeneration.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms also include the plural forms unless the context clearly dictates otherwise, and further, it is understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The composite material for treating unsymmetrical dimethylhydrazine pollutants is prepared from graphene oxide and carboxymethyl chitosan by a solution blending method, and has the characteristics of no toxicity, no harm, no spontaneous combustion, combustion supporting, good adsorption performance and the like. The chitosan as a biopolymer with abundant natural resources has the advantages of low price, biodegradability, good biocompatibility, no toxicity and the like. Due to the existence of a large number of amino groups and hydroxyl groups in the molecular structure, the chitosan has excellent adsorption capacity and good chelating, crosslinking and adsorption properties. However, chitosan is insoluble in water at pH above 6.5 and has low mechanical strength, limiting its effective use in wastewater treatment. According to the invention, through research, carboxymethylation modification is carried out on chitosan to introduce carboxyl, so that not only can the adsorption active sites of the chitosan be increased, but also the solubility, flocculation and chelation of the chitosan are improved. Graphene Oxide (GO) has a large specific surface area and also contains a large number of oxygen-containing functional groups (hydroxyl, carboxyl, epoxy, etc.). Therefore, the graphene oxide is a good activity enhancing material with excellent adsorption performance. According to the embodiment of the invention, the biopolymer material carboxymethyl chitosan (CMC) and the inorganic nano material GO are prepared into the composite material, so that the respective defects are overcome, the specific surface area, the porosity, the mechanical strength and the stability of the composite material can be increased, and the GO is prevented from being greatly agglomerated. Furthermore, due to the many amino and hydroxyl groups in the CMC units and their amphiphilic polyelectrolyte nature, electrostatic attraction and hydrogen bonding between CMC and GO may be achieved and may result in a truly uniform co-dispersion of CMC and GO on a molecular scale. Wherein the weight ratio of the graphene oxide to the carboxymethyl chitosan is 1-25: 100. preferably 5-25: 100, more preferably 10 to 20: 100. if the addition ratio of the graphene oxide is too low, the adsorption effect of the composite material is limited. If the addition ratio of the graphene oxide is too high, the biotoxicity and the economic cost of the graphene oxide are higher than those of the carboxymethyl chitosan, the content is too high, the economy is not high, and the biological environment friendliness and the economy of the carboxymethyl chitosan cannot be exerted.
The composite material of the embodiment of the invention is prepared by adopting a solution blending method, and compared with other preparation methods, the solution blending method has the advantages that: the method is simple and easy to operate; the method specifically comprises the following steps:
s1, respectively preparing carboxymethyl chitosan dispersion liquid and graphene oxide dispersion liquid;
s2, mixing the graphene oxide dispersion liquid and the carboxymethyl chitosan dispersion liquid, and performing magnetic stirring and ultrasonic dispersion;
s3, adding absolute ethyl alcohol to terminate the reaction, and adjusting the pH value to be neutral;
s4, washing, drying, grinding and sieving to obtain the composite material.
The preparation reaction equation of the composite material of the embodiment of the invention is as follows:
in S1, the content of carboxymethyl chitosan in the carboxymethyl chitosan dispersion liquid is 0.01-0.05 g/L, preferably 0.02 g/L; the content of the graphene oxide in the graphene oxide dispersion liquid is 3-10 g/L, and preferably 5 g/L. If the concentration of the graphene oxide is too high, the graphene oxide cannot be dispersed by ultrasonic.
As an improvement of the embodiment of the invention, the preparation method of the carboxymethyl chitosan dispersion liquid comprises the following steps:
s11, preparing an isopropanol solution of chitosan, adding a NaOH solution with the mass fraction of 40%, and stirring at 55-65 ℃ for 1 h; the weight-volume ratio of chitosan to isopropanol is 5-8 g: 100mL, wherein the weight-volume ratio of the chitosan to the NaOH solution is 5-8 g: 120 mL;
s12, adding an isopropanol solution dissolved with chloroacetic acid, wherein the weight ratio of chitosan to chloroacetic acid is 1: 4-6; the adding speed is 1-2 mL/min,
s13, reacting for 4-6 h at 55-65 ℃ to obtain the carboxymethyl chitosan dispersion liquid.
As a specific embodiment, the preparation method of the carboxymethyl chitosan dispersion liquid comprises the following steps: 6g of chitosan and 100mL of isopropanol are respectively added into a 500mL conical flask, then 100mL of NaOH solution with the mass fraction of 40% is slowly added, and stirring and alkalization are carried out for 1h at 60 ℃. Slowly dropping 100mL of isopropanol solution dissolved with 30g of chloroacetic acid under the stirring condition, completing the reaction within 30min, and then continuing the reaction at 60 ℃ for 4h to obtain the CMC dispersion.
As an improvement of the embodiment of the present invention, in S1, the graphene oxide dispersion liquid is prepared by ultrasonic dispersion.
As a specific embodiment, the preparation method of the graphene oxide dispersion liquid comprises the following steps: weighing GO in a beaker, adding deionized water, and performing ultrasonic dispersion for 0.5-2 hours, preferably for 1 hour to obtain a GO dispersion liquid.
As an improvement of the embodiment of the invention, in S2, magnetic stirring is performed for 0.5 to 2 hours, preferably 1 hour; and ultrasonically dispersing for 0.5-2 hours, preferably for 1 hour. The magnetic stirring in the ultrasonic dispersion has the following advantages: the two dispersions were mixed homogeneously.
As a specific embodiment, the specific step of S3 is: the reaction was terminated by adding 500mL of absolute ethanol, adjusting the pH of the system to neutral with HCl solution (5mol/L), and the precipitate was washed by centrifugation with absolute ethanol.
As a modification of the embodiment of the present invention, in S4, the washing is performed with an organic solvent, and the organic solvent is preferably an alcohol organic solvent, and more preferably ethanol; the drying is carried out at the temperature of 50-55 ℃, and the sieving is preferably a 100-mesh sieve.
The second aspect of the embodiment of the invention provides a treatment method of unsymmetrical dimethylhydrazine pollutants, which is characterized in that the composite material is adopted for treatment, and the unsymmetrical dimethylhydrazine pollutants are wastewater containing 10-40 mg/L of unsymmetrical dimethylhydrazine. In the process of treating the unsymmetrical dimethylhydrazine, a plurality of wastewater containing the unsymmetrical dimethylhydrazine with low concentration can be generated, and the adsorption method used with low concentration has the advantages of simple process, relatively low cost, no generation of toxic intermediate products and the like. The problems of long treatment time, large energy consumption, high cost, difficult thorough degradation and the like in other advanced oxidation methods are solved. Therefore, the composite material can adsorb the metadimethylhydrazine in the wastewater, thereby achieving better treatment effect.
In order to further improve the treatment effect, the treatment conditions are further studied in the embodiment of the invention, and the adsorption performance of the composite material under different pH values is slightly different. When the pH value is 4, the unsymmetrical dimethylhydrazine removal rate is low, probably due to H+Competition with unsymmetrical dimethylhydrazine for adsorption sites on the adsorbent. With the increase of pH, the surface of the composite material is deprotonated, so that the surface of the composite material is negatively charged, unsymmetrical dimethylhydrazine is alkalescent in water, and the surface of a unsymmetrical dimethylhydrazine molecule is positively charged and interacts with the composite material. These results further demonstrate that pH and electrostatic force play a key role in the adsorption process, and the higher pH conditions make more active sites appear on the surface of the adsorbent, which affects the interaction between the composite material and unsymmetrical dimethylhydrazine molecules. When the pH value of the unsymmetrical dimethylhydrazine pollutant is greater than 7, more preferably greater than or equal to 12, the treatment effect is remarkably improved, and the adsorption capacity of the unsymmetrical dimethylhydrazine on the composite material is increased along with the increase of the pH value.
As an improvement of the embodiment of the invention, the research of the embodiment of the invention finds that the adsorption capacity of the unsymmetrical dimethylhydrazine is enhanced along with the increase of the temperature, and the higher the temperature is, the higher the adsorption capacity of the unsymmetrical dimethylhydrazine on the composite material is. The enhanced adsorption at higher temperatures may be due to increased adsorbent surface active site availability, porosity, and total adsorbent pore volume. The reason for the adsorption enhancement may be that the migration rate of unsymmetrical dimethylhydrazine molecules is increased along with the increase of kinetic energy of the unsymmetrical dimethylhydrazine molecules, the internal diffusion rate of the unsymmetrical dimethylhydrazine in the composite material is increased, and the thickness of a boundary layer around the unsymmetrical dimethylhydrazine adsorbed at a higher temperature is reduced, so that the mass transfer resistance adsorbed in the boundary layer is reduced, the actual processing capacity is integrated, and the processing temperature is preferably 20-40 ℃;
as an improvement of the embodiment of the invention, the removal rate of the composite material to the unsymmetrical dimethylhydrazine is gradually increased along with the increase of the addition amount, because the total active sites of the adsorbent are increased, when the volume of the solution and the initial concentration of the unsymmetrical dimethylhydrazine are fixed, the unsymmetrical dimethylhydrazine is easier to react with the active sites. Meanwhile, the adsorption capacity of the composite material to unsymmetrical dimethylhydrazine gradually decreases with the increase of the dosage, because the unused active sites on the adsorbent increase with the increase of the dosage of the adsorbent, thereby causing the reduction of the adsorption capacity per unit mass of the adsorbent. Preferably, the adding amount of the composite material is 4-16 g/L, and more preferably 8-12 g/L.
As an improvement of the embodiment of the invention, the adsorption capacity is rapidly increased within 30min after the composite material is added into the unsymmetrical dimethylhydrazine solution. After 30min, the adsorption capacity of the composite material to unsymmetrical dimethylhydrazine is slowly increased. When the reaction time reaches 600min, the adsorption capacity and the removal rate of the unsymmetrical dimethylhydrazine are not obviously improved along with the extension of the reaction time, and the adsorption balance is reached in about 720 min. It may be that the composite material has a higher adsorption active site on the surface at the beginning and the adsorption rate is faster, and then the surface active site is gradually occupied by unsymmetrical dimethylhydrazine molecules until the adsorbent reaches the adsorption equilibrium. In summary, the treatment time is preferably 30 to 720 min.
In a third aspect of the embodiments of the present invention, a composition for treating unsymmetrical dimethylhydrazine contamination is provided, wherein the composition comprises the composite material of the first aspect, and the composition further comprises an oxidizing agent.
As an improvement of the embodiments of the present invention, the oxidizing agent is selected from the group consisting of calcium hypochlorite (Ca (ClO))2). In the research, other common oxidants such as potassium permanganate and hydrogen peroxide have been found to generate too much heat during the treatment for high concentration unsymmetrical dimethylhydrazine. The exotherm was low with calcium hypochlorite, and oxidation of unsymmetrical dimethylhydrazine by excess calcium hypochlorite did not produce the carcinogen NDMA (nitrosodimethylamine).
As an improvement of the embodiment of the present invention, in order to further increase the reaction rate, the weight ratio of the composite material to the oxidant is 1: 4-6, more preferably 1: 5.
as an improvement of the embodiment of the invention, in order to further absorb the reaction gasThe composition also contains an inorganic phase-change material, and compared with an organic phase-change material, the inorganic phase-change material is not flammable and has higher heat energy storage capacity and larger melting enthalpy. The inorganic phase-change material is preferably Na2SO4·10H2O and Na2B4O7·10H2At least one of O. In terms of the maximum volatile concentration of the gas, Na is added2B4O7·10H2O effect is superior to Na2SO4·10H2O; in terms of reaction temperature change, Na2SO4·10H2The temperature of O is reduced more quickly, and the effect is better than that of Na2B4O7·10H2And O. The reason for the reduction of the maximum reaction temperature and the maximum volatile concentration of the gas may be two factors: the first is when Ca (ClO)2When reacting with unsym-dimethylhydrazine, the temperature of the reaction system rises rapidly, Na2SO4·10H2O and Na2B4O7·10H2O absorbs heat rapidly and loses water, resulting in the temperature reduction of the reaction system; secondly, after the inorganic phase-change material is added, the adsorbent and the oxidant are wrapped on the surface of the phase-change material particles, so that the specific surface area is increased, and the absorption effect is enhanced. The weight ratio of the composite material to the inorganic phase-change material is 1: 5-10, preferably 1: 6.
the fourth aspect of the embodiment of the invention provides a method for treating unsymmetrical dimethylhydrazine pollutants, which is characterized in that the composite material of the first aspect or the composition of the third aspect is adopted to cover the unsymmetrical dimethylhydrazine pollutants, and the mass percentage concentration of unsymmetrical dimethylhydrazine in the unsymmetrical dimethylhydrazine pollutants is 10-100%. In the actual working process, the unsymmetrical dimethylhydrazine is leaked, so that emergency treatment is required for the pollutants with high concentration. In the course of research, it was found that the use of the composition according to the third aspect of the present invention to coat the pollutants can avoid the volatilization of unsymmetrical dimethylhydrazine, so as to completely adsorb and oxidize the unsymmetrical dimethylhydrazine.
In order to further improve the treatment effect, the treatment conditions are further studied in the embodiments of the present invention, and since the oxidizing agent in the composition reacts to release heat, the treatment temperature is preferably room temperature, specifically, within a range of 15 to 25 ℃; the treatment time is 30-60 min; the dosage of the composite material or the composition is 1-10 g/mL, preferably 2-5 g/mL.
The product and the method can be applied to emergency treatment of unsymmetrical dimethylhydrazine waste liquid accidentally leaked in the processes of propellant production, transportation, transfer filling, storage and analysis. For example, the composite material or composition of the present invention may be mixed thoroughly, ground into powder, placed in a storage tank and pressurized to form a "fire extinguisher" spray canister. When the propellant is accidentally leaked, such as 'running, overflowing, dripping, leaking' and the like, the leaked unsymmetrical dimethylhydrazine liquid can be sprayed in an aiming mode, so that the unsymmetrical dimethylhydrazine liquid can be rapidly adsorbed and annihilated, and the purpose of emergency treatment is achieved. According to the emergency treatment disposal technology aiming at different leakage scenes, leaked substances are quickly and safely treated by physical adsorption and chemical reaction with leaked propellants through methods such as covering, wiping and spraying. Acute poisoning of people is caused by that in a large amount of leakage or closed environment, a large amount of unsymmetrical dimethylhydrazine vapor is inhaled by a human body through a respiratory tract; for workers who have been exposed to low-concentration doses of unsymmetrical dimethylhydrazine for a long period of time, chronic poisoning is caused by the accumulation of low-dose unsymmetrical dimethylhydrazine due to long-term ingestion. The adsorbent can be used for preventing acute poisoning of personnel caused by volatilization of a large amount of unsymmetrical dimethylhydrazine, and can also be placed in a laboratory or a missile position to adsorb a small amount of volatilized low-concentration unsymmetrical dimethylhydrazine gas so as to prevent chronic poisoning of the personnel. Can also be applied to treating the waste water and the waste liquid of the residual hydrazine fuel waste water.
The embodiment of the invention also provides an experimental method for treating the unsymmetrical dimethylhydrazine pollutant, the adopted device is shown in figure 1, the device is a closed experimental box 1, a sealable door for placing articles is reserved, a surface dish 3 is placed in the closed experimental box 1, an electric fan 2 is arranged in the closed experimental box, a unsymmetrical dimethylhydrazine gas detector is arranged on the outer wall of the closed experimental box and used for detecting the gas in the experimental box, and the unsymmetrical dimethylhydrazine gas detector is an unsymmetrical dimethylhydrazine electrochemical gas detector (model: HRP-BX 2000). The detection method comprises the following steps:
s1, turning on an electric fan inside the device;
s2, transferring the unsymmetrical dimethylhydrazine pollutant into a watch glass, and covering the unsymmetrical dimethylhydrazine pollutant by adopting an upper composite material or a composition; preferably, the mass percentage concentration of the unsymmetrical dimethylhydrazine in the unsymmetrical dimethylhydrazine pollutant is 10-100 percent;
s3, placing the cuvette into a closed experiment box, and detecting the concentration of unsymmetrical dimethylhydrazine in the air by using an unsymmetrical dimethylhydrazine gas detector.
The following further illustrates the embodiments of the invention by means of specific embodiments.
Example 1
Firstly, preparing a composite material:
1. under stirring, 3g of graphite powder and 70mL of concentrated H2SO4Mixing, then adding 1.5g NaNO in an ice-water bath3And 9g KMnO4Slowly added to the mixture. Transferring the beaker into a constant-temperature water bath kettle at 35 ℃ and magnetically stirring for 2h, then transferring the beaker into a constant-temperature water bath kettle at 95 ℃, then adding 150mL of deionized water and magnetically stirring for 15 min. Then 500mL of deionized water was added and 20mL of H was added slowly2O2Solution (30 wt%). The solution was filtered and washed several times with 200mL hydrochloric acid (10 wt%) and deionized water by centrifugation to bring the pH close to neutral. And finally, carrying out vacuum freeze drying on the obtained GO for 36 hours to obtain a GO block solid.
2. 6g of chitosan and 100mL of isopropanol are respectively added into a 500mL conical flask, then 100mL of NaOH solution with the mass fraction of 40% is slowly added, and stirring and alkalization are carried out for 1h at 60 ℃. Slowly dropping 100mL of isopropanol solution dissolved with 30g of chloroacetic acid under the stirring condition, completing the reaction within 30min, and then continuing the reaction at 60 ℃ for 4h to obtain the CMC dispersion.
3. Weighing a certain mass of GO in a beaker (the mass of GO is controlled to be m (GO): m (CMC) ═ 1%, 10% and 20%), adding 120mL of deionized water, and performing ultrasonic dispersion for 1h to obtain a GO dispersion liquid.
4. And then mixing the CMC dispersion liquid and the GO dispersion liquid, magnetically stirring for 1 hour, and then ultrasonically dispersing for 1 hour. The reaction was terminated by adding 500mL of absolute ethanol, adjusting the pH of the system to neutral with HCl solution (5mol/L), and the precipitate was washed by centrifugation with absolute ethanol. Drying at 50 ℃, grinding, and sieving (100 mesh) to obtain GO/CMC composites named 1% GO/CMC, 10% GO/CMC, and 20% GO/CMC, respectively.
CMC powders without GO doping were prepared in the same way.
Second, FT-IR analysis of composite materials
The chemical compositions of GO, CMC and GO/CMC composites were characterized by FT-IR. 1731 and 1617cm on GO, as shown in FIG. 2-1The peaks of (a) correspond to the C ═ O bond stretching of the carbonyl or carboxyl groups on GO and the deformation of the hydroxide bonds in water, respectively. At 1068cm-1The nearby peak corresponds to the stretching vibration of C-O-C in the epoxy group, carboxyl group (-COO)-) The absorption peak of the symmetric stretching vibration is positioned at 1426cm-1Nearby, 1617cm-1The nearby peaks correspond to the presence of epoxy groups and the stretching vibration of C ═ C, which indicates that carboxyl and epoxy groups are present in GO, CMC, and GO/CMC, and the peak strengths of CMC and GO/CMC are much stronger than GO, which indicates that the carboxyl and epoxy groups content in CMC and GO/CMC is much greater than GO.
Raman analysis of composite material
Raman analysis is a powerful means of characterizing carbon materials. Raman analysis of GO, CMC and GO/CMC is shown in FIG. 3. GO, 10% GO/CMC and 20% GO/CMC at 1350cm-1And 1595cm-1There are two distinct peaks corresponding to different values of D and G, respectively, and a 1% GO/CMC may show no corresponding peak due to too low GO content. ID of GO, 10% GO/CMC and 20% GO/CMC: the IG values were 0.903, 1.056 and 0.887, respectively. The results show that there is a presence of GO in 10% GO/CMC and 20% GO/CMC, and that 10% GO/CMC has more structural defects than GO.
Morphology analysis of composite material
FIG. 4 shows representative SEM images obtained for GO, CMC, and GO/CMC (scanning electron micrographs for (a) GO, (b) CMC, (c) 1% GO/CMC, (d) 10% GO/CMC, and (e) 20% GO/CMC, respectively, and (f) transmission electron micrographs for 10% GO/CMC). From the SEM images, there was slight agglomeration of GO in fig. 4a, and the sample was a flat layer stack structure. The GO/CMC surface was rougher compared to GO, indicating that GO/CMC may be suitable for adsorption studies. The TEM image is shown in FIG. 4f, GO is uniformly dispersed in the CMC matrix, a large amount of agglomeration phenomenon does not occur, the GO and the CMC are well compounded, and a sheet structure with wrinkled edges is formed.
Example 2
The composite material of example 1 was mixed with an oxidant, specifically consisting of: 0.5g 10% GO/CMC +2.5g Ca (ClO)2；
The composite of example 1 was mixed with oxidant and phase change material, 0.5g 10% GO/CMC +2.5g Ca (ClO)2+3g Na2SO4·10H2O、0.5g 10％GO/CMC+2.5g Ca(ClO)2+3gNa2B4O7·10H2O。
Example 3
The composite material in the embodiment 1 is adopted to treat unsymmetrical dimethylhydrazine pollutants, wherein the pH value of the unsymmetrical dimethylhydrazine pollutants is 8-12, the treatment temperature is 30 ℃, the adding amount is 10g/L, and the contact time is 600 min.
Example 4
The composition in the embodiment 2 is adopted to treat the unsymmetrical dimethylhydrazine waste liquid, and the mass percentage concentration of the unsymmetrical dimethylhydrazine in the unsymmetrical dimethylhydrazine waste liquid is 20 percent; the treatment temperature is room temperature, the adding amount is 3g/mL, and the contact time is 60 min.
Experimental example 1 evaluation of Effect of Low concentration adsorption experiment
The experimental method of the low concentration adsorption experiment comprises the following steps: 50mL of unsymmetrical dimethylhydrazine solution was added to a 150mL Erlenmeyer flask as unsymmetrical dimethylhydrazine contaminant, followed by addition of the composite material prepared in example 1: and (3) 10% of GO/CMC, then placing the conical flask in a 100r/min constant-temperature water bath oscillator for constant-temperature oscillation, sampling, filtering the sample through a needle filter with the porosity of 0.45 mu m, and taking the filtrate to determine the concentration of unsymmetrical dimethylhydrazine by a spectrophotometry method. All individual experiments were repeated three times and the average results were reported. The unsymmetrical dimethylhydrazine concentration was measured according to the sodium ferrocyanide spectrophotometry (GB/T14376).
First, influence of solution pH on adsorption property of composite material
The composite material prepared in example 1 was tested by changing the pH of unsymmetrical dimethylhydrazine contaminant: the effect of 10% GO/CMC on pollutant adsorption is realized, the experimental temperature is 30 ℃, the addition amount of the adsorbent is 10g/L, and the contact time is 720 min. The experimental results obtained are shown in fig. 5.
Figure 5 shows that the adsorption capacity of unsymmetrical dimethylhydrazine on GO/CMC increases with increasing pH. The higher pH condition causes more active sites to appear on the surface of the adsorbent, and influences the interaction between GO/CMC and unsymmetrical dimethylhydrazine molecules.
Secondly, influence of adsorption temperature on adsorption performance of composite material
The composite material prepared in example 1 was tested by varying the temperature of the unsymmetrical dimethylhydrazine contaminant and the temperature of the water bath: the effect of 10% GO/CMC on pollutant adsorption, the pH value of 8, the addition amount of the adsorbent of 10g/L and the contact time of 720 min. The results of the experiment are shown in FIG. 6.
Figure 6 shows the effect of different adsorption temperatures on unsymmetrical dimethylhydrazine adsorption. The adsorption capacity of unsymmetrical dimethylhydrazine increases with increasing temperature, indicating that higher temperature favors the adsorption of unsymmetrical dimethylhydrazine on GO/CMC.
Thirdly, the influence of the adding amount of the adsorbent on the adsorption performance of the composite material
The composite material prepared in example 1 was tested by varying the temperature of the unsymmetrical dimethylhydrazine contaminant and the temperature of the water bath: the effect of 10% GO/CMC on pollutant adsorption, pH value 8, temperature 30 deg.C, contact time 720 min. The results of the experiment are shown in FIG. 7.
FIG. 7 shows the effect of GO/CMC on unsymmetrical dimethylhydrazine adsorption performance when the adsorbent dosage was varied between 4-16 g/L. The removal rate of GO/CMC to unsymmetrical dimethylhydrazine is gradually increased along with the increase of the adding amount. Meanwhile, the adsorption capacity of GO/CMC to unsymmetrical dimethylhydrazine is gradually reduced along with the increase of the addition amount.
Fourth, influence of contact time on adsorption property of composite material
The contact time of the unsymmetrical dimethylhydrazine contaminant and the composite material was varied as measured for the composite material prepared in example 1: the effect of 10% GO/CMC on pollutant adsorption, the pH value is 8, the temperature is 30 ℃, and the adding amount is 10 g/L. The results of the experiment are shown in FIG. 8.
FIG. 8 shows the effect of GO/CMC on unsymmetrical dimethylhydrazine adsorption at different contact times. The adsorption capacity is rapidly increased within 30min after GO/CMC is added into the unsymmetrical dimethylhydrazine solution. After 30min, the adsorption capacity of the adsorbing material to the unsymmetrical dimethylhydrazine is slowly increased. When the reaction time reaches 600min, the adsorption capacity and the removal rate of the unsymmetrical dimethylhydrazine are not obviously improved along with the extension of the reaction time, the adsorption balance is achieved around 720min, the removal rate is 80.11 percent, and the adsorption capacity is 2.07 mg/g. The reason for this explanation may be that GO/CMC surface has higher active adsorption sites at the beginning, the adsorption rate is faster, then because the surface active sites are gradually occupied by unsymmetrical dimethylhydrazine molecules until the adsorbent reaches adsorption equilibrium.
Experimental example 2 treatment of high-concentration waste liquid
Absorption experiment: an experimental device for absorbing and treating high-concentration unsymmetrical dimethylhydrazine waste liquid is shown in figure 1. The experimental device is made of organic glass, the volume of the experimental box is about 4L, the electric fan is arranged in the experimental box, and the actual air flowing state can be simulated by turning on the electric fan. The unsymmetrical dimethylhydrazine gas detector can record the concentration of the unsymmetrical dimethylhydrazine gas in the device in real time. The ambient temperature was 18 ℃ and the air humidity was 35% during the experiment.
The experiment comprises the following specific steps: firstly, a unsymmetrical dimethylhydrazine gas detector is connected to an experimental device, and an electric fan in the device is turned on. Then 1mL of unsymmetrical dimethylhydrazine high-concentration waste liquid (the concentration of unsymmetrical dimethylhydrazine is 20 wt%) is transferred on a watch glass by using a pipette, and then a certain mass of absorbing material is uniformly covered on the surface of the waste liquid. In subsequent experiments, a certain proportion of oxidant and inorganic phase change material are further added into the absorbing material, and meanwhile, a visual thermal imager for temperature measurement is used for measuring the instantaneous reaction temperature in real time. Finally, the glass watch glass was placed in the experimental setup, the stopcock of the experimental setup was screwed on, and the initial time was recorded.
1. Experiments were performed with different composite materials: 2g of GO, 2g of CMC, 2g of 1% GO/CMC, 10% GO/CMC and 20% GO/CMC prepared in example 1, respectively, and the experimental results are shown in FIG. 9.
As can be seen from FIG. 9, the volatilization of the unsymmetrical dimethylhydrazine waste liquid gas alone is rapid, and the upper limit value (268 mg/m) of the instrument detection can be reached within 5min3). The absorption capacity of a certain proportion of GO/CMC is weaker than that of GOHowever, the absorption effect is better than that of CMC, wherein 10% GO/CMC has the best absorption effect, and 35min reaches the detection upper limit value.
2. The composite material and the oxidant are adopted for carrying out the experiment: are each 3g Ca (ClO)2、0.5g 10％GO/CMC+2.5g Ca(ClO)2、1.0g 10％GO/CMC+2.0g Ca(ClO)2、1.5g 10％GO/CMC+1.5g Ca(ClO)2And 2.0g 10% GO/CMC +1.0g Ca (ClO)2The reaction conditions were room temperature and the reaction time was 60 min. The results are shown in FIG. 10 and Table 1.
TABLE 1
As is clear from Table 1 and FIG. 10, the highest concentration of unsymmetrical dimethylhydrazine gas was obtained with the oxidizing agent alone, and the reason for this was unsymmetrical dimethylhydrazine and Ca (ClO)2The reaction temperature is increased, so that part of unsymmetrical dimethylhydrazine which is not reacted in time is heated to accelerate volatilization. After 10% GO/CMC is doped, the reaction intensity is reduced, and the reaction heat release is reduced along with the increase of the addition amount of 10% GO/CMC. Addition of Ca (ClO)2After the reaction, the reaction rate is high, and the concentration of volatilized unsymmetrical dimethylhydrazine gas can reach the maximum value after the reaction is carried out for about 3-4 min. The optimal mixture ratio is that the absorbent and the oxidant are 1: 5, the absorption and oxidation effects of the composite absorbent are optimal, and the maximum volatile concentration reached at 2.5min is only 58.69mg/m3。
3. The experiment is carried out by adding an oxidant and an inorganic phase-change material into the composite material: 0.5g 10% GO/CMC +2.5g Ca (ClO)2、0.5g 10％GO/CMC+2.5g Ca(ClO)2+3g Na2SO4·10H2O、0.5g 10％GO/CMC+2.5g Ca(ClO)2+3g Na2B4O7·10H2And O. The reaction conditions were room temperature and the reaction time was 60min, and the experimental results were as shown in fig. 11, 12 and table 2.
TABLE 2
Compared with organic phase change materials, inorganic phase change materials are not flammable and have higher heat energy storage capacity and larger melting enthalpy. Therefore, the effect of adding the inorganic phase change material on the absorption treatment effect is further added and examined. As is clear from Table 2, FIGS. 11 and 12, Na was added when added2SO4·10H2O and Na2B4O7·10H2After O, the temperature of the reaction system and the concentration of the unsymmetrical dimethylhydrazine gas are both reduced. In terms of the maximum volatile concentration of the gas, Na is added2B4O7·10H2O effect is superior to Na2SO4·10H2O; in terms of reaction temperature change, Na2SO4·10H2The temperature of O is reduced more quickly, and the effect is better than that of Na2B4O7·10H2O。
The reason for the reduction of the maximum reaction temperature and the maximum volatile concentration of the gas may be two factors: the first is when Ca (ClO)2When reacting with unsym-dimethylhydrazine, the temperature of the reaction system is rapidly increased by Na2SO4·10H2O and Na2B4O7·10H2O absorbs heat rapidly and loses water, resulting in the temperature reduction of the reaction system; secondly, after the inorganic phase-change material is added, the adsorbent and the oxidant are wrapped on the surface of the phase-change material particles, so that the specific surface area is increased, and the absorption effect is enhanced.
Experimental example 3
Since organic and inorganic ions dissolved in natural water can interact with organic pollutants to affect their transport and toxicity to test the effect of coexisting ions, tap water and lake water were used to prepare unsymmetrical dimethylhydrazine pollutants, wherein the concentration of unsymmetrical dimethylhydrazine was 25 mg/L. The water quality parameters of tap water and lake water are detailed in Table 3. The reaction temperature is 30 ℃, the pH of unsymmetrical dimethylhydrazine pollutant is 8, the adding amount of the 10 percent GO/CMC composite material prepared in the example 1 is 10g/L, and the processing time is 600 min. The experimental results are shown in FIG. 13.
TABLE 3
| Water quality parameter | Tap water | Lake water |
| UV254 | 0.020 | 0.138 |
| pH | 7.8 | 7.8 |
| Dissolved oxygen | 3.8 | 3.6 |
| Na+(mg L-1) | 101 | 38.8 |
| K+(mg L-1) | 2.44 | 2.50 |
| Mg2+(mg L-1) | 19.8 | 10.6 |
| Ca2+(mg L-1) | 31.0 | 29.2 |
| Cl-(mg L-1) | 49.9 | 17.0 |
| NO3 -(mg L-1) | 2.30 | 0.046 |
| SO4 2-(mg L-1) | 104 | 12.3 |
| TOC | 1.8 | 4.5 |
Fig. 13 shows a comparison between tap water, lake water and deionized water. The results show that tap water and lake water have certain inhibition effect on GO/CMC adsorbing unsymmetrical dimethylhydrazine; but the overall removal was good, 75.1% and 77.7%, respectively. The result shows that the GO/CMC in the embodiment of the invention has good anti-interference capability on natural water quality, which has important significance for practical application thereof.
Experimental example 4
Regeneration performance is one of the most important indicators for evaluating adsorbents. The used GO/CMC was regenerated by ultrasonic in absolute ethanol at room temperature, and then subjected to adsorption experiments (unsymmetrical dimethylhydrazine concentration 25mg/L, reaction temperature 30 ℃, unsymmetrical dimethylhydrazine contaminant pH 8, treatment time 600min, 10g/L addition amount of 10% GO/CMC composite material prepared in example 1) as shown in fig. 14.
Fig. 14 shows that the adsorption efficiency of unsymmetrical dimethylhydrazine decreases with increasing number of adsorption cycles. After the first cycle, the removal rate of the GO/CMC to unsymmetrical dimethylhydrazine is obviously reduced from 80.4 percent of the initial capacity to 63.1 percent. This reduction may be the reason for the release of GO and loss of adsorbent active sites from the GO/CMC composite. After five cycles, the adsorbent has good adsorption performance, which indicates that the adsorbent has regeneration capacity.
Although the present application has been described with reference to preferred embodiments, it is not intended to limit the scope of the claims, and many possible variations and modifications may be made by one skilled in the art without departing from the spirit of the application.
Claims (10)
1. The composite material for treating unsymmetrical dimethylhydrazine pollutants is characterized by being prepared from graphene oxide and carboxymethyl chitosan by a solution blending method, wherein the weight ratio of the graphene oxide to the carboxymethyl chitosan is (1-25): 100, preferably 5 to 20: 100.
2. the composite material for treating unsymmetrical dimethylhydrazine contaminant according to claim 1, wherein the preparation method of the composite material comprises the steps of:
s1, respectively preparing carboxymethyl chitosan dispersion liquid and graphene oxide dispersion liquid;
s2, mixing the graphene oxide dispersion liquid and the carboxymethyl chitosan dispersion liquid, and performing magnetic stirring and ultrasonic dispersion;
s3, adding absolute ethyl alcohol to terminate the reaction, and adjusting the pH value to be neutral;
s4, washing, drying, grinding and sieving to obtain the composite material.
3. The composite material for treating unsymmetrical dimethylhydrazine pollutant according to the claim 2, wherein in S1, the content of carboxymethyl chitosan in the carboxymethyl chitosan dispersion liquid is 0.01-0.05 g/L, preferably 0.02 g/L;
preferably, the preparation method of the carboxymethyl chitosan dispersion comprises the following steps:
s11, preparing an isopropanol solution of chitosan, adding a NaOH solution with the mass fraction of 40%, and stirring at 55-65 ℃ for 1 h; the weight-volume ratio of chitosan to isopropanol is 5-8 g: 100mL, wherein the weight-volume ratio of the chitosan to the NaOH solution is 5-8 g: 120 mL;
s12, adding an isopropanol solution dissolved with chloroacetic acid, wherein the weight ratio of chitosan to chloroacetic acid is 1: 4-6; the adding speed is 1-2 mL/min;
s13, reacting for 4-6 h at 55-65 ℃ to obtain the carboxymethyl chitosan dispersion liquid.
4. The composite material for treating unsymmetrical dimethylhydrazine pollutant according to the claim 2, wherein in S1, the concentration of graphene oxide in the graphene oxide dispersion liquid is 3-10 g/L, preferably 5 g/L; preferably prepared by ultrasonic dispersion;
preferably, in S2, the magnetic stirring is performed for 0.5 to 2 hours, and the ultrasonic dispersion is performed for 0.5 to 2 hours.
5. The composite material for treating unsymmetrical dimethylhydrazine pollutant according to claim 2, wherein in S4, the washing is washed with an organic solvent, preferably an alcoholic organic solvent, more preferably ethanol;
the drying is drying at 50-55 ℃, and the sieving is preferably a 100-mesh sieve.
6. A treatment method of unsymmetrical dimethylhydrazine pollutants is characterized in that the composite material of any one of claims 1 to 5 is adopted for treatment, and the unsymmetrical dimethylhydrazine pollutants are wastewater containing 10 to 40mg/L of unsymmetrical dimethylhydrazine.
7. The process according to claim 6, characterized in that the unsymmetrical dimethylhydrazine contaminant has a pH value greater than 7, more preferably greater than or equal to 12;
the treatment temperature is 20-40 ℃;
the adding amount of the composite material is 4-16 g/L, and preferably 8-12 g/L;
the treatment time is 30-720 min.
8. A composition for treating unsymmetrical dimethylhydrazine contamination, said composition comprising a composite material according to any of claims 1 to 5, wherein said composition further comprises an oxidizing agent, preferably Ca (ClO)2；
Preferably, the weight ratio of the composite material to the oxidant is 1: 4-6, preferably 1: 5.
more preferably, the composition further comprises an inorganic phase change material, and the inorganic phase change material is preferably Na2SO4·10H2O and Na2B4O7·10H2At least one of O;
further preferably, the weight ratio of the composite material to the inorganic phase change material is 1: 5-10, preferably 1: 6.
9. a treatment method of unsymmetrical dimethylhydrazine pollutants is characterized in that the composite material of any one of claims 1 to 5 or the composition of claim 8 is adopted to cover the pollutants, and the mass percent concentration of unsymmetrical dimethylhydrazine in the unsymmetrical dimethylhydrazine pollutants is 10-100%;
the treatment temperature is 15-25 ℃;
the treatment time is 30-60 min;
the dosage of the composite material or the composition is 1-10 g/mL, preferably 2-5 g/mL.
10. An experimental method for unsymmetrical dimethylhydrazine pollutant treatment is characterized by comprising the following steps:
s1, arranging an electric fan in the closed experiment box, connecting the unsymmetrical dimethylhydrazine gas detector to the experiment device, and turning on the electric fan in the device;
s2, removing unsymmetrical dimethylhydrazine pollutants in a watch glass, and covering the pollutants with the composite material of any one of claims 1 to 5 or the composition of claim 8;
s3, placing the cuvette into the closed experiment box, and detecting the concentration of unsymmetrical dimethylhydrazine in the air by using an unsymmetrical dimethylhydrazine gas detector;
preferably, the mass percentage concentration of the unsymmetrical dimethylhydrazine in the unsymmetrical dimethylhydrazine pollutant is 10-100%;
the unsymmetrical dimethylhydrazine gas detector is an unsymmetrical dimethylhydrazine electrochemical gas detector.
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