CN111514513B - Harmless treatment method for drugs - Google Patents
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F11/00—Treatment of sludge; Devices therefor
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- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
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- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a method for harmlessly treating drugs, which comprises the following steps: s100, fully dissolving a drug sample in an aqueous solution to form a drug solution; step S200, adding an oxidant into the drug solution, and putting the drug solution added with the oxidant into a reaction kettle for treatment through a supercritical water oxidation method; and S300, measuring the content of organic matters in the drug solution before and after the reaction to obtain the degradation rate of organic matter components. The effect is as follows: the invention has the advantages of high degradation efficiency (more than 99.99 percent), no secondary pollution and the like, particularly has more obvious advantages for treating drugs and high-toxicity, difficult-degradation and high-concentration toxin-making wastewater, and has the advantages of simple equipment structure, small unit volume and occupied area and the like required by degradation, thereby having wide popularization prospect.
Description
Technical Field
The invention relates to the technical field of drug treatment, in particular to a drug harmless treatment method.
Background
In the prior art, the main method adopted at home and abroad for destroying drugs is incineration or chemical neutralization, and on the basis of the incineration or chemical neutralization, the drugs are destroyed by adopting a plurality of means; however, most of the existing treatment methods cause certain pollution to the environment, and pollutants can also destroy underground water resources, so that the method for performing green and nontoxic drug harmless treatment by adopting supercritical water is found to solve the problem of burden and damage to the environment, and has important practical significance.
The drugs found at present are various in types, and can be classified into three major types from the sources of drugs: natural drugs, semi-synthetic drugs and synthetic drugs; the natural drug is drug extracted directly from original drug plant, such as opium; semi-synthetic drugs are synthesized from natural drugs and chemicals, such as heroin; synthetic drugs are manufactured entirely by organic synthetic methods, such as methamphetamine.
Disclosure of Invention
Therefore, the invention provides a harmless treatment method of drugs with good effect and simple operation, which aims to solve the problem of great environmental pollution generated in the treatment of drugs in the prior art and can treat drug organic matters such as ice toxin, heroin, hemp and the like or intermediates and solutions in the manufacturing process of the drug organic matters; the method for oxidizing the poisonous and harmful organic matters by utilizing the supercritical water solves the problems of secondary pollution and incomplete degradation of the traditional drug treatment.
In order to achieve the above purpose, the invention provides the following technical scheme:
according to a first aspect of the present invention, a method for detoxifying drugs, comprising the steps of: s100, fully dissolving a drug sample in an aqueous solution to form a drug solution; step S200, adding an oxidant into the drug solution, and putting the drug solution added with the oxidant into a reaction kettle for treatment through a supercritical water oxidation method; and S300, measuring the content of organic matters in the drug solution before and after the reaction to obtain the degradation rate of organic matter components.
Further, step S100 further includes: and weighing the drug sample by using an analytical balance, wherein the precision of the analytical balance is higher than 0.0001g, and the mass of the drug sample is 0.1-20% of that of the drug solution.
Further, step S100 further includes: and stirring the drug solution by using a magnetic stirrer for 5-60 minutes.
Furthermore, the drug sample is a drug organic substance or an intermediate and a solution in the drug organic substance manufacturing process.
Furthermore, the oxidant is hydrogen peroxide, and the mass of the hydrogen peroxide added into the drug solution is 5% -10% of that of the drug solution.
Further, the reaction temperature in the reaction kettle is 300-600 ℃, and the pressure is 17-30 MPa.
Further, the supercritical state of the supercritical water oxidation process is a temperature exceeding 374 ℃ and a pressure of 22.1 MPa.
Further, the method comprises a step S400 of judging whether the degradation rate of the organic matter component in the aqueous solution after the reaction is more than 99%, and if so, judging that the method is green and harmless.
Further, the method for separating the drug sample and the solution thereof from the intermediate solution is a liquid phase extraction method.
Further, the reaction kettle is a sealed container.
The invention has the following advantages: the method for harmlessly treating the drugs has the advantages of high treatment efficiency, short reaction time, thorough oxidation, generally removal rate of over 99 percent, and sustainable self-heating reaction when the concentration of organic matters reaches over 2 percent; the reaction is carried out in a sealed container, so that secondary pollution is avoided; the application range is wide, and the method can be almost used for treating all organic wastes; the reactor has simple structure and small volume, can save land occupation in the industrial application process, has lower maintenance cost of equipment and has better economic performance; the resource utilization and isolation of CO2 gas can be realized, and the greenhouse problem caused by emission of CO2 gas is reduced; the method is widely used for degrading toxic and harmful organic matters, and has predictable and great economic and social benefits.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.
The structures, ratios, sizes, and the like shown in the present specification are only used for matching with the contents disclosed in the specification, so as to be understood and read by those skilled in the art, and are not used to limit the conditions that the present invention can be implemented, so that the present invention has no technical significance, and any structural modifications, changes in the ratio relationship, or adjustments of the sizes, without affecting the effects and the achievable by the present invention, should still fall within the range that the technical contents disclosed in the present invention can cover.
Fig. 1 is a flow chart of a method for detoxifying a drug according to some embodiments of the present invention.
Fig. 2 is a phase diagram of water in a method for detoxifying a drug according to some embodiments of the present invention.
Fig. 3 is a graph showing the degradation rate of the methamphetamine under different pressures at 500 ℃ according to some embodiments of the present invention.
Fig. 4 is a graph of the degradation rate of heroin at 500 ℃ under different pressures for a method of detoxification according to some embodiments of the present invention.
Fig. 5 is a graph showing the degradation rate of cannabis at 500 ℃ under different pressures for a method of detoxification according to some embodiments of the present invention.
Fig. 6 is a degradation rate curve of the methamphetamine at different temperatures of 23MPa for a detoxification treatment method according to some embodiments of the present invention.
Fig. 7 is a graph showing the degradation rate of heroin at 23MPa for a method of detoxification according to some embodiments of the present invention.
FIG. 8 is a graph showing the degradation rate of cannabis at 23MPa for a method of detoxification according to some embodiments of the present invention.
Fig. 9 is a schematic diagram of the colloidal gold method detection principle and its determination standard of a harmless treatment method for drugs according to some embodiments of the present invention.
Fig. 10 is a graph showing the degradation rate of methamphetamine at different temperatures according to a method for detoxifying drugs according to some embodiments of the present invention.
Fig. 11 is a graph showing the degradation rate of heroin at different temperatures according to a method for detoxifying drugs according to some embodiments of the present invention.
Fig. 12 is a graph showing the degradation rate of cannabis at different temperatures according to a method for detoxifying drugs according to some embodiments of the present invention.
Fig. 13 is a graph showing degradation rates of amphetamine at different temperatures and under 25MPa for various reaction times in a detoxification method according to some embodiments of the present invention.
Fig. 14 is a graph showing the degradation rate of heroin at different temperatures under 25MPa for a method of detoxification treatment according to some embodiments of the present invention.
FIG. 15 is a graph showing the degradation rate of cannabis at 25MPa for various reaction times at different temperatures according to a method for detoxifying drugs according to some embodiments of the present invention.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. 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.
Example 1
As shown in fig. 1, in the method for detoxifying drugs in this embodiment, step S100 is to dissolve (mix) a drug sample (solid or liquid) in an aqueous solution sufficiently to form a drug solution; step S200, adding an oxidant into the drug solution, and putting the drug solution added with the oxidant into a reaction kettle for treatment through a supercritical water oxidation method; and S300, measuring the content of organic matters in the drug solution before and after the reaction to obtain the degradation rate of organic matter components.
The method comprises the steps of preparing a certain concentration of drugs and water, carrying out high-temperature high-pressure reaction degradation (not required to be soluble in water) in a reaction kettle, and detecting the content of residual organic matters in a treated reaction product to determine the degradation rate achieved after treatment; the supercritical water adopted in the embodiment refers to the reaction conditions that the water temperature and the pressure in the reaction kettle are higher than the critical temperature (374.3 ℃) and the pressure (22.1 MPa); the method takes supercritical water as a reaction medium and oxygen or hydrogen peroxide and the like as oxidants to oxidize drugs in an aqueous solution into H2O、CO2And N2The obtained data is reliable and effective.
The technical effect that this embodiment reaches does: the invention has the advantages of high degradation efficiency (more than 99.99 percent), no secondary pollution and the like, particularly has more obvious advantages for treating drugs and high-toxicity, difficult-degradation and high-concentration toxin-making wastewater, and has the advantages of simple equipment structure, small unit volume and occupied area and the like required by degradation, thereby having wide popularization prospect.
Example 2
As shown in fig. 1, the method for detoxifying drugs in this embodiment includes all the technical features of embodiment 1, and in addition, the method further includes weighing and stirring the drugs before the toxic drug powder is sufficiently dissolved in water, and step S100 further includes: weighing the drug sample by using an analytical balance, wherein the precision of the analytical balance is higher than 0.0001g, and the mass of the drug sample is 0.1-20% of that of the drug solution; step S100 further includes: stirring the drug solution by using a magnetic stirrer for 5-60 minutes; the drug sample is drug organic matter or intermediate and solution in the drug organic matter manufacturing process, such as, but not limited to, methamphetamine, heroin, hemp, etc., and can also be used for other toxic organic compounds, organic wastewater, sludge, solid waste, etc.; the oxidant is hydrogen peroxide, and the mass of the hydrogen peroxide added into the drug solution is 5-10% of that of the drug solution; the reaction temperature in the reaction kettle is 300-600 ℃, and the pressure is 17-30 MPa; the supercritical state of the supercritical water oxidation method is that the temperature exceeds 374 ℃ and the pressure is 22.1 MPa; the method also comprises a step S400 of judging whether the degradation rate of the organic matter components in the reacted aqueous solution is more than 99%, and if so, judging that the method is green and harmless; the method for separating the drug sample and the solution thereof from the intermediate solution is a liquid phase extraction method; the reaction kettle is a sealed container.
Specifically, the treatment method includes normal temperature and pressure state, subcritical state (near 374 deg.C, 22.1MPa) and supercritical state (over 374 deg.C, 22.1 MPa).
The beneficial effects in this embodiment are: the method for harmlessly treating the drugs has the advantages of high treatment efficiency, short reaction time, thorough oxidation, generally removal rate of over 99 percent, and sustainable self-heating reaction when the concentration of organic matters reaches over 2 percent; the reaction is carried out in a sealed container, so that secondary pollution is avoided; the application range is wide, and the method can be almost used for treating all organic wastes; the reactor has simple structure and small volume, can save land occupation in the industrial application process, has lower maintenance cost of equipment and has better economic performance; the resource utilization and isolation of CO2 gas can be realized, and the greenhouse problem caused by emission of CO2 gas is reduced; the method is widely used for degrading toxic and harmful organic matters, and has predictable and great economic and social benefits.
It should be noted that: under normal conditions, water always exists in one of three common states of water vapor, liquid water and ice, is considered to be a polar solvent, is suitable for dissolving most electrolytes including salts, is slightly soluble or insoluble to gas and most nonpolar organic matters, and the density of water at normal temperature hardly changes along with pressure; however, if the temperature and pressure of water are raised above the critical temperature (374.3 ℃) and critical pressure (22.1MPa), the density, dielectric constant, viscosity, diffusion coefficient, etc. of water are changed greatly, and the water is in a new fluid state different from the gas state, the liquid state and the solid state, i.e. supercritical state (as shown in fig. 2), the water in this state is called supercritical water, and compared with the water under the conventional conditions, the supercritical water has many unique physical and chemical properties, such as low polarity of water molecules, weak hydrogen bonds, low dielectric constant, and mutual solubility of organic matters and most gases with the supercritical water.
Wherein: the solubility of supercritical water compared to normal water is shown in the following table.
| Solute | Ordinary water | Supercritical water |
| Gas (es) | Slightly soluble/insoluble | Is easy to dissolve |
| Organic matter | Slightly soluble/insoluble | Is easy to dissolve |
| Inorganic substance | Is easy to dissolve | Slightly soluble/insoluble |
In the specific implementation process of the harmless treatment method for the drugs, firstly, a selected drug sample is mixed with water, then the mixture is stirred by a magnetic stirrer to be uniformly mixed with the water, a certain amount of hydrogen peroxide is added, then the mixture is placed into a high-temperature high-pressure container, and the content of organic matters in the mixture is detected to determine whether the drug can be well degraded or not; testing the treatment of various drugs according to the requirements, enabling samples of the drugs to react in supercritical water, and analyzing the components of the treated samples to obtain the change of organic components of the drugs before and after treatment; the above embodiment can also be used for other toxic organic compounds, organic wastewater, sludge, solid waste and the like; the technology can also recover chemical materials from the high molecular materials, and the method can decompose or degrade high molecular wastes to obtain gas, liquid or solid products; most toxic organic compounds can be reliably and effectively degraded and green-emitted by means of a supercritical oxidation method.
Specifically, the treatment method is a supercritical state (over 374 ℃ and 22.1MPa), the temperature for reaction is 300-600 ℃, and the pressure is 17-30 MPa; weighing and stirring the poisonous drug powder before the poisonous drug powder is fully dissolved in water; the drug which can be treated is drug organic matters such as ice toxin, heroin, hemp and the like or intermediate and solution in the manufacturing process thereof; the used oxidant is hydrogen peroxide, and the mass of the added hydrogen peroxide is 5 to 10 percent of the mass of the drug solution; when the degradation rate of organic matter components in the water solution after reaction is detected to be more than 99 percent, the method is judged to be green and harmless; the method for separating the drugs and the solution thereof from the intermediate solution is a liquid phase extraction method.
Specifically, the method for harmless treatment of drugs comprises the steps of taking drugs as treatment objects, accurately weighing the drugs, preparing the drugs and water into a certain concentration, and putting prepared drug solution and hydrogen peroxide into an experimental device for testing; and detecting the concentration change of the organic matters before and after the reaction to determine whether the drugs are degraded.
Specifically, the method for harmless treatment of drugs is a supercritical water oxidation method, i.e., a method for determining the degradation rate of drug organic matters or intermediates and solutions in the manufacturing process of the drug organic matters after treatment for a certain time under certain conditions (certain temperature, pressure, oxidant concentration and the like) by comparing the content change of the organic matters in the solutions before and after reaction; for drug destruction, the supercritical water oxidation method is a green and reliable method and can be widely applied.
Specifically, for the drug with determined components, the oxidation speed of the organic matter components of the drug under a certain temperature and pressure is determined, and the degradation rate of the drug is also determined; if there is a significant increase in degradation rate at a certain temperature and pressure, while other conditions (e.g., oxidant, residence time) are unchanged, it is presumed that this is due to the fact that the nature of the water in the reaction has changed; the water solution improves the oxidation speed of toxic and harmful organic components in the drugs, thereby improving the degradation rate; the influence of different temperature and pressure on the degradation rate is different, and the degradation rate of the conditions under different temperature and pressure can be determined through experiments; the influence of the temperature on the harmless treatment of the drugs is presumed by comparing the degradation rate differences of the drugs under the same pressure and different temperatures; under the same pressure, the temperature rise can obviously improve the degradation rate of toxic and harmful organic matter components in the drugs, and the degradation rate of the organic matter can reach more than 99 percent within 1 minute at 550 ℃ and more than 23 MPa.
Example 3
As shown in FIG. 3, in the method for detoxifying drugs in this embodiment, the sample is an aqueous solution of methamphetamine (methamphetamine), and the concentration of methamphetamine and water is 1.5mg/ml, and the mixture is stirred for use. Mixing glacial toxic water solution with 30% H2O2Adding the mixture into a reaction kettle, sealing a reaction heating device, checking the air tightness between each valve and each nut, inserting a thermocouple and starting heating after the checking is finished, horizontally arranging the reaction device at the reaction temperature of 500 ℃, wherein the horizontal distance from the reaction device to the wall is 1 meter, no shielding object is arranged around the reaction device, the horizontal distance from the reaction device to the air supply port side of a building is not less than 1 meter, and the pressure is 21MPa, 23MPa, 25MPa and 27MPa respectively, and the other conditions are not changed. As can be seen from the content and the change of the organic matter components, when the pressure reaches 23MPa, 25MPa and 27MPa, the ice toxicity in the solution after the reaction is basically degraded and has little change, and is less than 1 percent of the ice toxicity content in the initial solution. Indicating that the solution of methamphetamine has been converted to water and CO2However, the degradation rate at 21MPa is significantly higher than 23MPa or more, which indicates that the pressure has no significant effect on the promotion of the reaction when the reaction conditions reach a supercritical state.
Example 4
As shown in FIG. 4, in the method for detoxifying drugs in this example, a sample is an aqueous solution of heroin (diacetylmorphine), and the sample and water are mixed to a concentration of 1.5mg/ml, and stirred for later use. Mixing heroin water solution with 30% H2O2Adding the mixture into a reaction kettle, sealing a reaction heating device, checking the air tightness between each valve and each nut, inserting a thermocouple and starting heating after the checking is finished, horizontally arranging the reaction device at the reaction temperature of 500 ℃, and keeping the pressure at 21MPa, 23MPa, 25MPa and 27MPa, wherein the horizontal distance from the reaction device to the wall is 1m, no shielding object is arranged around the reaction device, and the horizontal distance to the air supply port side of a building is not less than 1 m. It can be seen from the content and change of organic components that when the pressure reaches 23MPa, 25MPa, 27MPa, the heroin component in the solution after reaction is basically degraded, and the change is not much less than 1% of the heroin content in the initial solution. Indicating that the heroin solution has been converted to H2O and CO2(ii) a But at 21MThe degradation rate at Pa is obviously not as high as 23MPa or more, which shows that the pressure has no obvious effect on promoting the reaction when the reaction conditions reach a supercritical state.
Example 5
As shown in fig. 5, in the method for detoxifying drugs in this embodiment, a sample is a hemp (tetrahydrocannabinol) aqueous solution, and the sample and water are mixed to a concentration of 1.5mg/ml, and stirred for use. Mixing hemp water solution with 30% H2O2Adding the mixture into a reaction kettle, sealing a reaction heating device, checking the air tightness between each valve and each nut, inserting a thermocouple and starting heating after the checking is finished, wherein the horizontal distance from the reaction device to a wall is 1 meter, no shielding object is arranged around the reaction device, the horizontal distance from the reaction device to the air supply opening of a building is not less than 1 meter, and the reaction device is horizontally installed. The reaction temperature is 500 ℃, the pressure is 21MPa, 23MPa, 25MPa and 27MPa, and other conditions are unchanged. As can be seen from the content and the change of the organic matter components, when the pressure reaches 23MPa, 25MPa and 27MPa, the hemp components in the solution after the reaction are basically degraded and have little change, and the content is less than 1 percent of the hemp content in the initial solution. Indicating that the hemp solution has been converted to water and CO2(ii) a However, the degradation rate at 21MPa was not significantly lower than that at 23MPa or more, indicating that the reaction promoting effect of pressure was not significant when the reaction conditions reached the supercritical state.
Example 6
As shown in FIG. 6, in the method for detoxifying drugs in this embodiment, the sample is an aqueous solution of methamphetamine (methamphetamine), the sample is mixed with water to a concentration of 1.5mg/ml, the mixture is stirred for use, and the sample is mixed with 30% H2O2Adding the mixture into a reaction kettle, sealing a reaction heating device, checking the air tightness between each valve and each nut, inserting a thermocouple and starting heating after the checking is finished, wherein the horizontal distance from the reaction device to a wall is 1 meter, no shielding object is arranged around the reaction device, the horizontal distance from the reaction device to the air supply opening of a building is not less than 1 meter, and the reaction device is horizontally installed. The reaction pressure is 23MPa, the temperature is 350 ℃, 400 ℃, 450 ℃ and 500 ℃, and other conditions are unchanged. It can be seen from the content and change of organic components that when the pressure reaches 400 deg.C, 450 deg.C and 500 deg.C, the ice toxicity in the solution after reaction is basically reducedThe degradation rate of the solution is improved by the temperature after the solution is completely dissolved, and is less than 10 percent of the ice toxicity content in the initial solution. Indicating that the solution of methamphetamine has been converted to water and CO2However, the degradation rate of only 42% at 350 ℃ is obviously not in accordance with the green and efficient treatment method, which indicates that the temperature has a great promoting effect on the reaction when the reaction condition reaches a supercritical state.
Example 7
As shown in FIG. 7, in the method for detoxifying drugs in this example, a sample is an aqueous solution of heroin (diacetylmorphine), the sample is mixed with water to a concentration of 1.5mg/ml, the mixture is stirred for use, and the resulting solution is mixed with 30% H2O2Adding the mixture into a reaction kettle, sealing a reaction heating device, checking the air tightness between each valve and each nut, inserting a thermocouple and starting heating after the checking is finished, wherein the horizontal distance from the reaction device to a wall is 1 meter, no shielding object is arranged around the reaction device, the horizontal distance from the reaction device to the air supply opening of a building is not less than 1 meter, and the reaction device is horizontally installed. The reaction pressure is 23MPa, the temperature is 350 ℃, 400 ℃, 450 ℃ and 500 ℃, and other conditions are unchanged. It can be seen from the content and change of organic components that when the conditions are reached, the heroin in the solution after the reaction is basically degraded at 400 ℃, 450 ℃ and 500 ℃, the temperature increases the degradation rate of the reaction system and is less than 10 percent of the heroin content in the initial solution. Indicating that the heroin solution has been converted to H2O and CO2(ii) a But the degradation rate at 350 ℃ only reaches 35 percent, which obviously does not meet the requirement of green and non-toxicity, and shows that the temperature has the function of promoting the degradation reaction when the reaction condition reaches the supercritical state.
Example 8
As shown in FIG. 8, in the method for detoxifying a drug in this example, a cannabis sativa (tetrahydrocannabinol) aqueous solution was used as a sample, the sample was mixed with water to a concentration of 1.5mg/ml, and the mixture was stirred and mixed with 30% H2O2Adding into a reaction kettle, sealing the reaction heating device, checking the air tightness between each valve and the nut, inserting a thermocouple and starting heating after the checking is finished, wherein the horizontal distance of the reaction device to the wall is 1m, no shielding object is arranged around the device, and the device is heated until reaching the buildingThe horizontal distance of the object air supply opening side is not less than 1m, and the device is horizontally installed. The reaction pressure is 23MPa, the temperature is 350 ℃, 400 ℃, 450 ℃ and 500 ℃, and other conditions are unchanged. As can be seen from the content and change of organic components, when the conditions are reached, the hemp in the solution is basically degraded at 400 ℃, 450 ℃ and 500 ℃, the degradation rate of the reactant is improved at high temperature, and the content of the hemp in the initial solution is below 5 percent. Indicating that the hemp sample solution had been converted to H2O and CO2However, the degradation rate of only 39% at 350 ℃ obviously does not meet the requirements of green and non-toxicity, which indicates that the temperature has the promotion effect on the reaction when the reaction condition reaches the supercritical state.
Example 9
As shown in fig. 9, a harmless treatment method for a drug in the present embodiment is a simplified diagram of colloidal gold method detection and determination criteria.
Example 10
As shown in FIG. 10, in the method for detoxifying drugs according to this embodiment, the solution of methamphetamine is tested by the colloidal gold method at room temperature, 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C, and 500 deg.C under one atmosphere. The results show that the detection results show positive at normal temperature, 300 ℃ and 350 ℃, the detection results show negative at 400 ℃, 450 ℃ and 500 ℃, the degradation effect is not obvious at the subcritical state (the degradation rate is 35-60 percent at the moment), when the reaction condition reaches the supercritical state (the degradation rate is more than 85 percent), the reaction is rapidly carried out, the macromolecules are decomposed into micromolecules, and finally the micromolecules are rapidly oxidized into nontoxic and harmless H2O、CO2、N2And the process of precipitation of inorganic salts.
Example 11
As shown in FIG. 11, in the method for detoxifying drugs according to this embodiment, heroin is detected by colloidal gold method at room temperature, 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C, and 500 deg.C under one atmosphere. The results show that the detection results at normal temperature, 300 ℃ and 350 ℃ show positive, the detection results at 400 ℃, 450 ℃ and 500 ℃ show negative, and the result shows that the degradation effect is not obvious (the degradation rate is 30-60%) when the subcritical condition is reached to the supercritical stateIn the state (the degradation rate is more than 87%), the reaction is rapidly carried out, large molecules are decomposed into small molecules, and finally the small molecules are rapidly oxidized into nontoxic and harmless H2O、CO2、N2And the process of precipitation of inorganic salts.
Example 12
As shown in FIG. 12, in the harmless treatment method of the drugs in this embodiment, the results of colloidal gold method detection of cannabis processed at normal temperature, 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C, and 500 deg.C under one atmosphere pressure are shown. The result shows that the detection result shows positive at normal temperature, 300 ℃ and 350 ℃, the detection result shows negative at 400 ℃, 450 ℃ and 500 ℃, and the result shows that the degradation effect is not obvious at the subcritical state (the degradation rate is 35-70 percent at the moment), but when the condition reaches the supercritical state (the degradation rate is more than 90 percent), the reaction is rapidly carried out, the macromolecule is decomposed into micromolecule, and finally the micromolecule is rapidly oxidized into nontoxic and harmless H2O、CO2、N2And inorganic salt precipitated materials.
Example 13
As shown in fig. 13, in the method for harmless treatment of drugs in this embodiment, the degradation results of the ice toxin at 25MPa at 350 ℃, 400 ℃, 450 ℃ and 500 ℃ show that the degradation rate does not reach the index of safe emission (the degradation rate is 46%) at 350 ℃, the degradation rate reaches the supercritical state at the temperature exceeding 375 ℃, the degradation rate is obviously improved at above 400 ℃, the degradation rate can reach 98.5%, and the reaction product is mainly non-toxic and harmless H2O、CO2、N2And inorganic salt precipitated materials.
Example 14
As shown in FIG. 14, in the harmless treatment method of the drug in this embodiment, the degradation results of heroin at 25MPa, 350 deg.C, 400 deg.C, 450 deg.C and 500 deg.C show that the degradation rate does not reach the standard of safe discharge (degradation rate of 59%) at 350 deg.C or lower, when the temperature exceeds 375 deg.C, the supercritical state is reached, when the humidity is above 400 deg.C, the degradation rate is obviously increased, when the humidity is above 99.2%, the reaction product is mainly H2O、CO2、N2And inorganic salt precipitated materials.
Example 15
As shown in FIG. 15, in the harmless treatment method of the drugs in this embodiment, the degradation results of cannabis at 350 deg.C, 400 deg.C, 450 deg.C and 500 deg.C under 25MPa show that the degradation rate does not reach the index of safe discharge (the degradation rate is 65%) at the temperature below 350 deg.C, the degradation rate reaches the supercritical state at the temperature above 375 deg.C, the degradation rate is significantly increased at the temperature above 400 deg.C, the degradation rate at this time can reach 99.7%, and the reaction product is mainly non-toxic and harmless H2O、CO2And inorganic salt precipitated materials.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
In the present specification, the terms "upper", "lower", "left", "right", "middle", and the like are used for clarity of description, and are not intended to limit the scope of the present invention, and changes or modifications in the relative relationship may be made without substantial changes in the technical content.
Claims (3)
1. A method for harmlessly treating drugs is characterized by comprising the following steps:
s100, fully dissolving a drug sample in an aqueous solution to form a drug solution;
step S200, adding an oxidant into the drug solution, and putting the drug solution added with the oxidant into a reaction kettle for treatment through a supercritical water oxidation method;
s300, measuring the content of organic matters in the drug solution before and after the reaction to obtain the degradation rate of organic matter components;
step S100 further includes: weighing the drug sample by using an analytical balance, wherein the precision of the analytical balance is higher than 0.0001g, and the mass of the drug sample is 0.1-20% of that of the drug solution;
step S100 further includes: stirring the drug solution by using a magnetic stirrer for 5-60 minutes;
the drug sample is any one of solid ice toxin, solid heroin, solid hemp, ice toxin solution, heroin solution and hemp solution;
the oxidant is hydrogen peroxide, and the mass of the hydrogen peroxide added into the drug solution is 5-10% of that of the drug solution;
the reaction temperature in the reaction kettle is 400-600 ℃, and the pressure is 23-30 MPa;
the supercritical state of the supercritical water oxidation method is that the temperature exceeds 374 ℃ and the pressure exceeds 22.1 MPa;
the method also comprises a step S400 of judging whether the degradation rate of the organic matter components in the reacted aqueous solution is more than 99%, and if the judgment result is yes, judging that the method is green and harmless.
2. The method of claim 1, wherein the separation of the drug sample and solution from the intermediate solution is liquid extraction.
3. The method according to claim 1, wherein the reaction vessel is a sealed vessel.
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| CN113105019A (en) * | 2021-04-08 | 2021-07-13 | 广西国睿工程咨询有限公司 | Method for decomposing morphine in pharmaceutical factory waste liquid |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6127591A (en) * | 1998-11-30 | 2000-10-03 | Battelle Memorial Institute | Method of digesting an explosive nitro compound |
| CN103403192A (en) * | 2010-11-01 | 2013-11-20 | 雷克燃料公司 | Process for controlled liquefaction of a biomass feedstock by treatment in hot compressed water |
| CN106563685A (en) * | 2016-10-14 | 2017-04-19 | 汉义生物科技（北京）有限公司 | Method for destroying tetrahydrocannabinol |
| CN110038251A (en) * | 2019-05-30 | 2019-07-23 | 汉义生物科技（北京）有限公司 | A method of degradation cannboid |
-
2020
- 2020-05-06 CN CN202010372945.1A patent/CN111514513B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6127591A (en) * | 1998-11-30 | 2000-10-03 | Battelle Memorial Institute | Method of digesting an explosive nitro compound |
| CN103403192A (en) * | 2010-11-01 | 2013-11-20 | 雷克燃料公司 | Process for controlled liquefaction of a biomass feedstock by treatment in hot compressed water |
| CN106563685A (en) * | 2016-10-14 | 2017-04-19 | 汉义生物科技（北京）有限公司 | Method for destroying tetrahydrocannabinol |
| CN110038251A (en) * | 2019-05-30 | 2019-07-23 | 汉义生物科技（北京）有限公司 | A method of degradation cannboid |
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