A method and catalyst preparation for catalytic degradation of morphine and fentanyl controlled substances at room temperature

Abstract

The application discloses a normal-temperature catalytic degradation method for morphine and fentanyl controlled drugs and preparation of a catalyst, and belongs to the technical field of harmless treatment of drugs, and comprises the following steps: step a, dissolving hematin and vitamin B12 in deionized water to obtain solution A; step b, dispersing silicon sol in deionized water to obtain solution B; step c, slowly adding solution A into solution B, and then stirring under heating, and then removing a solvent, and grinding a solid product obtained; placing the ground solid product in a tube furnace, and pyrolyzing the solid product to obtain a solid powder; and performing an etching step on the solid powder, washing the solid powder with deionized water until neutral, and drying the solid powder to obtain a bimetallic carbon-nitrogen catalyst. The catalyst can realize normal-temperature degradation of morphine and other controlled drugs.

Description

Technical Field

[0001] This invention belongs to the field of drug harmless treatment technology, and particularly relates to a method for room temperature catalytic degradation of morphine and fentanyl-class controlled drugs and the preparation of the catalyst. Background Technology

[0002] In the medical field, potent anesthetic and analgesic drugs such as morphine and fentanyl are frequently used during surgical anesthesia and postoperative analgesia. Due to individual patient differences and the uncertainty of surgical procedures, the standard dose package for a single use is often not completely used. According to the National Regulations on the Administration of Narcotic Drugs and Psychotropic Substances and related management regulations, any unused remaining drug solution must be destroyed and its leakage is strictly prohibited.

[0003] Currently, the conventional method for medical institutions to dispose of residual liquids from controlled drugs is to directly pour the liquid into the sewer system under monitoring equipment and dual supervision, ultimately discharging it into the institution's wastewater treatment system. However, this traditional method has significant drawbacks. On the one hand, residual anesthetic and analgesic drugs, as organic pollutants, may still pose potential ecological and health risks to surface water and groundwater sources, even after hospital wastewater treatment. On the other hand, the strict, traceable, and end-to-end control of anesthetic and psychotropic drugs is hampered by the cumbersome record-keeping and difficult-to-monitor methods of dumping disposal, necessitating a safer, more efficient, environmentally friendly, and controllable on-site disposal technology. Therefore, developing an environmentally friendly technology that can rapidly degrade residual controlled drugs into harmless inorganic substances (such as carbon dioxide, water, and inorganic salts) at room temperature has significant practical implications and application value. Summary of the Invention

[0004] In view of the above-mentioned shortcomings and deficiencies of the prior art, the present invention provides a room temperature catalytic oxidation degradation method, which relates to a room temperature catalytic degradation method and catalyst preparation for morphine and fentanyl-class controlled drugs, so as to achieve room temperature degradation of controlled drugs such as morphine.

[0005] To achieve the above objectives, the main technical solutions adopted by the present invention include: A method for preparing a catalyst for the room-temperature catalytic degradation of morphine and fentanyl-class controlled drugs includes the following steps: Step a, to add heme C 34 H 32 N4O4Fe and Vitamin B12C 63 H 88 CoN 14 O 14 P dissolves in deionized water to obtain solution A; Step b: Disperse the silica sol in deionized water to obtain solution B; Step c: Slowly add solution A dropwise to solution B, heat and stir at 40℃~80℃ for 3~6 hours, then remove the solvent by heating to obtain a solid product, and grind the obtained solid product; place the ground solid product in a tube furnace and heat to 600~900℃ under a nitrogen atmosphere to pyrolyze the product to obtain a pyrolysis solid powder; perform an etching step on the pyrolysis solid powder, including soaking the obtained pyrolysis solid powder in hydrofluoric acid, stirring at room temperature, centrifuging to remove the solution, and repeating the etching step until the silicon template agent is completely removed; wash with deionized water until neutral, and dry to obtain a bimetallic carbon-nitrogen catalyst.

[0006] Further, in step a, the molar ratio of heme to vitamin B12 is 1:1 to 3:1, and the concentration of the mixture in the aqueous solution is 10 to 50%.

[0007] Furthermore, in step b, the amount of silica sol used is such that the mass ratio of silica sol to heme is 1:1 to 4:1, and the mass concentration of silica sol in water is 6 to 10%.

[0008] Further, in step c, solution A is slowly added dropwise to solution B, and the mixture is heated and stirred at 60°C for 4 hours.

[0009] Furthermore, in step c, removing the solvent by heating means heating to 100°C to remove the solvent.

[0010] Further, in step c, the ground solid product is placed in a tube furnace and heated to 800°C under a nitrogen atmosphere for 2 hours to pyrolyze, thereby obtaining the pyrolyzed solid powder.

[0011] Furthermore, the catalyst is a porous carbon-nitrogen material containing cobalt and iron, with a specific surface area of ​​1100~1200 m² / g and a total pore volume of 1.5~1.6 cm³ / g; in the catalyst, the mass content of Fe is 1.8%~1.9% and the mass content of Co is 1.6%~1.7%.

[0012] A method for the room-temperature catalytic degradation of morphine and fentanyl-class controlled drugs is disclosed. The catalyst prepared by the catalyst preparation method is used for the room-temperature catalytic degradation of morphine. The catalyst is dispersed in deionized water, and morphine is added. The mass ratio of morphine to catalyst is 1:1 to 1:5. Hydrogen peroxide with a concentration of 3-7% is added to the solution at a molar ratio of hydrogen peroxide to morphine of 2:1 to 20:1 under stirring. The reaction is carried out at room temperature for 10-120 minutes to achieve the degradation and mineralization of morphine.

[0013] A method for the room-temperature catalytic degradation of morphine and fentanyl-class controlled drugs is disclosed. The catalyst prepared by the aforementioned catalyst preparation method is used for the room-temperature catalytic degradation of remifentanil. The catalyst is dispersed in deionized water, and remifentanil is added at a mass ratio of 1:1 to 1:5. Then, 3-7% hydrogen peroxide is added to the solution at a molar ratio of 2:1 to 20:1 between hydrogen peroxide and remifentanil under stirring. The reaction is carried out at room temperature for 10-120 minutes to achieve the degradation and mineralization of remifentanil.

[0014] A method for the room-temperature catalytic degradation of morphine and fentanyl-class controlled drugs is disclosed. The catalyst prepared by the catalyst preparation method is used for the room-temperature catalytic degradation of fentanyl. The catalyst is dispersed in deionized water, and fentanyl is added. The mass ratio of fentanyl to catalyst is 1:1 to 1:5. Then, 3-7% hydrogen peroxide is added to the solution at a molar ratio of hydrogen peroxide to remifentanil of 2:1 to 20:1 under stirring. The reaction is carried out at room temperature for 10-120 min to achieve the degradation and mineralization of remifentanil.

[0015] The beneficial effects of this invention are as follows: The catalyst prepared by this invention is a mesoporous bimetallic carbon-nitrogen material catalyst, which requires no additional energy input and can effectively degrade high concentrations of morphine under normal temperature and pressure conditions. The degradation efficiency is highly efficient and stable, and compared with traditional methods such as Fenton oxidation, it has advantages such as rapid reaction, small reagent dosage, and low cost, making it more environmentally friendly, clean, and energy-saving.

[0016] The bimetallic carbon-nitrogen catalyst of this invention has simple raw material availability, high yield, strong stability, and can be repeatedly recycled without causing secondary pollution. It can efficiently activate hydrogen peroxide to produce active oxides for the degradation and removal of organic matter. The catalyst of this invention catalyzes controlled sedatives such as morphine with advantages such as rapid reaction, small dosage, low cost, and no secondary pollution. It can effectively solve the environmentally friendly disposal problem of unused controlled drugs in the medical field and is suitable for the rapid on-site degradation treatment of controlled drugs such as morphine. Attached Figure Description

[0017] Figure 1 XPS spectrum of FeCo-NC; Figure 2 The fine structure spectrum of C 1s in the XPS spectrum of FeCo-NC; Figure 3 The fine structure spectrum of N 1s in the XPS spectrum of FeCo-NC; Figure 4 The fine structure spectrum of Fe 2p in the XPS spectrum of FeCo-NC; Figure 5 The fine structure spectrum of Co 2p in the XPS spectrum of FeCo-NC; Figure 6 SEM image of FeCo-NC at a unit length of 500 nm; Figure 7 This is a SEM image of FeCo-NC at a unit length of 250 nm. Detailed Implementation

[0018] To better explain and facilitate understanding of the present invention, the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

[0019] This invention provides a method for preparing a catalyst for the room-temperature catalytic degradation of morphine and fentanyl-class controlled drugs, comprising the following steps: Step a, to add heme C 34 H 32 N4O4Fe and Vitamin B12C 63 H 88 CoN 14 O 14 P is dissolved in deionized water to obtain solution A. Specifically, in step a, the molar ratio of heme to vitamin B12 is 1:1 to 3:1, and the concentration of the mixture in the aqueous solution is 10% to 50%.

[0020] Step b: Disperse the silica sol in deionized water to obtain solution B. Specifically, in step b, the mass ratio of silica sol to heme is 1:1 to 4:1, and the mass concentration of silica sol in water is 6% to 10%.

[0021] Step c: Slowly add solution A dropwise to solution B, heat and stir at 40℃~80℃ for 3~6 hours, specifically at 60℃ for 4 hours, then raise the temperature to 100℃ to remove the solvent, obtaining a solid product. Grind the obtained solid product. Place the ground solid product in a tube furnace and pyrolyze it at 600~900℃ under a nitrogen atmosphere, specifically at 800℃ for 2 hours, to obtain a pyrolysis solid powder. Etch the pyrolysis solid powder, including soaking it in hydrofluoric acid, stirring at room temperature, centrifuging to remove the solution, and repeating the etching step until the silicon template is completely removed; wash with deionized water until neutral, and dry to obtain a bimetallic carbon-nitrogen catalyst.

[0022] Example 1 Solution A was prepared by dissolving 5 mmol of heme and 5 mmol of vitamin B12 in 20 mL of deionized water. Then, 2.5 g of silica sol was dispersed in 40 mL of deionized water to obtain solution B. Solution A was slowly added dropwise to solution B, and the mixture was heated and stirred at 60 °C for 4 hours. The solvent was removed by raising the temperature to 100 °C, and the resulting solid was ground. The solid was then placed in a tube furnace and heated to the pyrolysis temperature of 800 °C at a rate of 5 °C / min under a nitrogen atmosphere, and held at this temperature for 2 hours. The resulting black powder was soaked in 10% hydrofluoric acid and stirred at room temperature for 12 hours. The solution was removed by centrifugation, and the etching steps were repeated to completely remove the silica template agent from the material. The material was then washed with deionized water until neutral and dried in a vacuum drying oven at 80 °C to obtain a high specific surface area bimetallic carbon-nitrogen material, Fe-Co-NC-X (where X is the calcination temperature).

[0023] ICP quantitative analysis: The metal content of Fe-Co-NC-800 was quantitatively analyzed by ICP. The results showed that the mass contents of Fe and Co in this catalyst were 1.87% and 1.62%, respectively.

[0024] N2 adsorption-desorption: The specific surface area of ​​N2 was measured to be 1150 m² / g through physical adsorption-desorption experiments. 2 .g -1 The total pore volume is 1.57 cm³. 3 .g -1 .

[0025] The following are the product characterization results of Fe-Co-NC-800 prepared in Example 1.

[0026] XPS characterization: The surface properties and chemical state of FeCo-NC were analyzed by XPS. Figure 1 shows the XPS spectrum of FeCo-NC, indicating the presence of C, N, O, Fe, and Co elements in the catalyst. Figure 2 The C 1s fine structure spectrum shows three distinct characteristic peaks at 287.9 ​​eV (O‒C=O), 285.8 eV (C=C‒N), and 284.6 eV (C‒C / C=C). Figure 3 The fine structure spectrum of N 1s can be fitted with four different characteristic peaks: pyridine N (398.4 eV), pyrrole N (400.2 eV), graphite N (401.0 eV) and M‒N (399.3 eV), which proves that nitrogen heteroatoms have been successfully doped into the carbon layer of the catalyst. Figure 4The fine structure spectrum of FeCo / NC can be decomposed into three sets of split doublets: Fe0 (707.2 eV and 719.9 eV), Fe2+ (710.3 eV and 725.1 eV) and Fe3+ (715.1 and 728.9 eV). Figure 5 The fine structure spectrum of Co 2p can be divided into a Co 2p 3 / 2 peak at 780.9 eV and a Co 2p 1 / 2 peak at 795.7 eV, as well as two satellite peaks at 786.8 eV and 804.8 eV, respectively, indicating that positively valent Co (close to +2 valence) forms a strong electronic coupling with the support.

[0027] The morphology and microstructure of the prepared FeCo / NC catalyst were analyzed using scanning electron microscopy (SEM), such as... Figure 6-7 As shown, FeCo / NC exhibits a polyhedral morphology with a size of approximately 300 nm to 500 nm. High-temperature pyrolysis results in a material with a large number of porous structures, which is beneficial for exposing a large number of active sites.

[0028] The crystal structure of the FeCo / NC sample was analyzed by X-ray diffraction (XRD) pattern. There was a distinct diffraction peak at 2θ=24.6°, which corresponds to the (002) crystal plane of graphite carbon. The main diffraction peak of FeCo / NC appeared at 42.9°, which belongs to Fe2C (JCPDS No.17-0897). The formation of Fe2C may be due to the interaction between the Fe component and the organic ligand in a high-temperature environment, which triggered a thermochemical reaction.

[0029] The following experiments verify the effectiveness of the catalyst of this invention in degrading morphine. The residual morphine concentration was determined by liquid chromatography. All experiments were conducted at room temperature and pressure, with a reaction time of 30 minutes. The reaction principle involves the catalyst activating hydrogen peroxide to generate hydroxyl radicals, which then initiate the breaking of chemical bonds. The catalyst-activated hydrogen peroxide degrades pollutants by utilizing the destructive power of •OH (hydroxyl radicals), specifically breaking the double bonds in the benzene ring, thus completely decomposing toxic and harmful macromolecules into harmless small molecules. Quenching experiments showed that adding tert-butanol to the reaction, which can remove •OH, almost halted the degradation reaction, demonstrating that •OH plays a crucial role.

[0030] Example 2 Effect of catalyst dosage on degradation efficiency: ; Take 100 ml of morphine solution with an initial concentration of 100 mg / L to be degraded, and add 50 mg of hydrogen peroxide (5% concentration) dropwise to the solution containing the catalyst while stirring. When the amount of catalyst is reduced to 10 mg, the degradation rate can still reach more than 98% when the mass ratio of catalyst to substrate is 1:1. If the amount of catalyst is further reduced, the degradation rate will decrease significantly. Therefore, the preferred mass ratio of catalyst to substrate is 5:1 to 1:1.

[0031] Example 3 Effect of substrate concentration on degradation efficiency: ; 100 ml of morphine solutions with different initial concentrations were taken, and the mass ratio of catalyst to substrate was kept at 5:1. Hydrogen peroxide (5% concentration) with a substrate molar ratio of 5 times was added dropwise to the solutions containing the catalyst while stirring. When the initial concentration of morphine was in the range of 100~10000 mg / L, the degradation rate remained above 98%. Further increasing the substrate concentration to 15000 mg / L, the degradation rate was still greater than 92%, indicating that the catalyst of the present invention can achieve efficient degradation in high-concentration morphine systems.

[0032] Example 4 The effect of hydrogen peroxide concentration on degradation efficiency: ; Under the conditions of catalyst dosage of 50mg and initial concentration of 100mg / L morphine in 100ml, the degradation rate is above 92% when the hydrogen peroxide concentration is in the range of 3-7%. Among them, the degradation rate of 99% can be achieved when the hydrogen peroxide concentration is 5%. Further increasing the hydrogen peroxide concentration does not significantly improve the degradation rate. Therefore, the preferred hydrogen peroxide concentration is 5%.

[0033] Example 5 The effect of hydrogen peroxide dosage on degradation efficiency: ; Under the conditions of 50 mg catalyst and 100 ml initial concentration of 100 mg / L morphine, when the hydrogen peroxide concentration is 5%, the degradation rate is above 98% when the molar ratio of hydrogen peroxide to substrate is kept above 2. Further reducing the amount of hydrogen peroxide significantly reduces the degradation rate. The upper limit of hydrogen peroxide dosage should not exceed 20 times. From an economic perspective, 5 times the molar amount is the optimal amount.

[0034] Example 6 The effect of pH on degradation efficiency: ; Under the conditions of 50 mg catalyst, 100 ml initial concentration of 100 mg / L morphine, 5% hydrogen peroxide concentration, and a molar ratio of hydrogen peroxide to substrate of 5, the pH of the system was adjusted by hydrochloric acid. The degradation rate was above 98% when the system acidity ranged from 1 to 5. However, the degradation efficiency was extremely low when the system approached neutrality.

[0035] The catalyst of this invention can also be used for the room-temperature catalytic degradation of remifentanil and fentanyl.

[0036] Example 7 Using the optimal conditions for morphine degradation, we also explored the catalytic degradation effects of remifentanil and fentanyl: with a catalyst-to-substrate mass ratio of 5:1, a system pH of 3, and the addition of 5% hydrogen peroxide at a substrate molar ratio of 5, and stirring at room temperature and pressure for 30 minutes, the degradation rates of both drugs could reach over 99%.

[0037] Example 8 By exploring the reaction conditions in Examples 2-6, it was found that the conditions for the degradation of remifentanil and fentanyl by the catalyst of the present invention are consistent with the conditions for the degradation of morphine by the catalyst of the present invention. The mass ratio of catalyst to substrate is 5:1 to 1:1. Hydrogen peroxide of 3-7% concentration is added to the solution at a molar ratio of hydrogen peroxide to fentanyl and remifentanil of 2:1 to 20:1 under stirring. The degradation and mineralization of fentanyl and remifentanil are achieved by reacting at room temperature for 10-120 min.

[0038] Example 9 The catalyst prepared in Example 1 was used to degrade morphine, fentanyl, and remifentanil at room temperature. The degradation conditions were that the mass ratio of catalyst to substrate was 5:1. Under stirring, hydrogen peroxide (5% concentration) at a molar ratio of 5 times that of substrate was added to the morphine, fentanyl, and remifentanil degradation solution containing the catalyst was added dropwise. The pH value of the system was adjusted by hydrochloric acid to maintain the pH value between 1 and 5. The degradation and mineralization of fentanyl and remifentanil were achieved by reacting at room temperature for 10 to 120 min.

[0039] The COD of the above-mentioned degradation solution was tested, and the results are as follows: .

[0040] The catalyst of this invention was used in catalytic degradation experiments of morphine, remifentanil, and fentanyl. Before degradation, morphine, remifentanil, and fentanyl contained benzene rings; after catalytic degradation, the benzene rings disappeared. The catalytic mechanism of the catalyst of this invention is as follows: the catalyst activates hydrogen peroxide to generate hydroxyl radicals, which initiate the breaking and degradation of the double bonds of the benzene ring. The catalyst-activated hydrogen peroxide degradation of pollutants utilizes the destructive force of •OH (•OH) to completely decompose toxic and harmful macromolecules into harmless small molecules.

[0041] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Any modifications, alterations, substitutions, and variations made by those skilled in the art to the above embodiments are within the scope of the present invention.

Claims

1. A method for preparing a catalyst for the room-temperature catalytic degradation of morphine and fentanyl-class controlled drugs, characterized in that, Includes the following steps: Step a, to add heme C 34 H 32 N4O4Fe and Vitamin B12C 63 H 88 CoN 14 O 14 P dissolves in deionized water to obtain solution A; Step b: Disperse the silica sol in deionized water to obtain solution B; Step c: Slowly add solution A dropwise to solution B, heat and stir at 40℃~80℃ for 3~6 hours, then remove the solvent by heating to obtain a solid product, and grind the obtained solid product; place the ground solid product in a tube furnace and heat to 600~900℃ under a nitrogen atmosphere to pyrolyze the product to obtain a pyrolysis solid powder; perform an etching step on the pyrolysis solid powder, including soaking the obtained pyrolysis solid powder in hydrofluoric acid, stirring at room temperature, centrifuging to remove the solution, and repeating the etching step until the silicon template agent is completely removed; wash with deionized water until neutral, and dry to obtain a bimetallic carbon-nitrogen catalyst.

2. The method for preparing a catalyst for the room-temperature catalytic degradation of morphine and fentanyl-class controlled drugs according to claim 1, characterized in that: In step a, the molar ratio of heme to vitamin B12 is 1:1 to 3:1, and the concentration of the mixture in the aqueous solution is 10 to 50%.

3. A method for preparing a catalyst for the room temperature catalytic degradation of morphine and fentanyl controlled drugs according to claim 1: In step b, the amount of silica sol used is such that the mass ratio of silica sol to heme is 1:1 to 4:1, and the mass concentration of silica sol in water is 6 to 10%.

4. The method for preparing a catalyst for the room-temperature catalytic degradation of morphine and fentanyl-class controlled drugs according to claim 1, characterized in that: In step c, solution A is slowly added dropwise to solution B, and the mixture is heated and stirred at 60°C for 4 hours.

5. The method for preparing a catalyst for the room-temperature catalytic degradation of morphine and fentanyl-class controlled drugs according to claim 1, characterized in that: In step c, removing the solvent by heating means heating to 100°C to remove the solvent.

6. A method for preparing a catalyst for the room-temperature catalytic degradation of morphine and fentanyl-class controlled drugs according to claim 1, characterized in that: In step c, the ground solid product is placed in a tube furnace and heated to 800°C under a nitrogen atmosphere for 2 hours to pyrolyze, thereby obtaining the pyrolyzed solid powder.

7. The catalyst obtained by any one of the catalyst preparation methods according to claims 1-6, characterized in that: The catalyst is a porous carbon-nitrogen material containing cobalt and iron, with a specific surface area of ​​1100~1200 m² / g and a total pore volume of 1.5~1.6 cm³ / g; in the catalyst, the mass content of Fe is 1.8%~1.9% and the mass content of Co is 1.6%~1.7%.

8. A method for the room-temperature catalytic degradation of morphine and fentanyl-class controlled drugs, characterized in that: The catalyst prepared by any one of the catalyst preparation methods of claims 1-6 is used for the catalytic degradation of morphine at room temperature. The catalyst is dispersed in deionized water, and morphine is added. The mass ratio of morphine to catalyst is 1:1 to 1:

5. Hydrogen peroxide with a concentration of 3-7% is added to the solution at a molar ratio of hydrogen peroxide to morphine of 2:1 to 20:1 under stirring. The reaction is carried out at room temperature for 10-120 min to achieve the degradation and mineralization of morphine.

9. A method for the room-temperature catalytic degradation of morphine and fentanyl-class controlled drugs, characterized in that: The catalyst prepared by any one of the catalyst preparation methods of claims 1-6 is used for the catalytic degradation of remifentanil at room temperature. The catalyst is dispersed in deionized water, and remifentanil is added. The mass ratio of remifentanil to catalyst is 1:1 to 1:

5. Then, 3-7% hydrogen peroxide is added to the solution at a molar ratio of hydrogen peroxide to remifentanil of 2:1 to 20:1 under stirring. The degradation and mineralization of remifentanil are achieved by reacting at room temperature for 10 to 120 minutes.

10. A method for the room-temperature catalytic degradation of morphine and fentanyl-class controlled drugs, characterized in that: The catalyst prepared by any one of the catalyst preparation methods of claims 1-6 is used for the catalytic degradation of fentanyl at room temperature. The catalyst is dispersed in deionized water, and fentanyl is added. The mass ratio of fentanyl to catalyst is 1:1 to 1:

5. Then, 3-7% hydrogen peroxide is added to the solution at a molar ratio of hydrogen peroxide to remifentanyl of 2:1 to 20:1 under stirring. The degradation and mineralization of remifentanyl are achieved by reacting at room temperature for 10 to 120 minutes.

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