CN115106365B

CN115106365B - Recovery method and recovery device for degradable medical supplies

Info

Publication number: CN115106365B
Application number: CN202210739768.5A
Authority: CN
Inventors: 吕国玉; 唐游; 罗湘; 罗琳; 刘莉
Original assignee: Sichuan Guona Technology Co ltd
Current assignee: Sichuan Guona Technology Co ltd
Priority date: 2022-06-28
Filing date: 2022-06-28
Publication date: 2024-01-12
Anticipated expiration: 2042-06-28
Also published as: CN115106365A

Abstract

The invention discloses a recovery method and a recovery device of degradable medical supplies, wherein the recovery method comprises the following steps: putting the degradable medical supplies, the solvent and the catalyst into a reaction kettle, and stopping vacuumizing when the vacuum in the kettle is below 2000 pa; heating the reaction kettle to 110-130 ℃, and stirring materials in the kettle to dissolve the degradable medical supplies to form a homogeneous solution; when the temperature in the kettle is increased to 180-250 ℃, reacting for 10-120 min to obtain a monomer; carrying out reduced pressure distillation on materials in the reaction kettle, and co-distilling a monomer, a coloring agent and a solvent from the reaction kettle, wherein the obtained mixed liquid is subjected to secondary reduced pressure distillation to obtain a colorless transparent monomer and solvent; dissolving the distillation residue, distilling under reduced pressure again, washing the distillation solid residue with water, and drying to obtain the colorant. The recovery device is used for realizing the recovery method. The monomer and the coloring agent recovered by the recovery method can be reused, so that the resource waste is avoided, and the production cost of medical supplies is reduced.

Description

Recovery method and recovery device for degradable medical supplies

Technical Field

The invention relates to the technical field of medical supplies, in particular to a recycling method and recycling device of a degradable medical supply.

Background

Many medical supplies used clinically are made of degradable materials such as ligating clips, sutures, bone plates, tissue repair materials, etc. The medical supplies can generate a large amount of waste materials or produce waste products in the production process, and the waste products and the expired products cannot flow out of the factory, so the waste products and the expired products are treated as solid wastes to be destroyed or destroyed in situ, thereby causing resource waste and high production cost.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a recovery method and a recovery device of the degradable medical supplies, and the recovery method can recover the monomers and the coloring agents in the degradable medical supplies, and the recovered monomers and the coloring agents can be recycled to prepare new medical supplies, thereby saving resources and reducing the production cost.

The technical scheme adopted by the invention is as follows:

a method of recycling a degradable medical article comprising the steps of:

step S1, putting degradable medical supplies, a solvent and a catalyst into a reaction kettle, vacuumizing the kettle, and stopping vacuumizing when the pressure in the kettle is reduced to below 2000 pa;

s2, heating the reaction kettle, and stirring materials in the kettle at a rotating speed of 50-500 r/min when the temperature in the kettle is raised to 110-130 ℃ so that the degradable medical supplies are dissolved in the solvent to form a homogeneous solution of the polymer and the coloring agent;

s3, calculating reaction time when the temperature in the kettle is increased to 180-250 ℃ and reacting for 10-120 min to obtain monomers, wherein materials in the kettle are subjected to condensation reflux in the reaction process;

s4, after the reaction is finished, vacuumizing the reaction kettle, performing reduced pressure distillation on materials in the reaction kettle, co-distilling monomers, a coloring agent and a solvent from the reaction kettle, and condensing to obtain mixed liquid of the monomers and the coloring agent;

s5, performing secondary reduced pressure distillation on the mixed liquid, wherein the distillation temperature is 50-220 ℃, the distillation speed is 60-100 r/min, the distillation pressure is not more than 200pa, and collecting fractions at the corresponding temperature to obtain colorless and transparent monomers and solvents respectively;

and S6, dissolving and filtering the distillation residues in the step S5 by using ethyl acetate, performing reduced pressure distillation on the filtrate again at the temperature of 30-40 ℃ and the pressure of less than 200pa, and washing and drying the distillation solid residues by using water to obtain the coloring agent.

In the method for recycling the degradable medical supplies disclosed in the application, in the step S1, the mass parts of the degradable medical supplies, the solvent and the catalyst are respectively as follows: 100 parts of degradable medical supplies, 20-200 parts of solvents and 0.1-5 parts of catalysts.

In the method of recycling a degradable medical article disclosed herein, the degradable medical article is an absorbable ligating clip, suture or other medical product that uses polydioxanone, a coloring agent as a raw material.

In the method for recycling the degradable medical supplies disclosed in the application, in the step S1, the solvent is an aromatic ester compound with the boiling point of 300-410 ℃, and the aromatic ester compound and the degradable medical supplies are mixed and dissolved under the heating condition.

In the method for recycling a degradable medical article disclosed in the application, in the step S2, the colorant is solvent violet 13, solvent violet 9, solvent yellow 93 or other colorants with boiling point higher than 450 ℃.

In the method for recovering a degradable medical article disclosed in the application, in the step S1, the catalyst is one or more of copper oxide, niobium pentoxide, attapulgite, activated clay or other transition metal oxides, and clay catalysts.

Based on the same inventive concept, the invention also discloses a recycling device for realizing the recycling method, in particular,

the utility model provides a degradable medical supplies's recovery unit for retrieve monomer and colorant in the degradable medical supplies, including taking rabbling mechanism, heating mechanism's reation kettle, still include:

the collecting tank is communicated with the reaction kettle through a material pipe; one end of the material pipe is connected with the top of the reaction kettle, and the other end of the material pipe extends to the upper part of the reaction kettle and is connected with the collecting tank in a downward inclined manner;

one end of the return pipe is communicated with the reaction kettle, and the other end of the return pipe is communicated with one end of the material pipe which is inclined downwards and is close to the collecting tank;

the vacuum mechanism is communicated with the collecting tank through a vacuum tube;

the distillation equipment is connected with the collecting tank, and materials in the collecting tank enter the distillation equipment for distillation;

wherein, the outer side of the pipe wall of the material pipe which inclines downwards is sleeved with a condensing pipe; after the degradable medical supplies react in the reaction kettle to generate monomers and coloring agents, the monomers and the coloring agents are distilled under reduced pressure in the reaction kettle under the evacuation action of the vacuum mechanism, enter the material pipe, are condensed by the condensing pipe and then flow into the collecting tank; and the materials in the collecting tank are subjected to secondary reduced pressure distillation through distillation equipment, and monomers, solvents and coloring agents are respectively recovered.

In the recycling device of the degradable medical supplies disclosed in the application, the vacuum mechanism is provided with a buffer tank, and the buffer tank is communicated with the collecting tank through the vacuum tube;

the buffer tank is provided with a vacuum pump port and a drain pipe;

the vacuum pump port is positioned on the upper side of the buffer tank and is connected with the vacuum pump;

the blow-down pipe is positioned at the bottom of the buffer tank and is provided with a fourth valve;

one end of the vacuum tube is connected with the top of the collecting tank, and the other end of the vacuum tube extends from the top of the buffer tank to the inside of the buffer tank to the lower part of the vacuum pump port.

In the recovery device of the degradable medical supplies disclosed in the present application, the collection tank includes:

the emptying pipe is arranged at the top of the collecting tank and communicated with the atmosphere, and an exhaust valve is arranged on the emptying pipe;

the discharging pipe is arranged at the bottom of the collecting tank and is provided with a fifth valve;

the manhole is arranged on the upper side of the tank body of the collecting tank;

and one end of the collecting pipe is connected with the material pipe, and the other end of the collecting pipe extends inwards from the top of the collecting tank to the observation area of the manhole.

In the recycling device of the degradable medical supplies disclosed in the application, the recycling device further comprises a controller; the controller is connected with the heating mechanism, the stirring mechanism and the vacuum mechanism;

the reaction kettle is provided with a temperature sensor and a pressure sensor; the temperature sensor and the pressure sensor are connected with the controller.

Compared with the prior art, the invention has the beneficial effects that:

(1) The degradable medical supplies are heated and dissolved in the reaction kettle to obtain a degradable material and a coloring agent, the degradable material, the coloring agent and the solvent form a homogeneous solution, the degradable material is subjected to cracking reaction in the reaction kettle under the action of a catalyst to generate a monomer, the coloring agent and the solvent are distilled out of the reaction kettle through reduced pressure distillation and condensed to obtain a mixed liquid, the mixed liquid is relatively directly cracked, the cracking stirring resistance of a solution phase is small, the mass transfer and the heat transfer are more uniform, the influence of the local heating unevenness of the direct cracking on the product quality can be effectively avoided, meanwhile, the monomer and the solvent form the homogeneous solution to be distilled out together, the solidification and the blockage of a pipeline after the monomer is contacted with a pipe wall and cooled can be prevented, and the industrialized production can be realized more favorably; and the molecular chains of the polymer in the solution are fully stretched and moved, which is beneficial to increasing the contact area of the polymer and the catalyst and improving the reaction efficiency.

(2) And the mixed liquid is subjected to secondary reduced pressure distillation by a rotary evaporator, so that colorless and transparent monomers, solvents and coloring agents can be respectively obtained, and the recovery of degradable medical supplies is realized. The method is used for recovering the monomer and the coloring agent, the recovery rate is 75-86%, and the purity of the monomer can reach more than 99%. The recovered monomer and the recovered coloring agent can be reused, so that the resource waste is avoided, the production cost of medical supplies is reduced, and the separated solvent can be recycled for homogeneous phase pyrolysis of materials.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.

FIG. 1 is a schematic flow chart of a method of recycling a degradable medical supply;

FIG. 2 is a schematic view of an absorbable ligating clip;

FIG. 3 is a schematic diagram of a mixed liquid distilled off under reduced pressure from a reaction vessel;

FIG. 4 is a schematic illustration of recovered monomer;

FIG. 5 is a schematic illustration of recovered solvent;

FIG. 6 is a schematic diagram of a recovered stain;

FIG. 7 is a schematic structural view of a recycling device for degradable medical supplies;

fig. 8 is a schematic structural view of the collecting pipe and the manhole.

Reference numerals:

1. a reaction kettle; 11. a stirring mechanism; 12. a heating mechanism; 13. a heating jacket; 14. a heat preservation layer; 15. a pressure sensor; 16. a temperature sensor; 17. an air inlet pipe; 18. a cooling tube;

2. a collection tank; 21. an evacuation tube; 22. a discharge pipe; 23. a manhole; 24. a collection pipe; 25. an exhaust valve; 26. a fifth valve;

3. a material pipe; 31. a first valve; 32. a condensing tube; 33. a condensate inlet; 34. a condensed water outlet; 35. a return pipe; 36. a second valve; 37. a third valve;

4. a vacuum mechanism; 41. a buffer tank; 42. a vacuum tube; 43. a vacuum pump port; 44. a blow-down pipe; 45. and a fourth valve.

Detailed Description

In order to make the above objects, features and advantages of the present application more comprehensible, embodiments accompanied with figures are described in detail below. It is to be understood that the specific embodiments described herein are for purposes of illustration only and are not limiting. It should be further noted that, for convenience of description, only some, but not all of the structures related to the present application are shown in the drawings. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.

The terms "comprising" and "having" and any variations thereof herein are intended to cover a non-exclusive inclusion. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those listed steps or elements but may include other steps or elements not listed or inherent to such process, method, article, or apparatus.

Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present application, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.

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 invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.

Reference in the specification to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the application. The appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of skill in the art will explicitly and implicitly appreciate that the embodiments described herein may be combined with other embodiments.

Referring to fig. 1 to 8, the embodiment of the application provides a recycling method and a recycling device for degradable medical supplies, which mainly aims to solve the problems of waste and waste products generated in the production process of the degradable medical supplies, resource waste caused by the fact that expired products are destroyed in situ as solid wastes, and high production cost.

The degradable medical articles are made of degradable materials, such as high molecular poly-p-dioxanone (PPDO), and the like, and the degradable materials are all formed by polymerizing monomers, and can undergo a cracking reaction under certain conditions to generate monomer materials. The medical supplies are also typically added with colorants such as solvent violet 13, solvent violet 9, solvent yellow 93, and the like. Waste materials and waste products generated in the production process of the degradable medical supplies and expired products are destroyed in situ as solid wastes, so that resource waste is caused, the production cost is high, and based on the waste materials and the waste products, the degradable medical supplies are put into a reaction kettle for cracking reaction in homogeneous phase solution, monomers and coloring agents in the medical supplies can be recovered, the recovered monomers and coloring agents can be recycled, new medical supplies are prepared, resources are saved, and the production cost is reduced.

Referring to fig. 1 to 6, the method for recycling the degradable medical supplies disclosed in the application comprises the following steps:

and S1, putting the degradable medical supplies, the solvent and the catalyst into a reaction kettle, vacuumizing the kettle, and stopping vacuumizing when the pressure in the kettle is reduced to below 2000 pa.

And S2, heating the reaction kettle, and stirring materials in the kettle at a rotating speed of 50-500 r/min when the temperature in the kettle is raised to 110-130 ℃ so that the degradable medical supplies are dissolved in the solvent to form a homogeneous solution of the polymer and the coloring agent. After the reaction kettle is heated, the degradable medical supplies are dissolved, the degradable materials, the coloring agent and the solvent form a homogeneous solution, the mass transfer and the heat transfer of the homogeneous solution are more uniform, the influence of uneven local heating on the product quality can be effectively avoided, meanwhile, the molecular chains of the polymer in the solution are fully stretched and moved, the contact surface between the polymer and the catalyst is favorably increased, and the reaction efficiency is improved.

And step 3, calculating the reaction time when the temperature in the kettle is increased to 180-250 ℃ and reacting for 10-120 min to obtain monomers, wherein materials in the kettle are subjected to condensation reflux in the reaction process. The degradable material is subjected to cracking reaction under the action of a catalyst at high temperature and low pressure to generate a monomer.

And S4, after the reaction is finished, vacuumizing the reaction kettle, performing reduced pressure distillation on materials in the reaction kettle, co-distilling the monomer, the coloring agent and the solvent from the reaction kettle, and condensing to obtain mixed liquid of the monomer and the coloring agent. The monomer and the solvent form homogeneous solution to be distilled off, so that the monomer can be prevented from being solidified to block the pipeline after contacting the pipe wall for cooling, and the recovery rate of the monomer is improved.

And S5, performing secondary reduced pressure distillation on the mixed liquid, wherein the distillation temperature is 50-220 ℃, the distillation speed is 60-100 r/min, the distillation pressure is not more than 200pa, and collecting fractions at the corresponding temperature to obtain colorless and transparent monomers and solvents respectively.

The degradable medical supplies are heated and dissolved in the reaction kettle to obtain a degradable material and a coloring agent, the degradable material, the coloring agent and the solvent form a homogeneous solution, the degradable material is subjected to cracking reaction in the reaction kettle under the action of a catalyst to generate a monomer, the coloring agent and the solvent are distilled out of the reaction kettle through reduced pressure distillation and condensed to obtain a mixed liquid, the mixed liquid is relatively directly cracked, the cracking stirring resistance of a solution phase is small, the mass transfer and the heat transfer are more uniform, the influence of the local heating unevenness of the direct cracking on the product quality can be effectively avoided, meanwhile, the monomer and the solvent form the homogeneous solution to be distilled out together, the solidification and the blockage of a pipeline after the monomer is contacted with a pipe wall and cooled can be prevented, and the industrialized production can be realized more favorably; and the molecular chains of the polymer in the solution are fully stretched and moved, which is beneficial to increasing the contact area of the polymer and the catalyst and improving the reaction efficiency. And the mixed liquid is subjected to secondary reduced pressure distillation by a rotary evaporator, so that colorless and transparent monomers, solvents and coloring agents can be respectively obtained, and the recovery of degradable medical supplies is realized. The method is used for recovering the monomer and the coloring agent, the recovery rate is 75-86%, and the purity of the monomer can reach more than 99%. The recovered monomer and the recovered coloring agent can be reused, so that the resource waste is avoided, the production cost of medical supplies is reduced, and the separated solvent can be recycled for homogeneous phase pyrolysis of materials.

In one embodiment, in step S1, the mass parts of the degradable medical article, the solvent and the catalyst are respectively: 100 parts of degradable medical supplies, 20-200 parts of solvents and 0.1-5 parts of catalysts.

In one embodiment, in step S1, the degradable medical article is an absorbable ligating clip, suture, or other medical product that is made from polydioxanone, a colorant, or the like.

In one embodiment, in step S1, the solvent is an aromatic ester compound having a boiling point of 300 ℃ to 410 ℃, and the aromatic ester compound is miscible with the degradable medical article under heating. Specifically, the solvent is dimethoxyethyl phthalate (DMEP), dibutyl phthalate (DBP), diethylene glycol dibenzoate (DEDB). Preferably, the solvent is dimethoxyethyl phthalate. The dimethoxy ethyl phthalate can be mutually dissolved with degradable materials after being heated to form homogeneous solution, and the homogeneous solution can be formed with monomers at normal temperature. Compared with direct pyrolysis, the mass transfer and heat transfer of the pyrolysis reaction of the solution phase are more uniform, the influence of local uneven heating caused by direct pyrolysis on the product quality can be effectively avoided, meanwhile, the monomer and the solvent form homogeneous solution to be distilled off together, and the phenomenon that the monomer is solidified and blocked in a pipeline after being contacted with the pipe wall for cooling can be prevented.

In one embodiment, in step S2, the colorant is solvent violet 13, solvent violet 9, solvent yellow 93, or other colorant having a boiling point above 450 ℃.

In one embodiment, in step S1, the catalyst is one or more of copper oxide, niobium pentoxide or other transition metal oxides, or one or more of attapulgite, activated clay or other clay-based catalysts, preferably copper oxide. The catalyst can promote the cracking of the degradable material, effectively improve the recovery speed of the degradable material, shorten the reaction time and reduce the reaction temperature.

Detailed description of the embodiments

Example 1

100 parts of ligature clamp, 20 parts of dimethoxyethyl phthalate and 0.1 part of copper oxide are put into a reaction kettle, the kettle is vacuumized, and when the pressure in the kettle is reduced to 1500pa, the vacuumizing is stopped; heating the reaction kettle, and stirring materials in the kettle at a rotating speed of 50r/min when the temperature in the kettle is raised to 110 ℃; when the temperature in the kettle is raised to 190 ℃, calculating the reaction time, reacting for 20min, and condensing and refluxing materials in the kettle in the reaction process; after the reaction is finished, vacuumizing the reaction kettle, performing reduced pressure distillation on materials in the reaction kettle, co-distilling monomer dioxanone (PDO), dimethoxyethyl phthalate and solvent violet 13 from the reaction kettle, and condensing to obtain mixed liquid; and (3) carrying out secondary reduced pressure distillation on the mixed liquid, wherein the distillation temperature is 60 ℃, the distillation speed is 60r/min, the distillation pressure is 150pa, collecting fractions at the temperature to obtain colorless and transparent monomer dioxanone (PDO), the net yield is 85.3%, the purity is 99.68%, after no fractions are generated, replacing a collecting bottle, continuously heating to 200 ℃, collecting fractions at the temperature to obtain a reaction solvent, dissolving the residual substances in the distilling bottle by ethyl acetate after the solvent is collected, filtering, carrying out reduced pressure distillation on the filtrate at 35 ℃ and 80pa, and washing and drying the solid products in the distilling bottle by clear water to obtain the solvent purple 13.

Example 2

Putting 100 parts of suture, 100 parts of dimethoxyethyl phthalate and 1 part of niobium pentoxide into a reaction kettle, vacuumizing the kettle, and stopping vacuumizing when the pressure in the kettle is reduced to 2000 pa; heating the reaction kettle, and stirring materials in the kettle at a rotating speed of 200r/min when the temperature in the kettle is raised to 120 ℃; when the temperature in the kettle is raised to 210 ℃, calculating the reaction time, reacting for 70min, and condensing and refluxing materials in the kettle in the reaction process; after the reaction is finished, vacuumizing the reaction kettle, performing reduced pressure distillation on materials in the reaction kettle, co-distilling PDO, dimethoxyethyl phthalate and solvent yellow 93 from the reaction kettle, and condensing to obtain mixed liquid; and (3) carrying out secondary reduced pressure distillation on the mixed liquid, wherein the distillation temperature is 80 ℃, the distillation speed is 80r/min, the distillation pressure is 100pa, collecting fractions at the temperature to obtain colorless and transparent PDO, the yield is 85.5%, the purity is 99.29%, after no fractions are generated, replacing a collecting bottle, continuously heating to 190 ℃, collecting fractions at the temperature to obtain a reaction solvent, dissolving and filtering residual substances in the distilling bottle by ethyl acetate after the solvent is collected, carrying out reduced pressure distillation on filtrate at 30 ℃ and 75pa, washing a solid product in the distilling bottle by clear water, and drying to obtain solvent yellow 93.

Example 3: putting 100 parts of suture, 200 parts of diethylene glycol dibenzoate and 5 parts of copper oxide into a reaction kettle, vacuumizing the kettle, and stopping vacuumizing when the pressure in the kettle is reduced to 1000 pa; heating the reaction kettle, and stirring materials in the kettle at a rotating speed of 500r/min when the temperature in the kettle is raised to 130 ℃; when the temperature in the kettle is raised to 250 ℃, calculating the reaction time, reacting for 120min, and condensing and refluxing materials in the kettle in the reaction process; after the reaction is finished, vacuumizing the reaction kettle, performing reduced pressure distillation on materials in the reaction kettle, co-distilling PDO, diethylene glycol dibenzoate and solvent purple 9 from the reaction kettle, and condensing to obtain mixed liquid; and (3) carrying out secondary reduced pressure distillation on the mixed liquid, wherein the distillation temperature is 95 ℃, the distillation speed is 100r/min, the distillation pressure is 110pa, collecting fractions at the temperature to obtain colorless and transparent PDO, the yield is 85.9%, the purity is 98.36%, after no fractions are generated, replacing a collecting bottle, continuously heating to 195 ℃, collecting fractions at the temperature to obtain a reaction solvent, dissolving and filtering the residual substances in the distilling bottle by ethyl acetate after the solvent is collected, carrying out reduced pressure distillation on the filtrate at the temperature of 40 ℃ and the pressure of 100pa, washing and drying the solid products in the distilling bottle by clear water to obtain the solvent purple 9.

Example 4: 100 parts of ligature clamp, 20 parts of dibutyl phthalate and 1.5 parts of attapulgite are put into a reaction kettle, the kettle is vacuumized, and when the pressure in the kettle is reduced to 800pa, the vacuumizing is stopped; heating the reaction kettle, and stirring materials in the kettle at a rotating speed of 90r/min when the temperature in the kettle is raised to 110 ℃; when the temperature in the kettle is increased to 220 ℃, calculating the reaction time, reacting for 40min, and condensing and refluxing materials in the kettle in the reaction process; after the reaction is finished, vacuumizing the reaction kettle, performing reduced pressure distillation on materials in the reaction kettle, co-distilling PDO, dibutyl phthalate and solvent violet 13 from the reaction kettle, and condensing to obtain mixed liquid; and (3) carrying out secondary reduced pressure distillation on the mixed liquid, wherein the distillation temperature is 75 ℃, the distillation speed is 60r/min, the distillation pressure is 90pa, collecting fractions at the temperature to obtain colorless and transparent PDO with the net yield of 80.2% and the purity of 98.68%, changing a collecting bottle after no fractions are generated, continuously heating to 200 ℃, collecting fractions at the temperature to obtain a reaction solvent, dissolving and filtering residual substances in the distilling bottle by ethyl acetate after the solvent is collected, carrying out reduced pressure distillation on filtrate at the temperature of 32 ℃ and the pressure of 85pa, and washing and drying solid products in the distilling bottle by clear water to obtain the solvent purple 13.

Example 5: 100 parts of ligature clamp, 150 parts of dimethoxyethyl phthalate and 0.5 part of activated clay are put into a reaction kettle, the kettle is vacuumized, and when the pressure in the kettle is reduced to 1600pa, the vacuumizing is stopped; heating the reaction kettle, and stirring materials in the kettle at a rotating speed of 100r/min when the temperature in the kettle is raised to 110 ℃; when the temperature in the kettle is increased to 230 ℃, calculating the reaction time, reacting for 10min to obtain a material monomer PDO, and condensing and refluxing materials in the kettle in the reaction process; after the reaction is finished, vacuumizing the reaction kettle, performing reduced pressure distillation on materials in the reaction kettle, co-distilling PDO, dimethoxyethyl phthalate and solvent violet 13 from the reaction kettle, and condensing to obtain mixed liquid; and (3) carrying out secondary reduced pressure distillation on the mixed liquid, wherein the distillation temperature is 70 ℃, the distillation speed is 60r/min, the distillation pressure is 180pa, collecting fractions at the temperature to obtain colorless and transparent PDO with the net yield of 85.3 percent and the purity of 99.18 percent, changing a collecting bottle after no fractions are generated, continuously heating to 210 ℃, collecting fractions at the temperature to obtain a reaction solvent, dissolving and filtering residual substances in the distilling bottle by ethyl acetate after the solvent is collected, carrying out reduced pressure distillation on filtrate at the temperature of 30 ℃ and the pressure of 70pa, washing a solid product in the distilling bottle by clear water, and drying to obtain the solvent violet 13.

Example 6: the solvent dimethoxyethyl phthalate recovered in example 5 was used for depolymerization of the degraded material. 100 parts of ligature clamp, 100 parts of dimethoxyethyl phthalate and 2 parts of activated clay are put into a reaction kettle, the kettle is vacuumized, and when the pressure in the kettle is reduced to 1200pa, the vacuumizing is stopped; heating the reaction kettle, and stirring materials in the kettle at a rotating speed of 200r/min when the temperature in the kettle is raised to 120 ℃; when the temperature in the kettle is increased to 200 ℃, calculating the reaction time, reacting for 100min, and condensing and refluxing materials in the kettle in the reaction process; after the reaction is finished, vacuumizing the reaction kettle, performing reduced pressure distillation on materials in the reaction kettle, co-distilling PDO, dimethoxyethyl phthalate and solvent violet 13 from the reaction kettle, and condensing to obtain mixed liquid; and (3) carrying out secondary reduced pressure distillation on the mixed liquid, wherein the distillation temperature is 70 ℃, the distillation speed is 80r/min, the distillation pressure is 80pa, collecting fractions at the temperature to obtain colorless and transparent PDO with the net yield of 80.8 percent and the purity of 98.27 percent, changing a collecting bottle after no fractions are generated, continuously heating to 185 ℃, collecting fractions at the temperature to obtain a reaction solvent, dissolving and filtering residual substances in the distilling bottle by ethanol after the solvent is collected, carrying out reduced pressure distillation on filtrate at 36 ℃ and 88pa, and washing and drying solid products in the distilling bottle by clear water to obtain the solvent purple 13.

Please refer to fig. 2-6, which are each a physical diagram of the absorbable ligation clip recycling process. FIG. 2 is a schematic view of an absorbable ligating clip; FIG. 3 is a schematic illustration of a mixed liquid obtained by distillation under reduced pressure, wherein the absorbable ligation clip is reacted in a reaction kettle; FIG. 4 is a schematic illustration of recovered colorless transparent monomers; FIG. 5 is a schematic illustration of recovered solvent; FIG. 6 is a schematic of recovered stain.

Referring to Table 1, under different experimental conditions, the yields of monomer, solvent and dye were compared, and when the solvent was DEDB, the reaction temperature was 250deg.C, the reaction pressure was 1000Pa, the yield of monomer was 85.9% and the yield of dye was 81.2%.

TABLE 1 experimental results for the examples

Examples	Solvent(s)	Boiling point/. Degree.C	Reaction temperature/. Degree.C	Reaction pressure/Pa	Monomer yield/%	Solvent yield/%	Stain yield/%
								1	DMEP	350	190	1500	85.3	90.3	77.5
2	DMEP	350	210	2000	85.5	92.5	78.4
								3	DEDB	408	250	1000	85.9	91.2	81.2
4	DBP	337	220	800	80.2	94.1	75.5
								5	DMEP	350	230	1600	85.3	90.1	79.2
6	DMEP	350	200	1200	80.8	89.6	78.3

The embodiments given above describe in more detail the method of recycling of degradable medical supplies, and the following embodiments will attempt to briefly describe the means by which this is achieved, i.e. the recycling means of degradable medical supplies.

Referring to fig. 7 to 8, a recycling device for degradable medical supplies is disclosed, and is used for recycling monomers and colorants in the degradable medical supplies. The recovery device comprises a reaction kettle 1 with a stirring mechanism 11 and a heating mechanism 12. The stirring mechanism 11 is used for stirring materials in the reaction kettle 1. The heating mechanism 12 is provided with a heating sleeve 13 and an insulating layer 14, the heating sleeve 13 is used for heating the reaction kettle 1, and the insulating layer 14 is used for insulating the reaction kettle 1, so that heat loss is avoided.

The recovery device further includes:

the collecting tank 2 is communicated with the reaction kettle 1 through a material pipe 3. Referring to fig. 1, one end of a material pipe 3 is connected to the top of the reaction kettle 1, and the other end extends to the upper part of the reaction kettle 1 and is connected to a collection tank 2 in a downward inclined manner. The material pipe 3 is provided with a first valve 31. The material pipe 3 extends to the upper part of the reaction kettle 1 and then inclines downwards, so that materials in the reaction kettle 1 can flow into the collecting tank 2 after being distilled and condensed.

And a return pipe 35, wherein one end of the return pipe 35 is communicated with the reaction kettle 1, and the other end is communicated with one end of the material pipe 3 which is inclined downwards and is close to the collecting tank 2. The return pipe 35 is provided with a second valve 36 at one end close to the material pipe 3, and a third valve 37 at one end close to the reaction kettle 1. During the reaction of the materials in the reaction kettle 1, the materials are condensed and returned through a return pipe 35.

The vacuum mechanism 4 is communicated with the collection tank 2 through a vacuum tube 42. The vacuum mechanism 4 is used for evacuating the inside of the collection tank 2 and the reaction kettle 1, and reducing the pressure in the collection tank 2 and the reaction kettle 1.

Distillation equipment (not shown) is connected with the collecting tank 2, and the materials in the collecting tank 2 enter the distillation equipment for distillation. The distillation equipment is a rotary evaporator and is used for distilling the materials collected in the collecting tank 2 and recycling the material monomers and the coloring agent.

Wherein, the pipe wall outside of the downward inclined material pipe 3 is sleeved with a condensing pipe 32. The condensate pipe 32 is provided at both ends thereof with a condensate inlet 33 and a condensate outlet 34, respectively. The condensed water enters the condensing pipe 32 from the condensed water inlet 33 at the lower part, can condense the materials in the material pipe 3 into liquid, flows into the collecting tank 2, and then is discharged from the condensing pipe 32 from the condensed water outlet 34 at the upper part.

After the degradable medical supplies react in the reaction kettle 1 to generate monomers and coloring agents, the monomers and the coloring agents are decompressed and distilled in the reaction kettle 1 under the evacuation action of the vacuum mechanism 4, enter the material pipe 3, are condensed by the condensing pipe 32, and flow into the collecting tank 2. The materials in the collecting tank 2 are distilled under reduced pressure by a distillation device, and the monomers and the coloring agent are respectively recovered.

The main raw materials of the degradable medical supplies are degradable materials and a coloring agent, and after the degradable materials and the coloring agent react in the reaction kettle 1, the monomer, the coloring agent and the solvent can be separated from the reaction kettle 1 through reduced pressure distillation. The monomer, the coloring agent and the solvent are distilled under reduced pressure by a rotary evaporator, so that the monomer, the coloring agent and the solvent can be obtained respectively, the recovery of the degradable medical supplies is realized, and the recovery rate is 75-86%. The recovered monomers, the recovered coloring agent and the recovered solvent can be reused, so that the resource waste is avoided, and the production cost of medical supplies is reduced.

In one embodiment, referring to FIG. 7, the vacuum mechanism 4 has a buffer tank 41. The buffer tank 41 communicates with the collection tank 2 through a vacuum tube 42. The buffer tank 41 is provided with a vacuum pump port 43 and a drain pipe 44. The vacuum pump port 43 is located at the upper side of the buffer tank 41 and is connected to a vacuum pump (not shown). A drain pipe 44 is located at the bottom of the surge tank 41, on which a fourth valve 45 is provided.

Specifically, one end of the vacuum tube 42 is connected to the top of the collection tank 2, and the other end extends from the top of the buffer tank 41 to the inside of the buffer tank 41 to below the vacuum pump port 43, so that the material is prevented from being pumped into the vacuum pump and damaging the vacuum pump when the vacuum pump is evacuated.

By providing the buffer tank 41, the vacuum pump is prevented from being sucked back into the collection tank 2, and the buffer function is provided for vacuum pumping, so that the sudden pressure change of the reaction system is prevented.

In one embodiment, the collection tank 2 includes an evacuation tube 21, a discharge tube 22, a manhole 23, and a collection tube 24. An evacuation pipe 21 is provided at the top of the collection tank 2, communicating with the atmosphere, and an exhaust valve 25 is provided thereon. The discharge pipe 22 is arranged at the bottom of the collection tank 2, on which a fifth valve 26 is arranged. A manhole 23 is provided at the upper side of the tank body of the collection tank 2 for observing the condition inside the collection tank 2. Referring to fig. 8, a collection pipe 24 is connected to the material pipe 3 at one end and extends inwardly from the top of the collection tank 2 to the observation area of the manhole 23 at the other end. The collecting pipe 24 can be observed to drop the liquid through the manhole 23, and whether distillation is finished or not can be judged.

In one embodiment, the recycling apparatus further comprises a controller. The controller is connected with the heating mechanism 12, the stirring mechanism 11 and the vacuum mechanism 4, and can control the opening and closing of the heating mechanism 12, the stirring mechanism 11 and the vacuum mechanism 4. The reaction kettle 1 is provided with a temperature sensor 16 and a pressure sensor 15, and the temperature sensor 16 and the pressure sensor 15 are connected with a controller. The controller can adjust the heating mechanism 12, the stirring mechanism 11 and the vacuum mechanism 4 according to the temperature and the pressure detected by the temperature sensor 16 and the pressure sensor 15.

In one embodiment, the recovery device further comprises an air inlet pipe 17. Referring to fig. 7, one end of the air inlet pipe 17 extends into the reaction kettle 1 to the bottom of the kettle body, and the other end is connected to an inert gas tank (not shown). The air inlet pipe 17 is used for introducing inert gas into the reaction kettle 1, so that the recovery device can be used for reaction under the inert gas atmosphere, and the whole reaction kettle 1 can be purged and dried by adopting the inert gas through the air inlet pipe 17 after the reaction is finished.

In one embodiment, the recovery device further includes a cooling tube 18. The cooling pipe 18 is located inside the reaction vessel 1, and has one end connected to a cooling water inlet of a cooling water tank (not shown) and the other end connected to a cooling water outlet. Cooling water in the cooling water tank enters the cooling pipe 18 through the cooling water outlet, the cooling pipe 18 cools the reaction kettle 1, and the cooling water enters the cooling water tank from the cooling water inlet.

The working mode of the recovery device of the degradable medical supplies is as follows:

putting the degradable medical supplies, the solvent and the catalyst into a reaction kettle 1, starting a vacuum pump, vacuumizing the kettle to below 2000pa, closing the vacuum pump, and starting a heating mechanism 12; when the temperature in the kettle is increased to 110-130 ℃, starting a stirring mechanism 11, and stirring materials in the kettle by the stirring mechanism 11 at a rotating speed of 50-500 r/min to dissolve the degradable medical supplies in the solvent to form a homogeneous solution of the polymer and the coloring agent; when the temperature in the kettle is increased to 180-250 ℃, calculating the reaction time, reacting for 10-120 min to obtain a monomer, and condensing and refluxing materials in the kettle through a reflux pipe 35 in the reaction process; after the reaction is finished, opening condensed water, starting a vacuum pump, performing reduced pressure distillation on materials in the reaction kettle 1, co-distilling monomers, a coloring agent and a solvent from the reaction kettle 1, entering a material pipe 3, condensing the condensed water in a condensing pipe 32, and flowing into a collecting tank 2; observing the collecting pipe 24 through the manhole 23, when the collecting pipe 24 does not generate liquid drops any more, closing the vacuum pump, opening the exhaust valve 25 to restore the system to normal pressure, and closing the heating mechanism 12 and the stirring mechanism 11; when the temperature in the kettle is reduced to below 200 ℃, opening a cooling pipe 18 in the kettle, accelerating the temperature reduction of the kettle body, opening a kettle cover after the temperature is reduced to below 100 ℃, and cleaning the kettle body and the stirring mechanism 11; and (3) placing the materials in the collecting tank 2 into a rotary evaporator for distillation to obtain colorless and transparent monomers, a coloring agent and a solvent respectively.

The recovery device can recover the monomer and the coloring agent in the degradable medical supplies, the degradable medical supplies are heated and dissolved in the reaction kettle 1 to obtain the degradable materials and the coloring agent, the degradable materials, the coloring agent and the solvent form a homogeneous phase solution, the degradable materials react in the reaction kettle 1 to generate the monomer under the action of the catalyst, the monomer, the coloring agent and the solvent are distilled out of the reaction kettle 1 through reduced pressure distillation, and the mixed liquid is obtained through condensation. And the mixed liquid is subjected to secondary reduced pressure distillation by a rotary evaporator, so that monomers, a coloring agent and a solvent can be respectively obtained, and the recovery of degradable materials is realized. The recovered monomer, the recovered coloring agent and the recovered solvent can be reused, so that the resource waste is avoided, and the production cost of medical supplies is reduced.

The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for recycling a degradable medical article, comprising the steps of:

s6, dissolving and filtering the distillation residues in the step S5 by using ethyl acetate, performing reduced pressure distillation on filtrate again at the temperature of 30-40 ℃ and the pressure of less than 200pa, washing the distillation solid residues by using water, and drying to obtain a coloring agent;

in the step S1, the degradable medical supplies are absorbable ligature clips, suture lines or other medical products which take polydioxanone and coloring agents as raw materials;

the solvent is an aromatic ester compound with the boiling point of 300-410 ℃, and the aromatic ester compound is mixed and dissolved with the degradable medical supplies under the heating condition;

in the step S2, the coloring agent is solvent violet 13, solvent violet 9, solvent yellow 93 or other coloring agents with boiling point higher than 450 ℃.

2. The method for recycling degradable medical supplies according to claim 1, wherein in the step S1, the mass parts of the degradable medical supplies, the solvent and the catalyst are respectively: 100 parts of degradable medical supplies, 20-200 parts of solvents and 0.1-5 parts of catalysts.

3. The method according to claim 1, wherein in the step S1, the catalyst is one or more of copper oxide, niobium pentoxide, attapulgite, activated clay or other transition metal oxides, and clay-based catalysts.

4. A recycling device for degradable medical supplies, which adopts the recycling method for the degradable medical supplies according to any one of claims 1-3, is used for recycling monomers and coloring agents in the degradable medical supplies, and comprises a reaction kettle with a stirring mechanism and a heating mechanism, and is characterized by further comprising:

wherein, the outer side of the pipe wall of the material pipe which inclines downwards is sleeved with a condensing pipe; after the degradable medical supplies react in the reaction kettle to generate monomers and coloring agents, the monomers and the coloring agents are distilled under reduced pressure in the reaction kettle under the evacuation action of the vacuum mechanism, enter the material pipe, are condensed by the condensing pipe and then flow into the collecting tank; and the materials in the collecting tank are distilled under reduced pressure by a distillation device, and the monomers, the solvent and the coloring agent are respectively recovered.

5. The device of claim 4, wherein the vacuum mechanism has a buffer tank in communication with the collection tank via the vacuum tube;

the buffer tank is provided with a vacuum pump port and a drain pipe;

6. The device for recycling of degradable medical supplies according to claim 4, characterized in that the collection tank comprises:

7. The retrieval device of claim 4, wherein the retrieval device further comprises a controller; the controller is connected with the heating mechanism, the stirring mechanism and the vacuum mechanism;