CN112358563A - Macroporous adsorption resin for lincomycin extraction and synthetic method thereof - Google Patents
Macroporous adsorption resin for lincomycin extraction and synthetic method thereof Download PDFInfo
- Publication number
- CN112358563A CN112358563A CN202011383202.0A CN202011383202A CN112358563A CN 112358563 A CN112358563 A CN 112358563A CN 202011383202 A CN202011383202 A CN 202011383202A CN 112358563 A CN112358563 A CN 112358563A
- Authority
- CN
- China
- Prior art keywords
- resin
- lincomycin
- reaction
- extraction
- macroporous adsorption
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/14—Acyclic radicals, not substituted by cyclic structures attached to a sulfur, selenium or tellurium atom of a saccharide radical
- C07H15/16—Lincomycin; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/02—Alkylation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/042—Nanopores, i.e. the average diameter being smaller than 0,1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/08—Copolymers of styrene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Analytical Chemistry (AREA)
- Genetics & Genomics (AREA)
- General Health & Medical Sciences (AREA)
- Biotechnology (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a macroporous adsorption resin for lincomycin extraction and a synthesis method thereof, which adopts a suspension polymerization mode to stir and dissolve to prepare a water phase; dissolving a monomer, an initiator and a pore-forming agent together, and stirring until the monomers are completely dissolved to prepare an oil phase; then putting the oil phase into the water phase, standing until the oil phase and the water phase are completely layered, heating and preserving heat; and after the reaction is finished, putting the resin into a steam generator for extraction, recovering the pore-foaming agent, and then washing and drying to obtain the dry polystyrene-divinylbenzene copolymer. Adding the prepared dry polystyrene-divinylbenzene copolymer into a reaction kettle, swelling with dichloroethane, adding a catalyst twice, heating for reaction, washing the resin with water after the reaction is finished until the resin is neutral, discharging, and screening macroporous adsorption resin to obtain the macroporous adsorption resin for extracting lincomycin. The macroporous adsorption resin prepared by the method has high adsorption capacity and high desorption rate on lincomycin, and is simple in synthesis process, green, environment-friendly, low in cost and easy to produce in an enlarged mode.
Description
Technical Field
The invention belongs to the technical field of chemical engineering and medicine, and particularly relates to macroporous adsorption resin for lincomycin extraction and a synthesis method thereof.
Background
Lincomycin, also called lincomycin and lincomycin, is a basic broad-spectrum antibiotic, belongs to macrolide antibiotics and is effective on most gram-positive bacteria. And in clinical practice, lincomycin is mainly used for treating infection caused by pneumococci, green streptococcus, staphylococcus aureus and the like. Thus, lincomycin has an extremely important position in the medical industry.
For the extraction of lincomycin, the method firstly adopts a plate-frame filtration mode to extract lincomycin from fermentation liquor through processes of solid-liquid separation, extraction, back extraction, concentration crystallization and the like. The method has the defects of complex extraction process, serious emulsification phenomenon in the extraction process, low total yield and the like. With the continuous optimization and improvement of the extraction process, the extraction method and the resin adsorption method are mainly adopted in the extraction industry of lincomycin in recent years. The extraction method mainly uses n-butyl alcohol as an extraction agent to realize industrial production of lincomycin, but the extraction method has the defects of poor extraction effect, large solvent consumption, high energy consumption, large operation environment pollution and the like in the production process, so that the large-scale production of the lincomycin is limited. For the extraction of lincomycin by an extraction method, many researchers in China also develop a novel extraction system for extracting the lincomycin, for example, the extraction system adopts a neutral phosphine extraction agent, an oxime extraction agent, a lipid extraction agent and the like, and the problems of poor extraction effect and the like in the extraction process are solved in a targeted manner, but the extraction agents generally have the problem of difficult recovery, so that the industrial application of the extraction agents is limited to a certain extent.
In recent years, when the macroporous adsorption resin is used for extracting lincomycin, broken balls are easy to generate in the operation process due to low mechanical strength, so that the production efficiency is reduced, and meanwhile, a series of problems such as reduction of adsorption quantity, deterioration of desorption efficiency, reduction of total yield, improvement of production cost caused by continuous replacement of the resin and the like also occur.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art, and provides a macroporous adsorption resin for lincomycin extraction and a synthesis method thereof, which solve the problems of high production cost, large organic solvent emission, small adsorption amount, low desorption rate, low finished product purity and the like of the conventional macroporous adsorption resin in lincomycin extraction.
The invention adopts the following technical scheme:
a synthetic method of macroporous adsorption resin for lincomycin extraction comprises the following steps:
s1, adding the dispersing agent and the methylene blue into water, heating and stirring until the dispersing agent and the methylene blue are completely dissolved to prepare a water phase; uniformly mixing a monomer, a pore-forming agent and an initiator to obtain an oil phase; adding the oil phase into the water phase, standing, controlling the particle size of the oil phase after the oil phase and the water phase are completely layered, stirring at a constant speed, and then heating and preserving heat; after the reaction is finished, extracting a pore-foaming agent, washing with water and drying to obtain a polystyrene-divinylbenzene copolymer;
s2, adding the polystyrene-divinylbenzene copolymer prepared in the step S1 into a reaction kettle, swelling with dichloroethane, adding a catalyst twice, heating for reaction, washing the resin until the resin is neutral after the reaction is finished, discharging, and screening macroporous adsorption resin with the diameter of 0.315-1.25 mm to obtain the macroporous adsorption resin for lincomycin extraction.
Specifically, in step S1, the mass ratio of water, dispersant and methylene blue is 100 (0.1-0.5) to (0.01-0.05).
Specifically, in step S1, the dispersant is polyvinyl alcohol and hydroxyethyl cellulose.
Specifically, in step S1, the mass ratio of the monomer, the initiator and the pore-forming agent is (0.5-1.5): 100-150).
Further, the monomer is one or more of divinylbenzene, styrene, ethyl styrene, methyl acrylate, methyl methacrylate, acrylic acid and acrylonitrile; the initiator is one or more of benzoyl oxide, azobisisobutyronitrile, azobisisovaleronitrile and cyclohexanone peroxide; the pore-foaming agent is one or more of saturated hydrocarbon, toluene, xylene and tetramethylbenzene.
Specifically, in step S1, the temperature is increased to 80-95 ℃ and the heat preservation time is 8-12 hours.
Specifically, in step S1, the particle size of the oil phase is 0.285-1.0 mm.
Specifically, in the step S2, the mass-volume ratio of the polystyrene-divinylbenzene copolymer to the dichloroethane is 1 (5-8), and the swelling time is 2-4 h.
Specifically, in the step S2, the mass ratio of the polystyrene-divinylbenzene copolymer to the catalyst is 1 (0.1-0.3), the catalyst is anhydrous aluminum trichloride or anhydrous ferric trichloride, after swelling for 2-4 h, half of the catalyst is added at room temperature, the temperature is raised to 80 +/-1 ℃ at a speed of 5 ℃/10min, the reaction is kept for 3-5 h, then the temperature is lowered to below 75 ℃, the remaining half of the catalyst is added, and the temperature is raised to 80 +/-1 ℃ for continuous reaction for 6-8 h.
The invention also provides a macroporous adsorption resin for lincomycin extraction, which is prepared by the method.
Compared with the prior art, the invention has at least the following beneficial effects:
a synthetic method of macroporous adsorption resin for lincomycin extraction is provided, on one hand, organic solvents such as pore-forming agents of tetramethylbenzene, toluene, saturated alkane and dichloroethane can be respectively recovered in the synthetic process, the recovered pore-forming agents can be directly used for the synthesis of resins of the next batch, on the other hand, in the synthetic method, a process link of extracting the pore-forming agents by adopting steam to replace the organic solvents is adopted, the use of the organic solvents is reduced, the pollution is reduced, the cost is reduced, the strength of the resin can be further improved by carrying out secondary crosslinking on polystyrene-divinylbenzene copolymer, and the specific surface area in the resin can be increased. The macroporous adsorption resin prepared by the method also has the advantages of large adsorption capacity, high desorption rate, high finished product purity and the like in the lincomycin extraction process.
Furthermore, the mass ratio of the water to the dispersant to the methylene blue is 100 (0.1-0.5) to 0.01-0.05, so that on one hand, the dispersant can well disperse the monomers, and on the other hand, the methylene blue is used as an aqueous phase polymerization inhibitor and can prevent the monomers from emulsion polymerization and the like in an aqueous phase.
Furthermore, the polyvinyl alcohol and the hydroxyethyl cellulose are added into the water phase, so that the viscosity of the water phase can be increased, and the particle size can be controlled more easily in the balling process.
Further, too large amount of initiator can cause monomers to implode, and too small amount of monomers can cause too slow free radical polymerization reaction speed; the pore-forming agent is too little to achieve the pore-forming effect, and too much resin has too large pore diameter to achieve the effect of adsorbing lincomycin. Therefore, the macroporous adsorption resin with high adsorption performance on lincomycin can be prepared by careful selection in the proportion range.
Furthermore, the pore-foaming agent is one or more of saturated hydrocarbon, toluene, xylene and tetramethylbenzene, and the monomer, the initiator and the pore-foaming agent are adopted, and the macroporous adsorption resin with a pore channel structure with a specific size can be prepared by adjusting the proportion of the monomer, the initiator and the pore-foaming agent.
Further, when the temperature is about 80 ℃, the initiator can initiate the monomer to perform radical polymerization, and with the occurrence of the radical polymerization, a large amount of polymerization heat is generated, the monomer is imploded due to the excessively high system temperature, and the radical polymerization speed of the monomer is too slow due to the low temperature. Finally, the temperature is raised to 95 ℃, and the resin is ensured to be completely shaped at the temperature.
Furthermore, the polystyrene-divinylbenzene copolymer can swell in the post-crosslinking process to increase the granularity, and the oil phase granularity in the range can ensure that the finished resin has higher yield between 0.315 and 1.25 mm.
Furthermore, the mass-volume ratio of the dry polystyrene-divinyl benzene copolymer to the dichloroethane mainly ensures that the dichloroethane can completely swell the polystyrene-divinyl benzene copolymer, the swelling time of the polystyrene-divinyl benzene copolymer in the dichloroethane cannot be less than 2 hours, and the polystyrene-divinyl benzene copolymer cannot completely swell in the dichloroethane if the swelling time is too short, so that the secondary crosslinking reaction degree is influenced, and the performance of the finished resin is further influenced; the swelling time is too long, which causes the strength of the resin to be lowered, and is not favorable for practical use of the resin.
Furthermore, the addition amount of the catalyst is too low, the speed of secondary crosslinking reaction in the polystyrene-divinyl benzene copolymer is too slow, the reaction is not complete, the activity of anhydrous aluminum trichloride or anhydrous ferric trichloride is higher, the reaction is too violent when the addition amount is too large, certain influence is generated on the performance of the resin, particularly the strength of the resin, and on the other hand, the synthesis cost is increased when the addition amount of the catalyst is too large; and the catalyst is added twice, so that the reaction can be stably carried out, and the suspended double bonds on the polystyrene-divinylbenzene copolymer can be more thoroughly reacted, so that the crosslinking degree is increased.
The macroporous adsorption resin prepared by the invention has high adsorption capacity and high desorption rate on lincomycin, and the obtained lincomycin finished product has high purity, and can realize high-efficiency extraction and industrial production of lincomycin.
In conclusion, the synthesis method of the macroporous adsorption resin, which is simple in synthesis process, green and environment-friendly, is easy to amplify production and has a good lincomycin extraction effect, can realize green and environment-friendly production of the macroporous adsorption resin and can realize efficient extraction of lincomycin.
The technical solution of the present invention is further described in detail by the following examples.
Detailed Description
The invention relates to a synthetic method of macroporous adsorption resin for lincomycin extraction, which comprises the following steps:
s1, synthesizing a polystyrene-divinylbenzene copolymer;
adding a dispersing agent and methylene blue into water, heating, and stirring until the dispersing agent and the methylene blue are completely dissolved to prepare a water phase; uniformly mixing a monomer, a pore-forming agent and an initiator to obtain an oil phase; adding the oil phase into the prepared water phase, standing for 5-10 minutes, adjusting the height and the rotating speed of a stirring paddle after the oil phase and the water phase are completely layered to control the particle size of the oil phase, uniformly stirring after the particle size is proper, and then heating and preserving heat; after the reaction is finished, washing away the dispersing agent on the surface of the resin by hot water, extracting a pore-foaming agent in the resin by a water vapor extraction method, and then washing and drying to obtain a polystyrene-divinylbenzene copolymer;
the mass ratio of the water to the dispersant to the methylene blue is 100 (0.1-0.5) to (0.01-0.05), wherein the dispersant is polyvinyl alcohol and hydroxyethyl cellulose, and the purpose of adding the polyvinyl alcohol and the hydroxyethyl cellulose is to uniformly disperse an oil phase and to facilitate balling.
The mass ratio of the monomer, the initiator and the pore-foaming agent is (0.5-1.5) to (100-150), wherein the monomer is one or more of divinylbenzene and styrene, ethyl styrene, methyl acrylate, methyl methacrylate, acrylic acid and acrylonitrile; the initiator is one or more of benzoyl oxide, azobisisobutyronitrile, azobisisovaleronitrile and cyclohexanone peroxide; the pore-foaming agent is one or more of saturated hydrocarbon, toluene, xylene and tetramethylbenzene.
The oil phase granularity is controlled to be 0.285-1.0 mm.
The temperature is increased and maintained at 80-95 ℃ for 8-12 hours.
S2, Friedel-crafts alkylation reaction;
adding the polystyrene-divinylbenzene copolymer prepared in the step S1 into a reaction kettle, adding dichloroethane for swelling, adding a catalyst twice after swelling, heating to start reaction, adding tap water into the system after the reaction is finished, recovering dichloroethane through azeotropy of water and dichloroethane, washing the resin until the resin is neutral, discharging, and screening out macroporous adsorption resin with the diameter of 0.315-1.25 mm to obtain the macroporous adsorption resin for lincomycin extraction.
The mass ratio of the polystyrene-divinylbenzene copolymer to the catalyst is 1 (0.1-0.3), the catalyst is anhydrous aluminum trichloride or anhydrous ferric trichloride, after swelling for 2-4 h, half of the catalyst is added at room temperature, the temperature is raised to 80 +/-1 ℃ at the speed of 5 ℃/10min, the reaction is kept for 3-5 h, then the temperature is lowered to below 75 ℃, the rest half of the catalyst is added, and the temperature is raised to 80 +/-1 ℃ for continuous reaction for 6-8 h.
The mass ratio of the polystyrene-divinyl benzene copolymer to the catalyst is 1 (0.1-0.3), and the catalyst is anhydrous aluminum trichloride or anhydrous ferric trichloride.
The macroporous adsorption resin for lincomycin extraction prepared by the method has good extraction effect on lincomycin, and the main factors influencing the extraction effect of the resin on the lincomycin comprise the factors such as specific surface area, average pore diameter, strength and the like of the resin, and the adsorption effect is optimal when the average pore diameter in the general resin is about 5-8 times of the molecular diameter of an adsorbed substance through theoretical calculation; when the resin is ensured to have the pore diameter with proper size, the larger the specific surface area is, the more adsorption sites are, the more adsorption of the adsorbed substances is facilitated; the higher the strength of the resin is, the longer the service life of the resin can be prolonged in the actual use process, so that the cost is reduced.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. The components of embodiments of the present invention generally described and illustrated herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Adding an oil phase mixture containing 100g of divinylbenzene (content of 80%), 150g of tetramethylbenzene and 1.5g of benzoyl peroxide into an aqueous phase solution consisting of 500ml of tap water, 2.5g of polyvinyl alcohol, 2.5g of hydroxyethyl cellulose and 0.025g of methylene blue, standing for 5-10 minutes, adjusting the stirring speed to form uniform droplets with a certain size after the oil phase and the aqueous phase are completely layered, keeping stirring at a constant speed, slowly heating to 80 ℃ for reaction for 2 hours, reacting at 90 ℃ for 2 hours, and reacting at 95 ℃ for 6 hours. After the reaction is finished, the polystyrene-divinylbenzene copolymer is washed by hot water, then the polystyrene-divinylbenzene copolymer is added into a steam extractor, steam purging is carried out at 90 ℃ to recover the pore-foaming agent tetramethylbenzene, the extraction is stopped until the outlet condensate almost does not contain oily substances, and finally the temperature is reduced to discharge the materials, wherein the recovery rate of the tetramethylbenzene is 98.7%. Drying the extracted polystyrene-divinylbenzene copolymer at 105 deg.C for 5 hr, and drying until the water content is less than or equal to 2%.
Weighing 50g of polystyrene-divinylbenzene copolymer, adding 400ml of dichloroethane, stirring and swelling for 4 hours at room temperature, then adding 2.5g of anhydrous aluminum trichloride, preserving heat for 3 hours at 80 ℃, then reducing the temperature to be below 75 ℃, then adding 2.5g of anhydrous aluminum trichloride, and preserving heat for 6 hours at 80 ℃. After the reaction is finished, adding tap water into the system, heating until the water and dichloroethane are azeotroped, recovering the dichloroethane, then washing the resin to be neutral, and finally obtaining the yellow opaque macroporous adsorption resin.
Example 2
Adding an oil phase mixture containing 100g of divinylbenzene (content of 80%), 150g of recovered tetramethylbenzene and 1.5g of benzoyl peroxide into an aqueous phase solution consisting of 500ml of tap water, 2.5g of polyvinyl alcohol, 2.5g of hydroxyethyl cellulose and 0.025g of methylene blue solution, standing for 5-10 minutes, adjusting the stirring speed to form uniform droplets with a certain size after the oil phase and the aqueous phase are completely layered, keeping stirring at a constant speed, slowly heating to 80 ℃ for reaction for 2 hours, reacting at 90 ℃ for 2 hours, and reacting at 95 ℃ for 6 hours. After the reaction is finished, the polystyrene-divinylbenzene copolymer is washed by hot water, then the polystyrene-divinylbenzene copolymer is added into a steam extractor, steam purging is carried out at the temperature of 95 ℃ to recover the pore-foaming agent tetramethylbenzene, the extraction is stopped until the outlet condensate almost does not contain oily substances, and finally the temperature is reduced to discharge the material, wherein the recovery rate of the tetramethylbenzene is 97.5%. Drying the extracted polystyrene-divinylbenzene copolymer at 105 deg.C for 5 hr, and drying until the water content is less than or equal to 2%.
Weighing 50g of polystyrene-divinylbenzene copolymer, adding 400ml of recycled dichloroethane, stirring and swelling for 4 hours at room temperature, then adding 2.5g of anhydrous aluminum trichloride, preserving heat for 3 hours at 80 ℃, then reducing the temperature to be below 75 ℃, then adding 2.5g of anhydrous aluminum trichloride, and preserving heat for 6 hours when the temperature is raised to 80 ℃. After the reaction is finished, adding tap water into the system, heating until the water and dichloroethane are azeotroped, recovering the dichloroethane, then washing the resin to be neutral, and finally obtaining the yellow opaque macroporous adsorption resin.
Example 3
Adding an oil phase mixture containing 100g of divinylbenzene (content of 80%), 90g of toluene, 10g of isododecane and 0.5g of benzoyl peroxide into an aqueous phase solution consisting of 500ml of tap water, 0.5g of polyvinyl alcohol, 0.5g of hydroxyethyl cellulose and 0.05g of methylene blue, standing for 5-10 minutes, adjusting stirring speed to form uniform droplets with a certain size after the oil phase and the aqueous phase are completely layered, keeping stirring at a constant speed, slowly heating to 80 ℃ for reaction for 2 hours, reacting at 90 ℃ for 2 hours, reacting at 95 ℃ for 4 hours, and recovering toluene (recovery rate is 95.3%). After the reaction is finished, the polystyrene-divinylbenzene copolymer is washed by hot water, then the polystyrene-divinylbenzene copolymer is added into a water vapor extractor, steam purging is carried out at 105 ℃ to recover residual pore-forming agent isododecane, the extraction is stopped until the outlet condensate almost does not contain oily substances, and finally the temperature is reduced to discharge the materials, wherein the recovery rate of the isododecane is 96.2%. Drying the extracted polystyrene-divinylbenzene copolymer at 105 deg.C for 5 hr, and drying until the water content is less than or equal to 2%.
Weighing 50g of polystyrene-divinylbenzene copolymer, adding 300ml of dichloroethane, stirring and swelling for 2 hours at room temperature, then adding 7.5g of anhydrous ferric trichloride, preserving heat for 5 hours at 80 ℃, then reducing the temperature to be below 75 ℃, then adding 7.5g of anhydrous ferric trichloride, and preserving heat for 8 hours at 80 ℃. After the reaction is finished, adding tap water into the system, heating to raise the temperature until the water and dichloroethane are azeotroped, recovering the dichloroethane, then washing the resin to be neutral, and finally obtaining the yellow opaque macroporous adsorption resin.
Example 4
Adding an oil phase mixture containing 100g of divinylbenzene (content of 80%), 120g of xylene and 1.0g of benzoyl peroxide into an aqueous phase solution consisting of 500ml of tap water, 1.0g of polyvinyl alcohol, 1.0g of hydroxyethyl cellulose and 0.015g of methylene blue, standing for 5-10 minutes, adjusting the stirring speed to form uniform droplets with a certain size after the oil phase and the aqueous phase are completely layered, keeping stirring at a constant speed, slowly heating to 85 ℃ for reaction for 2 hours, reacting at 90 ℃ for 3 hours, and reacting at 95 ℃ for 5 hours. After the reaction is finished, the polystyrene-divinylbenzene copolymer is washed by hot water, then the polystyrene-divinylbenzene copolymer is added into a water vapor extractor, steam purging is carried out at 105 ℃ to recover a pore-foaming agent xylene, the extraction is stopped until an outlet condensate liquid almost does not contain oily substances, and finally the temperature is reduced to discharge the material, wherein the recovery rate of the xylene is 98.1%. Drying the extracted polystyrene-divinylbenzene copolymer at 105 deg.C for 5 hr, and drying until the water content is less than or equal to 2%.
Weighing 50g of polystyrene-divinylbenzene copolymer, adding 350ml of dichloroethane, stirring and swelling for 4 hours at room temperature, then adding 5g of anhydrous ferric trichloride, preserving heat for 3 hours at 80 ℃, then reducing the temperature to be below 75 ℃, then adding 5g of anhydrous ferric trichloride, and raising the temperature to 80 ℃ and preserving heat for 8 hours. After the reaction is finished, adding tap water into the system, heating to raise the temperature until the water and dichloroethane are azeotroped, recovering the dichloroethane, then washing the resin to be neutral, and finally obtaining the yellow opaque macroporous adsorption resin.
TABLE 1 macroporous adsorbent resin Performance test results
Table 1 shows the performance indexes of the macroporous adsorbent resins synthesized by the above examples and the comparison with the performance of the currently marketed macroporous adsorbent resins for lincomycin extraction, and it can be seen from the table that the specific surface areas of the four examples of the present invention are all larger than the specific surface area of the marketed macroporous adsorbent resin LX-20, the large specific surface areas can provide more adsorption sites, and are more helpful for improving the lincomycin adsorption capacity, and the mechanical strength is higher than LX-20, and the occurrence of ball crushing is not easy in the practical application process. Meanwhile, the recovered tetramethylbenzene is used as a new pore-foaming agent and the recovered dichloroethane is used as a solvent in the later Friedel-crafts alkylation reaction, and the synthesized macroporous adsorption resin is basically similar to the macroporous adsorption resin in the example 1.
In order to further prove the extraction effect of lincomycin and the comparison with the commercial macroporous adsorption resin LX-20, experiments of specific application examples are used for verifying.
Application of the Experimental examples
(1) Adding 2mol/L sodium hydroxide solution into 5000ml of lincomycin fermentation stock solution (the lincomycin content is 31.25g), and adjusting the pH value of the fermentation liquor to 11-12.
(2) The pretreated macroporous adsorption resin prepared in the above examples 1, 2, 3 and 4 and the commercially available lincomycin extraction resin LX-20 are respectively filled with 100ml of wet resin into a resin column, the lincomycin fermentation liquor is adsorbed by the resin column at 1BV/h, the adsorption is stopped when the lincomycin leaks from the effluent liquid of the resin column, the resin column saturated in adsorption is desorbed by 50 percent methanol water solution at the desorption flow rate of 0.5BV/h, then the desorption liquid is respectively desalted and decolored by passing through cation exchange resin D-001 and anion exchange resin LS-807A at the flow rate of 1BV/h, and finally the column liquid is collected.
(3) And (3) carrying out the next cycle of adsorption experiment on the desorbed macroporous adsorption resin, repeating three cycles, and testing the content and purity of lincomycin in the finally collected column-passing liquid, wherein the results are shown in table 2.
Table 2: lincomycin dynamic adsorption and desorption experiment
The results show that the macroporous adsorption resins synthesized in the four embodiments of the invention have adsorption capacity of more than 57mg/ml for lincomycin in the fermentation stock solution, desorption rate of more than 97%, total yield of more than 86%, and purity of the finished product of more than 98%, and meet the lincomycin hydrochloride standard of Chinese pharmacopoeia 2010, and the extraction effect of the macroporous adsorption resins on lincomycin is kept stable after three cycles of recycling. In contrast, the adsorption capacity, desorption rate, total yield and finished product purity of the commercially available macroporous adsorption resin LX-20 on lincomycin are all lower than those of the macroporous adsorption resin synthesized by the method, and the extraction effect on lincomycin is gradually reduced through three-period adsorption experiments.
The application experiments prove that the macroporous adsorption resin prepared by the method has a good extraction effect on lincomycin, and the resin synthesis process has the advantages of low cost, high strength, easiness in amplification, environmental friendliness, low energy consumption and the like.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A synthetic method of macroporous adsorption resin for lincomycin extraction is characterized by comprising the following steps:
s1, adding the dispersing agent and the methylene blue into water, heating and stirring until the dispersing agent and the methylene blue are completely dissolved to prepare a water phase; uniformly mixing a monomer, a pore-forming agent and an initiator to obtain an oil phase; adding the oil phase into the water phase, standing, controlling the particle size of the oil phase after the oil phase and the water phase are completely layered, stirring at a constant speed, and then heating and preserving heat; after the reaction is finished, extracting a pore-foaming agent, washing with water and drying to obtain a polystyrene-divinylbenzene copolymer;
s2, adding the polystyrene-divinylbenzene copolymer prepared in the step S1 into a reaction kettle, swelling with dichloroethane, adding a catalyst twice, heating for reaction, washing the resin until the resin is neutral after the reaction is finished, discharging, and screening macroporous adsorption resin with the diameter of 0.315-1.25 mm to obtain the macroporous adsorption resin for lincomycin extraction.
2. The method according to claim 1, wherein in step S1, the mass ratio of water, the dispersant and the methylene blue is 100 (0.1-0.5) to (0.01-0.05).
3. The method of claim 1, wherein in step S1, the dispersing agent is polyvinyl alcohol and hydroxyethyl cellulose.
4. The method of claim 1, wherein in step S1, the mass ratio of the monomer to the initiator to the porogen is 100 (0.5-1.5) to (100-150).
5. The method of claim 4, wherein the monomer is divinylbenzene and one or more of styrene, ethylstyrene, methyl acrylate, methyl methacrylate, acrylic acid and acrylonitrile; the initiator is one or more of benzoyl oxide, azobisisobutyronitrile, azobisisovaleronitrile and cyclohexanone peroxide; the pore-foaming agent is one or more of saturated hydrocarbon, toluene, xylene and tetramethylbenzene.
6. The method according to claim 1, wherein the temperature of the heating and maintaining step S1 is 80-95 ℃ and the maintaining time is 8-12 hours.
7. The method of claim 1, wherein in step S1, the oil phase has a particle size of 0.285-1.0 mm.
8. The method according to claim 1, wherein in step S2, the mass-to-volume ratio of the polystyrene-divinylbenzene copolymer to the dichloroethane is 1 (5-8), and the swelling time is 2-4 h.
9. The method according to claim 1, wherein in step S2, the mass ratio of the polystyrene-divinylbenzene copolymer to the catalyst is 1 (0.1-0.3), the catalyst is anhydrous aluminum trichloride or anhydrous ferric trichloride, after swelling for 2-4 h, half of the catalyst is added at room temperature, the temperature is raised to 80 + -1 ℃ at a rate of 5 ℃/10min, the reaction is kept at the temperature for 3-5 h, then the temperature is lowered to below 75 ℃, the remaining half of the catalyst is added, and the temperature is raised to 80 + -1 ℃ for further reaction for 6-8 h.
10. Macroporous adsorption resin for lincomycin extraction prepared according to the synthetic method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011383202.0A CN112358563B (en) | 2020-12-01 | 2020-12-01 | Macroporous adsorption resin for lincomycin extraction and synthesis method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011383202.0A CN112358563B (en) | 2020-12-01 | 2020-12-01 | Macroporous adsorption resin for lincomycin extraction and synthesis method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112358563A true CN112358563A (en) | 2021-02-12 |
| CN112358563B CN112358563B (en) | 2023-04-25 |
Family
ID=74536900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011383202.0A Active CN112358563B (en) | 2020-12-01 | 2020-12-01 | Macroporous adsorption resin for lincomycin extraction and synthesis method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112358563B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113045794A (en) * | 2021-05-06 | 2021-06-29 | 陕西蓝深特种树脂有限公司 | Macroporous adsorption resin for extracting chlorogenic acid from eucommia leaves and synthetic method thereof |
| CN113262762A (en) * | 2021-05-06 | 2021-08-17 | 西安蓝深环保科技有限公司 | Adsorbing material for blood perfusion and preparation method thereof |
| CN113698524A (en) * | 2021-08-24 | 2021-11-26 | 陕西蓝深特种树脂有限公司 | Macroporous adsorption resin and synthetic method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101612552A (en) * | 2008-06-26 | 2009-12-30 | 罗门哈斯公司 | Friedel-crafts reaction post-crosslinking adsorbent and preparation method thereof |
| CN102295724A (en) * | 2010-06-24 | 2011-12-28 | 于杰 | Synthesis formula for hypercrosslinked styrene macroporous adsorbent and process route thereof |
| CN103772578A (en) * | 2014-01-07 | 2014-05-07 | 中国农业科学院特产研究所 | Method of removing procymidone residue in ginseng and American ginseng extracts by resin method |
| CN106008811A (en) * | 2016-06-27 | 2016-10-12 | 深圳职业技术学院 | Past-crosslinking macroporous resin and application thereof to purification of effective ingredient of peucedanum praeruptorum dunn |
-
2020
- 2020-12-01 CN CN202011383202.0A patent/CN112358563B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101612552A (en) * | 2008-06-26 | 2009-12-30 | 罗门哈斯公司 | Friedel-crafts reaction post-crosslinking adsorbent and preparation method thereof |
| CN102295724A (en) * | 2010-06-24 | 2011-12-28 | 于杰 | Synthesis formula for hypercrosslinked styrene macroporous adsorbent and process route thereof |
| CN103772578A (en) * | 2014-01-07 | 2014-05-07 | 中国农业科学院特产研究所 | Method of removing procymidone residue in ginseng and American ginseng extracts by resin method |
| CN106008811A (en) * | 2016-06-27 | 2016-10-12 | 深圳职业技术学院 | Past-crosslinking macroporous resin and application thereof to purification of effective ingredient of peucedanum praeruptorum dunn |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113045794A (en) * | 2021-05-06 | 2021-06-29 | 陕西蓝深特种树脂有限公司 | Macroporous adsorption resin for extracting chlorogenic acid from eucommia leaves and synthetic method thereof |
| CN113262762A (en) * | 2021-05-06 | 2021-08-17 | 西安蓝深环保科技有限公司 | Adsorbing material for blood perfusion and preparation method thereof |
| CN113698524A (en) * | 2021-08-24 | 2021-11-26 | 陕西蓝深特种树脂有限公司 | Macroporous adsorption resin and synthetic method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112358563B (en) | 2023-04-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112358563A (en) | Macroporous adsorption resin for lincomycin extraction and synthetic method thereof | |
| CN100509142C (en) | Macroporous adsorption resin special for extracting cephalosporin C and preparation method thereof | |
| CN108355626B (en) | Modified styrene series adsorption resin, preparation method thereof and application thereof in refining lignocellulose hydrolysate | |
| CN100467120C (en) | Macroporous adsorption resin special used for separating antibiotic and its preparation method | |
| CN111269345B (en) | Synthetic method of macroporous adsorption resin | |
| CN111530432B (en) | Preparation method of adsorbing material for blood perfusion | |
| CN112029028B (en) | Macroporous adsorption resin for extracting vitamin B12 and preparation method thereof | |
| CN107337764B (en) | The preparation method and application of the hydrophobic thermo-sensitive gel of corn stalk stalks of rice, wheat, etc. hemicellulose group | |
| CN103509148A (en) | Macropore-crosslinked styrene polymer bead and preparation method thereof | |
| CN104292383A (en) | Gallium-adsorbing chelating resin and preparation method thereof | |
| CN104004131B (en) | High specific surface area amphoteric adsorption resin containing pyrrolidone bases and preparation method thereof | |
| CN111793176A (en) | Lignin-based hypercrosslinked polymer with hierarchical pore structure and preparation method and adsorption application thereof | |
| CN109320650B (en) | Preparation method of macroporous weakly-alkaline acrylic anion exchange resin | |
| CN113698524A (en) | Macroporous adsorption resin and synthetic method thereof | |
| CN109833854A (en) | A kind of macroporous absorbent resin and preparation method thereof | |
| CN108940198A (en) | Spherical activated charcoal, the preparation method and use of carried metal ferro element | |
| CN115945181B (en) | Multistage pore size distribution high specific surface area adsorption resin, preparation method and application thereof | |
| JPH07100375A (en) | High-density large surface area adsorbent | |
| CN113045794A (en) | Macroporous adsorption resin for extracting chlorogenic acid from eucommia leaves and synthetic method thereof | |
| CN105665015A (en) | Solid acid catalyst, preparation method and application thereof | |
| CN114671970A (en) | Method for removing cane molasses pigment by using ultrahigh cross-linked adsorption resin | |
| CN114573864A (en) | Porous adsorption resin and preparation method and application thereof | |
| CN114832797A (en) | Lanthanum modified magnetic resin containing two types of quaternary ammonium sites for efficiently adsorbing phosphorus, preparation method thereof and high-density circulating reflux device | |
| CN111087558A (en) | Modified acrylic-based high-strength salt-resistant high-absorptivity resin and preparation method thereof | |
| CN114797801B (en) | Sewage landscape recycling advanced treatment magnetic resin containing two types of quaternary ammonium sites for synchronously removing nitrogen and phosphorus and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: Room 10911, 9 / F, unit 1, building 2, block D, city gate, high tech Zone, Xi'an City, Shaanxi Province, 710065 Applicant after: XI'AN LANSHEN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Address before: Room 10911, floor 9, unit 1, building 2, block D, metropolitan gate, new high tech Zone, Xi'an City, Shaanxi Province, 710065 Applicant before: XI'AN LANSHEN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: Room 10911, 9 / F, unit 1, building 2, block D, city gate, high tech Zone, Xi'an City, Shaanxi Province, 710065 Applicant after: Xi'an Lanshen New Material Technology Co.,Ltd. Address before: Room 10911, 9 / F, unit 1, building 2, block D, city gate, high tech Zone, Xi'an City, Shaanxi Province, 710065 Applicant before: XI'AN LANSHEN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |