CN114572993B - Method and device for refining potassium fluoborate as byproduct in synthesis of medical intermediate - Google Patents
Method and device for refining potassium fluoborate as byproduct in synthesis of medical intermediate Download PDFInfo
- Publication number
- CN114572993B CN114572993B CN202210491036.9A CN202210491036A CN114572993B CN 114572993 B CN114572993 B CN 114572993B CN 202210491036 A CN202210491036 A CN 202210491036A CN 114572993 B CN114572993 B CN 114572993B
- Authority
- CN
- China
- Prior art keywords
- potassium fluoborate
- refining
- synthesis
- potassium
- stage
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/06—Boron halogen compounds
- C01B35/063—Tetrafluoboric acid; Salts thereof
- C01B35/066—Alkali metal tetrafluoborates
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
- B01J8/38—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it
- B01J8/384—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it being subject to a circulatory movement only
- B01J8/386—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it being subject to a circulatory movement only internally, i.e. the particles rotate within the vessel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention belongs to the technical field of medical synthesis wastewater treatment, and particularly relates to a method and a device for refining by-product potassium fluoborate in the synthesis of a medical intermediate, wherein the method comprises the following steps: adding boron trifluoride for passivation at the final stage of the production process of a medical intermediate, adding a saturated KCL aqueous solution into a mother solution to generate a potassium fluoborate crystal mixed aqueous solution, performing centrifugal separation and deionized water washing on a filter cake to obtain a first-stage refined potassium fluoborate product, transferring the first-stage refined potassium fluoborate to a potassium fluoborate refining tank, adding deionized water for soaking, stirring and washing, adding a high-selectivity and high-activity complex enzyme preparation and hydrogen peroxide for enzymolysis and oxidation, separating by a secondary centrifuge, dehydrating, washing by uninterrupted deionized water, and spin-drying to obtain the refined potassium fluoborate product. The application of the method and the device can produce a refined potassium fluoborate product as a byproduct, effectively recycle fluorine-containing compounds, reduce pollution disposal and consumption of natural fluorine resources, reduce carbon emission and have important social and economic benefits.
Description
Technical Field
The invention belongs to the technical field of medical synthesis wastewater treatment, and particularly relates to a method and a device for refining a byproduct potassium fluoborate in medical intermediate synthesis.
Background
Boron trifluoride-acetonitrile complex (molecular formula is BF) 3 -CH 3 CN) is a catalyst with strong activity, and is widely applied to the production process of medical intermediates such as azoline and cefpiramide, when the reaction is carried out to the tail end, in order to ensure the purity of the intermediates, the catalytic activity of a boron trifluoride-acetonitrile complex needs to be quenched, the reaction is mainly realized by adding an alkaline solution into a reaction system, boron trifluoride is changed into a sodium fluoborate solution, pharmaceutical enterprises generally change sodium fluoborate into potassium fluoborate, and potassium fluoborate is separated from a mother solution through crystallization.
At present, boron trifluoride can be prepared by reacting diboron trioxide or borate with hydrogen fluoride, or by reacting potassium fluoborate with diboron trioxide and concentrated sulfuric acid, and either way requires hydrofluoric acid, potassium fluoborate and other fluorine-containing compounds, so that a large amount of fluorine-containing compounds are consumed for preparation, and fluorine-containing wastewater is generated. The fluorine-containing compound mainly comes from fluorite, cryolite and brucite, and with the vigorous development of the fluorine chemical industry in China, the gap of fluorine-containing mineral resources in China will be continuously increased in the future. The fluoborate solid waste generated in the production of the medical intermediate is recycled, so that the consumption of natural fluorine resources can be effectively reduced, the emission of a large amount of greenhouse gases generated in the whole life cycle of production, transportation, sale and disposal of fluorine-containing raw materials and products is reduced, and carbon peaking and carbon neutralization can be realized by effectively assisting power.
However, potassium fluoborate generated in the existing intermediate production process contains part of antibiotics, organic matters, solvents and other impurities to remain, and in the process of directly using the potassium fluoborate as a byproduct, the impurities can be transferred to waste water, waste gas and waste residues in the secondary processing and utilization process, so that indirect secondary pollution is caused. Therefore, the problem of efficiently removing residual substances in the potassium fluoborate in the resource recycling process needs to be highly regarded, and secondary influence on the environment is effectively avoided.
Disclosure of Invention
In order to solve the problems in the prior art, and to greatly improve the efficiency and reduce the consumption, the invention combines the impurity removal and refining process of the potassium fluoborate with the production process of the medical intermediate to form a secondary purification process method and a special device. The method and the device are mainly used for resource utilization of potassium fluoborate in the synthesis process of the medical intermediate with boron trifluoride as a catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for refining by-product potassium fluoborate in the synthesis of medical intermediates comprises the following steps:
(1) adding a boron trifluoride passivating reagent into a solution at the later stage of the synthesis reaction of the medical intermediate by taking boron trifluoride as a catalyst, adjusting the pH value of the solution to 6-8, and then adding a saturated potassium chloride solution into the mother liquor containing the fluoborate to obtain a mixed water solution of fluoborate crystals.
(2) And after the potassium fluoborate is completely crystallized, carrying out centrifugal separation on potassium fluoborate crystals, continuously and alternately washing by using a saturated potassium chloride solution and deionized water in the centrifugal process to obtain a first-stage refined potassium fluoborate product, and conveying the solution obtained by centrifugation to a reflux tower to recover the organic solvent.
(3) Then transferring the first-stage refined potassium fluoborate to a potassium fluoborate refining tank, adding deionized water for soaking, continuously stirring and washing, simultaneously adding a certain amount of complex enzyme preparation and hydrogen peroxide for enzymolysis and oxidation treatment, wherein the process comprises two procedures of enzymolysis and oxidation treatment, potassium fluoborate particles are in a fluidized state in a refining system, impurities on the surfaces of the potassium fluoborate particles can be efficiently washed and dissolved, certain temperature and reaction time (20-50 ℃ and 1-2 h) are kept, and residual organic matter impurities, CN, of the potassium fluoborate are removed by biochemical, chemical and physical means - And the like water-soluble impurities;
adding hydrogen peroxide in two stages, wherein in the first stage, enzymolysis is carried out to remove impurities, the content of hydrogen peroxide in a reaction system needs to be controlled, and 1L of hydrogen peroxide is uniformly dropwise added within 1 h; the second stage is chemical oxidation impurity removal, the remaining 1L is added at one time, and the reaction is continued for 1 h.
(4) In the processes of separation by a secondary centrifuge and dehydration by a centrifuge, deionized water is continuously adopted to wash the centrifugal filter material, and the step can efficiently remove F - 、CN - And (3) drying the obtained potassium fluoborate at 105 ℃ to obtain a potassium fluoborate refined product, and refluxing the secondary centrifugal filtrate to the primary centrifugal process section for reuse so as to achieve the purposes of saving water and improving the utilization efficiency of water resources.
The obtained potassium fluoborate is white powdery solid, the content is more than 98 percent, the TOC is lower than 10mg/kg, and CN - Less than 0.5mg/kg, F - Below 0.5mg/kg, the residual potency of antibiotic is 0.
Preferably, the boron trifluoride passivating agent comprises a sodium carbonate solution, and the concentration of the boron trifluoride passivating agent is 0.5-10 mol/L.
Preferably, the peroxidase is a complex enzyme, and the complex enzyme preparation comprises the following components in parts by weight: 1 part of lucid ganoderma laccase (with the enzyme activity of 20000-50000 IU), 2 parts of cyano hydrolase (with the enzyme activity of 20000-50000 IU) and 1 part of bromine peroxidase. The compound enzyme is derived from Ganoderma fungus fermentation broth, and is respectively subjected to ultrafiltration with molecular weight of 10 ten thousand and ultrafiltration with molecular weight of 1 ten thousand daltonsIntercepting the filtrate by a sodium filter membrane with the molecular weight of 1000 dalton, and taking the filtrate with the molecular weight of 1000-10000 dalton, wherein the interior of the filtrate contains high-activity ganoderma laccase and the enzyme activity of 20000-10000 IU. Can effectively reduce antibiotic residue, organic cyanogen and CN - And the like.
The invention also discloses a device for refining the byproduct potassium fluoborate in the synthesis of the medical intermediate, which comprises a primary treatment system and a secondary refining system, wherein a discharge hole of the primary treatment system is connected with a feed hole of the secondary refining system, the primary treatment system is used for crystallization and primary centrifugal treatment, and the secondary refining system is used for enzymolysis, oxidation and secondary centrifugal treatment.
Preferably, the second-stage refining system comprises a potassium fluoborate bin, a discharge port of the potassium fluoborate bin is connected with a feed inlet of a fluidized bed impurity removal reactor, an air inlet at the bottom of the fluidized bed impurity removal reactor is connected with a Roots pressing fan, the top of the fluidized bed impurity removal reactor is respectively connected with an outlet of a hydrogen peroxide storage tank and an outlet of a compound enzyme preparation dispensing tank, the compound enzyme preparation dispensing tank is connected with an outlet of the compound enzyme storage tank, a discharge port at the bottom of the fluidized bed is connected with a feed inlet of a second-stage centrifuge through a pipeline, and a discharge port of the second-stage centrifuge is connected with a feed inlet of the second-stage refining bin.
Preferably, a filtrate discharge port of the secondary centrifuge is connected with a liquid inlet of a filtrate collection water tank, and a liquid outlet of the filtrate collection water tank is connected with the compound enzyme preparation dispensing tank through a reflux pump.
The resource utilization method and the resource utilization device can obtain a refined potassium fluoborate product as a byproduct, effectively recycle fluorine-containing compounds, reduce pollution disposal and consumption of natural fluorine resources, reduce carbon emission and have important social and economic benefits.
Advantageous effects
The invention discloses a refining method of potassium fluoborate as a byproduct in the synthesis of a medical intermediate, which prepares potassium fluoborate by carrying out processes of saturated saline washing, water washing, centrifugal primary refining, peroxidase/double-oxidized water advanced oxidation, water washing, centrifugation, reduced pressure distillation secondary refining and the like on solid waste of fluoborate generated in the production of the medical intermediate.
According to the invention, impurities carried by potassium fluoborate can be washed into water through repeated washing by deionized water, the compound enzyme and hydrogen peroxide are added in the process of washing water circulation to effectively degrade, and secondary washing water is circulated to a primary centrifugation procedure to be used as washing water for the first time. The selected high-selectivity high-activity complex enzyme is clean, pollution-free and harmless to the environment, and can quickly and efficiently degrade residual antibiotics and reaction intermediates thereof in the potassium fluoborate.
Drawings
FIG. 1: two pathways for enzymatic hydrolysis of nitriles;
FIG. 2: the potential mechanism by which cyano hydratase catalyzes the hydrolysis of cyano groups;
FIG. 3: a schematic diagram of a secondary refining system;
FIG. 4 is a schematic view of: a flow chart of a secondary refining combined process of potassium fluoborate;
in the figure, 1: a potassium fluoborate bin; 2: a fluidized bed impurity removal reactor; 3: a high-pressure Roots blower; 4: a secondary centrifuge; 5: a secondary refining bin; 6: a filtrate collection water tank; 7: a reflux pump; 8: a compound enzyme preparation dispensing tank; 9: storing a complex enzyme preparation; 10: a hydrogen peroxide storage tank; 11: a deionized water pipe; 12: a sewage treatment system.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description is made, it should be understood that the terms used in the present specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the invention, so it should be understood that other equivalents and modifications could be made thereto without departing from the spirit and scope of the invention.
The following examples are given by way of illustration of embodiments of the invention and are not to be construed as limiting the invention, as those skilled in the art will appreciate that various modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
Example 1
Under the condition of continuous stirring, controlling the reaction temperature at 40 ℃, adding 1mol/L sodium carbonate solution into a 2000mL solution system at the last stage of a medical intermediate reaction (a medical intermediate synthesis reaction with a boron trifluoride acetonitrile complex as a catalyst), adjusting the pH value to 6.0 to obtain an intermediate crystallization solution, performing centrifugal separation to obtain an intermediate wet product, and further refining and processing; the centrifugal filtrate mainly contains sodium fluoborate solution, 200-300mL of saturated potassium chloride solution is added, the temperature is kept below 20 ℃, potassium fluoborate particle solid is crystallized under stirring, the crystal growing time is controlled to be not less than 60min, then centrifugally separating, alternately washing potassium fluoborate crystals for many times by 200mL of deionized water to obtain wet potassium fluoborate solid, transferring the wet potassium fluoborate solid into a fluidized bed oxidation impurity removal reactor, through enzymolysis and oxidation impurity removal technologies, 10g of compound enzyme liquid (1 part of lucid ganoderma laccase, 2 parts of cyano hydrolase, 1 part of bromine peroxidase and 50000IU of compound enzyme activity) is added, the reaction is controlled to be 30-50 ℃, the reaction time is 1-2h, 2mL of 30% hydrogen peroxide is added, the hydrogen peroxide is added in two stages, the first stage is enzymolysis impurity removal, the content of the hydrogen peroxide in a reaction system needs to be controlled, and 1L of hydrogen peroxide is dropwise added within 1 h; the second stage is chemical oxidation impurity removal, the rest 1L is added at one time, and the reaction is continued for 1 h; after 2h centrifugation was started and the filter cake was washed several times with 100mL of deionized water, which was the most acceptable operationRemoving soluble impurities on the filter cake to a large extent, and finally drying the dehydrated filter cake at 105 ℃ for 4 hours to obtain the potassium fluoborate with the purity of 99.5 percent, the TOC of 7mg/kg and the CN - 0.3mg/kg, F - Below 0.2mg/kg, the residual potency of antibiotic is 0.
Example 2
Under the condition of continuous stirring, controlling the reaction temperature at 40 ℃, adding 1mol/L of sodium carbonate passivator into a 2000L of medical intermediate reaction final-stage solution system, adjusting the pH to 6.5-7, adding 200L of saturated potassium chloride solution to obtain an intermediate crystallization solution, performing centrifugal separation to obtain an intermediate wet product, and further refining and processing; the centrifugal filtrate mainly contains sodium fluoborate solution, 200L of deionized water is used for alternately washing potassium fluoborate crystals, then the crystals are conveyed to a fluidized bed oxidation impurity removal reactor by an automatic screw machine, 10g of compound enzyme liquid (ganoderma laccase: cyano hydrolase: bromine peroxidase =1:2:1, compound enzyme activity 20000 plus 50000 IU) is added through enzymolysis and oxidation technologies, the reaction is controlled to be 20-30 ℃, the reaction time is 2h, 2L of hydrogen peroxide is added in two stages, the first stage is enzymolysis impurity removal, the content of hydrogen peroxide in a reaction system needs to be controlled, 1L of hydrogen peroxide is dropwise added in 1h, the second stage is chemical oxidation impurity removal, the rest 1L of hydrogen peroxide is added at one time and continuously reacts for 1h, after 2h, centrifugal separation is started, 100L of deionized water is used for multiple washing in the period, water-soluble impurities can be fully removed, the purity of potassium fluoborate is dried for 2h at 105 ℃, 98.0 percent is obtained, TOC 5mg/kg, CN - 0.2mg/kg, F - Below 0.3mg/kg, the residual potency of antibiotic is 0.
The base material of the compound enzyme is derived from ganoderma lucidum fungus fermentation liquor, the fermentation is stopped within 48h, the fermentation liquor is respectively subjected to ultrafiltration with 10 ten thousand molecular weight and ultrafiltration cut-off with 1 ten thousand dalton molecular weight, the filtered solution is cut-off by a 1000 dalton molecular weight sodium filter membrane, the filtrate with the molecular weight of 1000-10000 dalton is taken, the interior of the filtrate contains high-activity ganoderma lucidum laccase, and the enzyme activity is 20000-50000 IU.
The mixture ratio of the compound enzyme is as follows: ganoderma laccase (enzyme activity 20000-50000 IU): cyano hydrolase (enzyme activity 20000-50000 IU): bromoperoxidase =1:2: 1. Can effectively reduce antibiotic residue, organic cyanogen and CN - And the like.
The impurities carried by the potassium fluoborate can be washed into water through repeated washing by deionized water, and the impurities can be effectively degraded by adding the complex enzyme and the hydrogen peroxide in the circulating process of the washing water. The immobilized laccase has the advantages of strong enzyme activity, cleanness, no pollution, no toxic or harmful effect on the environment and the like, can quickly and efficiently degrade antibiotics in wastewater when being used for treating antibiotic wastewater, and has better adaptability to the environment. The principle is shown in fig. 1 and 2.
Example 3
The utility model provides a by-product potassium fluoborate refining plant in synthesis of medical intermediate, includes primary treatment system and second grade refining system, primary treatment system's discharge gate is connected with second grade refining system's feed inlet, primary treatment system is used for crystallization and one-level centrifugal treatment, second grade refining system is used for enzymolysis, oxidation and second grade centrifugal treatment. The primary treatment system comprises a crystallization tank and a primary centrifuge.
As shown in fig. 3, the second-stage refining system comprises a potassium fluoborate bin 1, a discharge port of the potassium fluoborate bin is connected with a feed inlet of a fluidized bed impurity removal reactor 2, an air inlet at the bottom of the fluidized bed impurity removal reactor is connected with a high-pressure roots blower 3, the top of the fluidized bed impurity removal reactor is respectively connected with an outlet of a hydrogen peroxide storage tank 10 and an outlet of a complex enzyme preparation dispensing tank 8, the complex enzyme preparation dispensing tank is connected with an outlet of a complex enzyme storage tank 9, a discharge port at the bottom of the fluidized bed is connected with a feed inlet of a second-stage centrifuge 4 through a pipeline, and a discharge port of the second-stage centrifuge is connected with a feed inlet of a second-stage refining bin 5. And a water inlet at the top of the secondary centrifuge 4 is connected with a deionized water pipeline 11.
The filtrate discharge port of the secondary centrifuge is connected with the liquid inlet of the filtrate collection water tank 6, and the liquid outlet of the filtrate collection water tank is connected with the compound enzyme preparation dispensing tank 8 through the reflux pump 7. The overflow-proof port at the upper part of the filtrate collecting water tank 6 is connected with a sewage treatment system 12.
As shown in fig. 4, the combined process flow for the secondary refining of potassium fluoborate is as follows:
the potassium fluoborate from a primary treatment system enters a potassium fluoborate bin 1 after centrifugal dehydration, the potassium fluoborate is added into a fluidized bed impurity removal reactor 2 by automatically controlling the feeding speed through a screw, air is introduced into a center barrel of the fluidized bed impurity removal reactor through a Roots blower 3, the circulation of materials in the fluidized bed is formed through gas lift, the mass transfer efficiency of liquid and solid is enhanced, the gas amount introduced into the center barrel is controlled, the circulation frequency of water in the fluidized bed can be effectively controlled, hydrogen peroxide and a complex enzyme preparation are added into the top of the fluidized bed impurity removal reactor, a certain temperature and Oxidation Reduction Potential (ORP) in the reactor are maintained in the internal water circulation process, and organic matters (including TOC, antibiotics, organic cyanogen and CN) carried by potassium fluoborate solid can be effectively degraded - Etc.), the bottom of the fluidized bed impurity removal reactor is a discharge port, the fluidized bed impurity removal reactor enters a secondary centrifuge 4 for dehydration and washing treatment, deionized water enters the secondary centrifuge 4 through a deionized water pipeline 11, the deionized water is washed by deionized water for many times, solid potassium fluoborate is a byproduct after impurity removal and enters a secondary refining bin 5 for standby, centrifugal filtrate is collected by a filtrate collection water tank 6, a reflux pump 7 reflows to a dispensing tank 8, and the centrifugal filtrate automatically flows into the fluidized bed reactor after being supplemented with a certain amount of mixed enzyme liquid to perform impurity removal reaction treatment. When the filtrate in the filtrate collecting water tank 6 exceeds the limit, the filtrate will enter the sewage treatment system 12 through the overflow preventing port.
The adding amount of hydrogen peroxide and mixed enzyme is controlled on line by ORP, temperature and liquid level on the fluidized bed impurity removal reactor according to ORP, temperature sensor controls the valve of heating steam to keep the temperature in the reactor in a set range, and liquid level sensor controls the feeding and discharging speed to keep the liquid level constant.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described in the foregoing embodiments, or equivalents may be substituted for some of the features thereof; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (8)
1. A method for refining potassium fluoborate as a byproduct in the synthesis of a medical intermediate is characterized by comprising the following process steps:
(1) and (3) crystallization: adding a boron trifluoride passivating reagent into a solution at the later stage of a synthesis reaction of a medical intermediate by using boron trifluoride as a catalyst, and then adding a saturated potassium chloride solution to obtain a potassium fluoborate crystal mixed aqueous solution;
(2) first-stage centrifugation: after the potassium fluoborate is completely crystallized, carrying out centrifugal separation on potassium fluoborate crystals, and washing for multiple times in the centrifugal process to obtain a first-grade refined potassium fluoborate product;
(3) enzymolysis and oxidation: transferring the first-stage refined potassium fluoborate obtained in the step (2) to a second-stage refining system, adding deionized water for soaking, continuously stirring and washing, simultaneously adding a certain amount of peroxidase and hydrogen peroxide, keeping a certain temperature and reaction time, and removing residual organic impurities and water-soluble impurities of the potassium fluoborate;
(4) secondary impurity removal and refining: performing secondary centrifugal separation on the product obtained in the step (3), washing the product with deionized water continuously in the centrifugal dehydration process to remove water-soluble impurities, and drying the obtained potassium fluoborate to obtain a refined potassium fluoborate product;
in the step (3), the peroxidase is a complex enzyme preparation, and the complex enzyme preparation comprises the following components in parts by weight: 1 part of ganoderma laccase with enzyme activity of 20000-50000IU, 2 parts of cyanogen hydrolase with enzyme activity of 20000-50000IU and 1 part of bromine peroxidase; the lucid ganoderma laccase in the compound enzyme preparation is derived from lucid ganoderma fungus fermentation liquor, ultrafiltration with molecular weight of 10 ten thousand and ultrafiltration cutoff with molecular weight of 1 ten thousand daltons are respectively carried out, the filtrate is cutoff through a sodium filter membrane with molecular weight of 1000 daltons, the filtrate with molecular weight of 1000 plus materials and molecular weight of 10000 daltons is taken, and the interior of the filtrate contains the lucid ganoderma laccase with high activity;
in the step (3), the reaction temperature is kept at 20-50 ℃, the reaction time is 2 hours, hydrogen peroxide is added in two stages, the first stage is enzymolysis impurity removal, the content of the hydrogen peroxide in the reaction system needs to be controlled, and 1L of hydrogen peroxide is dropwise added within 1 hour; the second stage is chemical oxidation impurity removal, the remaining 1L is added at one time, and the reaction is continued for 1 h.
2. The method for refining potassium fluoroborate as a byproduct in the synthesis of a pharmaceutical intermediate according to claim 1, wherein in the step (1), the boron trifluoride passivating agent comprises a sodium carbonate solution and a sodium hydroxide solution, the concentration of the boron trifluoride passivating agent is 0.5 to 10mol/L, and the pH value of the solution is adjusted to 6 to 8 after the boron trifluoride passivating agent is added.
3. The method for refining potassium fluoborate as a byproduct in the synthesis of a medical intermediate, according to claim 2, wherein in the step (2), a saturated potassium chloride solution and deionized water are used for alternate washing in a centrifugal process, and the solution obtained by centrifugation is sent to a reflux tower to recover the organic solvent.
4. The method for refining potassium fluoborate as a byproduct in the synthesis of a medical intermediate, according to claim 1, wherein in the step (4), the secondary centrifugal filtrate is refluxed to the primary centrifugal process stage for reuse.
5. The method for purifying potassium fluoroborate as a byproduct in the synthesis of a pharmaceutical intermediate according to claim 1, wherein in the step (4), the obtained potassium fluoroborate is dried at 105 ℃.
6. A device capable of realizing the refining method of the byproduct potassium fluoborate in the synthesis of the medical intermediate as claimed in any one of claims 1 to 5, which is characterized by comprising a primary treatment system and a secondary refining system, wherein a discharge port of the primary treatment system is connected with a feed port of the secondary refining system, the primary treatment system is used for realizing the crystallization in the step (1) and the primary centrifugation process in the step (2) as claimed in claim 1, and the secondary refining system is used for realizing the enzymolysis and oxidation in the step (3) and the secondary impurity removal and refining process in the step (4) as claimed in claim 1.
7. The device according to claim 6, wherein the secondary refining system comprises a potassium fluoborate bin, a discharge port of the potassium fluoborate bin is connected with a feed port of a fluidized bed impurity removal reactor, an air inlet at the bottom of the fluidized bed oxidation impurity removal reactor is connected with a high-pressure Roots blower, the top of the fluidized bed impurity removal reactor is respectively connected with an oxygen solution storage tank and an outlet of a complex enzyme preparation dosing tank, a discharge port at the bottom of the fluidized bed is connected with a feed port of a secondary centrifuge through a pipeline, and a discharge port of the secondary centrifuge is connected with a feed port of the secondary refining bin.
8. The device of claim 7, wherein the filtrate discharge port of the secondary centrifuge is connected with the liquid inlet of the filtrate collection water tank, and the liquid outlet of the filtrate collection water tank is connected with the compound enzyme preparation dosing tank through a reflux pump.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210491036.9A CN114572993B (en) | 2022-05-07 | 2022-05-07 | Method and device for refining potassium fluoborate as byproduct in synthesis of medical intermediate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210491036.9A CN114572993B (en) | 2022-05-07 | 2022-05-07 | Method and device for refining potassium fluoborate as byproduct in synthesis of medical intermediate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114572993A CN114572993A (en) | 2022-06-03 |
| CN114572993B true CN114572993B (en) | 2022-07-26 |
Family
ID=81767753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210491036.9A Active CN114572993B (en) | 2022-05-07 | 2022-05-07 | Method and device for refining potassium fluoborate as byproduct in synthesis of medical intermediate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114572993B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120082608A1 (en) * | 2009-06-19 | 2012-04-05 | Stella Chemifa Corporation | Method for producing tetrafluoroborate |
| CN102730710A (en) * | 2012-07-06 | 2012-10-17 | 江苏华盛精化工股份有限公司 | Method for separating potassium chloride and potassium fluoride |
| CN105731482A (en) * | 2016-01-15 | 2016-07-06 | 江苏新泰材料科技股份有限公司 | Method for preparing potassium fluoborate from fluorine-containing wastewater |
| CN109354034A (en) * | 2018-11-22 | 2019-02-19 | 山东罗欣药业集团股份有限公司 | A kind of fluorine-containing waste liquid borofluoride exchange crystallization recovery technology of cephalo |
| CN113845123A (en) * | 2021-11-01 | 2021-12-28 | 石药集团中诺药业（石家庄）有限公司 | Method for recovering potassium fluoborate from azolin intermediate wastewater |
-
2022
- 2022-05-07 CN CN202210491036.9A patent/CN114572993B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120082608A1 (en) * | 2009-06-19 | 2012-04-05 | Stella Chemifa Corporation | Method for producing tetrafluoroborate |
| CN102730710A (en) * | 2012-07-06 | 2012-10-17 | 江苏华盛精化工股份有限公司 | Method for separating potassium chloride and potassium fluoride |
| CN105731482A (en) * | 2016-01-15 | 2016-07-06 | 江苏新泰材料科技股份有限公司 | Method for preparing potassium fluoborate from fluorine-containing wastewater |
| CN109354034A (en) * | 2018-11-22 | 2019-02-19 | 山东罗欣药业集团股份有限公司 | A kind of fluorine-containing waste liquid borofluoride exchange crystallization recovery technology of cephalo |
| CN113845123A (en) * | 2021-11-01 | 2021-12-28 | 石药集团中诺药业（石家庄）有限公司 | Method for recovering potassium fluoborate from azolin intermediate wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114572993A (en) | 2022-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110981099A (en) | Method for producing ethanol by recycling biogas slurry and vinasse clear liquid and reusing | |
| CN201658945U (en) | Sintering smoke purifying system based on heat pipe afterheat recovery technology | |
| CN113955839A (en) | Method for treating chlorinated polyethylene production wastewater | |
| CN114572993B (en) | Method and device for refining potassium fluoborate as byproduct in synthesis of medical intermediate | |
| CN108569812B (en) | Treatment system and treatment method for wastewater containing low-concentration sulfuric acid | |
| CN104058539A (en) | Semi-fiber treatment process based on industrial waste water of viscose | |
| CN109231331B (en) | CO removal of sludge digestion biogas slurry2Special deamination device and process | |
| CN203754551U (en) | Device for recycling and treating waste water produced during preparation of decanedioic acid by utilizing castor oil | |
| CN110562987A (en) | Method and equipment for reducing production amount of sewage in sodium fluosilicate production and recycling sewage | |
| CN203976474U (en) | A kind of eddy current revolves mixed anaerobic reactor | |
| CN110559818A (en) | Flue gas desulfurization method using secondary zinc oxide soot as desulfurizer | |
| CN103771611B (en) | The solid-liquid separating method of cellulose alcoholic fermentation waste liquid | |
| CN202542834U (en) | Polycrystalline silicon waste acid reclaiming device and polyaluminium chloride (PAC) production device using same | |
| CN106590752A (en) | Method for increasing activity and recovery rate of catalyst in catalytic gasification of coal | |
| CN111320332B (en) | Leather sewage emission reduction treatment method | |
| CN212383460U (en) | Treatment system for absorbing tail gas sulfur dioxide gas | |
| CN109160660B (en) | Method for recovering glycolic acid from sodium carboxymethylcellulose production wastewater | |
| CN113651465A (en) | Chemical strong brine pretreatment device and pretreatment method | |
| CN114684953A (en) | Method and device for treating ethylene waste alkali liquor | |
| CN218232124U (en) | High-concentration waste acid recycling process device | |
| CN111777514A (en) | Comprehensive utilization method of mixed gas containing hydrogen fluoride and hydrogen chloride | |
| CN220277008U (en) | System for regenerating ion exchange purification phosphoric acid resin | |
| CN107501206A (en) | Solvent purifications method rubber accelerator M synthesis sulfenamide type accelerators TBBS method | |
| CN110590509A (en) | Production method for carbon dioxide cyclic decomposition coking crude phenol coproduction desulfurizer | |
| CN112979036B (en) | System and method for recycling waste alkali liquor |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |