A device for purifying pyrroloquinoline quinone

Abstract

The utility model discloses a kind of pyrroloquinoline quinone's purification device, it is related to pyrroloquinoline quinone production technical field, the outlet of fermentation liquid tank is communicated with ceramic membrane device, the outlet of ceramic membrane device is communicated with first regulating tank, the inlet of regulating tank is communicated with first acid liquid tank, the outlet of first regulating tank is communicated with ion exchange resin column, the outlet of ion exchange resin column is communicated with first effluent tank and second effluent tank, the outlet of second effluent tank is communicated with nanofiltration membrane device, the outlet of nanofiltration membrane device is communicated with second regulating tank, the inlet of second regulating tank is communicated with sodium chloride's bisodium hydrogen sulfate buffer solution tank and second acid liquid tank, the outlet of second regulating tank is communicated with first filter, the solid phase outlet of first filter is communicated with product tank, obtained product purity and quality are high, and environment friendly.

Description

Technical Field

[0001] This utility model relates to the field of pyrroloquinoline quinone production technology, specifically to a purification device for pyrroloquinoline quinone. Background Technology

[0002] Pyrroloquinoline quinone (PQQ) is a coenzyme that can be utilized by dehydrogenases in the human body and is classified as a B vitamin. PQQ was discovered by researchers in 1979. After being isolated and purified from methyltrophic bacteria, studies have shown that it is a coenzyme for dehydrogenases that metabolize methanol in bacteria. It couples with the respiratory electron transport chain and plays a role in promoting bacterial metabolism.

[0003] Traditional PQQ production methods primarily rely on chemical synthesis, but its drawbacks—numerous synthesis steps, numerous byproducts, and high purification costs—are difficult to eliminate. Fermentation-based PQQ production has developed rapidly in recent decades, gradually replacing chemical synthesis as the mainstream method due to its cost advantage. However, the fermentation process generates numerous metabolic impurities with complex structures and physicochemical properties similar to the finished product, resulting in low purity and severely impacting product quality. Summary of the Invention

[0004] The technical problem to be solved by this utility model is to provide a purification device for pyrroloquinoline quinone, which provides pyrroloquinoline quinone with high purity and good quality, in order to address the shortcomings of the existing technology.

[0005] To solve the above-mentioned technical problems, the technical solution of this utility model is as follows:

[0006] A purification apparatus for pyrroloquinoline quinone includes a fermentation broth tank. The outlet of the fermentation broth tank is connected to a ceramic membrane device via a pipeline. The clear liquid outlet of the ceramic membrane device is connected to a first regulating tank via a pipeline. The inlet of the regulating tank is connected to a first acid tank via a pipeline. The outlet of the first regulating tank is connected to an ion exchange resin column via a pipeline. The outlet of the ion exchange resin column is connected to a first effluent tank and a second effluent tank via pipelines. The outlet of the second effluent tank is connected to a nanofiltration membrane device via a pipeline. The concentrated liquid outlet of the nanofiltration membrane device is connected to a second regulating tank via a pipeline. The inlet of the second regulating tank is connected to a sodium chloride-disodium bisulfate buffer solution tank and a second acid tank via pipelines. The outlet of the second regulating tank is connected to a first filter via a pipeline. The solid phase outlet of the first filter is connected to a product tank via a pipeline.

[0007] As an improved technical solution, the solid phase outlet of the first filter is connected to a third regulating tank via a pipeline. The inlet of the third regulating tank is connected to a first purified water tank, a sodium hydroxide tank, and an activated carbon tank via pipelines. The outlet of the third regulating tank is connected to a second filter via a pipeline. The liquid phase outlet of the second filter is connected to a crystallization tank via a pipeline. The inlet of the crystallization tank is connected to a first dilute sulfuric acid solution tank via a pipeline. The outlet of the crystallization tank is connected to the third filter via a pipeline. The solid phase outlet of the third filter is connected to a dryer via a pipeline. The outlet of the dryer is connected to the product tank via a pipeline.

[0008] As an improved technical solution, the outlet of the fermentation broth tank is connected to a pretreatment tank via a pipeline, the inlet of the pretreatment tank is connected to a second dilute sulfuric acid solution tank, a polyaluminum chloride tank and a diatomaceous earth tank via pipelines, the outlet of the pretreatment tank is connected to a plate and frame filter press via a pipeline, the liquid phase outlet of the plate and frame filter press is connected to a filtrate tank via a pipeline, and the outlet of the filtrate tank is connected to the ceramic membrane device via a pipeline.

[0009] As an improved technical solution, the outlet of the filtrate tank is connected to a purification tank via a pipeline, the inlet of the purification tank is connected to an ammonium sulfate tank and a third acid tank via pipelines, and the outlet of the purification tank is connected to the ceramic membrane device via a pipeline.

[0010] As an improved technical solution, the clear liquid outlet of the ceramic membrane device is connected to an ultrafiltration membrane device via a pipeline, and the clear liquid outlet of the ultrafiltration membrane device is connected to the first regulating tank via a pipeline.

[0011] The ultrafiltration membrane device has a molecular weight cutoff of 5000-10000 Da.

[0012] As an improved technical solution, the filtration pore size of the ceramic membrane device is 50-100 nm, and the molecular weight cutoff of the nanofiltration membrane device is 150-300 Da.

[0013] As an improved technical solution, the outlet of the first outflow tank is connected to the inlet of the first regulating tank via a pipeline.

[0014] As a preferred technical solution, the inlet of the ion exchange resin column is connected to an acid water tank via a pipeline, the outlet of the ion exchange resin column is connected to a washing liquid tank via a pipeline, and the outlet of the washing liquid tank is connected to the inlet of the first regulating tank via a pipeline.

[0015] As a preferred technical solution, the inlet of the ion exchange resin column is connected to a phosphate buffer solution tank via a pipeline, the outlet of the ion exchange resin column is connected to an eluent tank via a pipeline, and the outlet of the eluent tank is connected to the inlet of the first regulating tank via a pipeline.

[0016] Due to the adoption of the above technical solution, the beneficial effects of this utility model are:

[0017] This invention discloses a purification device for pyrroloquinoline quinone, comprising a fermentation broth tank, the outlet of which is connected to a ceramic membrane device via a pipeline; the clear liquid outlet of the ceramic membrane device is connected to a first regulating tank via a pipeline; the inlet of the regulating tank is connected to a first acid tank via a pipeline; the outlet of the first regulating tank is connected to an ion exchange resin column via a pipeline; the outlet of the ion exchange resin column is connected to a first effluent tank and a second effluent tank via pipelines; the outlet of the second effluent tank is connected to a nanofiltration membrane device via a pipeline; the concentrated liquid outlet of the nanofiltration membrane device is connected to a second regulating tank via a pipeline; the inlet of the second regulating tank is connected to a sodium chloride-disodium bisulfate buffer solution tank and a second acid tank via pipelines; the outlet of the second regulating tank is connected to a first filter via a pipeline; and the solid phase outlet of the first filter is connected to a product tank via a pipeline. The fermentation broth is first filtered using a ceramic membrane device, which efficiently removes impurities such as bacterial cells and large protein molecules, preventing interference from impurities in subsequent purification steps. The LS-1808 ion exchange resin column has a strong adsorption capacity for impurities, but a relatively weak adsorption capacity for pyrroloquinoline quinone. When the effluent from the LS-1808 ion exchange resin column turns light red, the effluent is switched to a second effluent tank. The purity of pyrroloquinoline quinone in the second effluent reaches >90%, eliminating the need for gradient elution, simplifying the process, saving costs, and improving product yield and purity. The nanofiltration membrane device further removes small molecule impurities and allows only the pyrroloquinoline quinone-related components that meet the requirements to enter subsequent steps through the concentrate outlet, reducing the loss of effective components. The second conditioning tank uses a sodium chloride-disodium bisulfate buffer solution to increase the precipitation of pyrroloquinoline quinone. The buffer solution maintains a stable pH, preventing fluctuations and ensuring product quality stability. The entire process does not require the use of highly toxic or difficult-to-degrade chemical reagents. The waste generated during the filtration and adsorption processes is easy to handle and will not cause serious pollution to the environment, thus balancing product quality and environmental protection requirements.

[0018] The solid phase outlet of the first filter of this utility model is connected to a third regulating tank via a pipeline. The inlet of the third regulating tank is connected to a first purified water tank, a sodium hydroxide tank, and an activated carbon tank via pipelines. The outlet of the third regulating tank is connected to a second filter via a pipeline. The liquid phase outlet of the second filter is connected to a crystallization tank via a pipeline. The inlet of the crystallization tank is connected to a first dilute sulfuric acid solution tank via a pipeline. The outlet of the crystallization tank is connected to the third filter via a pipeline. The solid phase outlet of the third filter is connected to a dryer via a pipeline. The outlet of the dryer is connected to the product tank via a pipeline. After initial separation by the first filter, purified water is added to the third regulating tank to dilute any remaining impurities. Activated carbon adsorbs pigments and small organic molecules (such as residual fermentation byproducts) to further purify the pyrroloquinoline quinone solution. The second filter retains precipitates and activated carbon, preventing them from entering the crystallization process and affecting product purity. A first dilute sulfuric acid solution is added to the crystallization tank to adjust the system to a suitable pH for crystallization, promoting the precipitation of pyrroloquinoline quinone in crystalline form. The crystalline product not only has higher purity but is also easier to separate and dry. The dryer uses a gentle drying method to avoid damaging the pyrroloquinoline quinone structure with high temperatures, ensuring stable product quality. During this process, activated carbon can be regenerated and reused, reducing solid waste generation. The amounts of purified water and dilute sulfuric acid are controllable, resulting in no large amounts of harmful wastewater discharge. This improves product purity and quality while reducing environmental impact.

[0019] The outlet of the fermentation broth tank is connected to a pretreatment tank via a pipeline. The inlet of the pretreatment tank is connected to a second dilute sulfuric acid solution tank, a polyaluminum chloride tank, and a diatomaceous earth tank via pipelines. The outlet of the pretreatment tank is connected to a plate and frame filter press via a pipeline. The liquid phase outlet of the plate and frame filter press is connected to a filtrate tank via a pipeline. The outlet of the filtrate tank is connected to the ceramic membrane device via a pipeline. Adding the second dilute sulfuric acid solution to the pretreatment tank adjusts the pH of the fermentation broth, causing some proteins in the broth to denature and coagulate. Polyaluminum chloride, as a flocculant, adsorbs dispersed small impurity particles to form large flocs. Diatomaceous earth acts as a filter aid, improving subsequent filtration efficiency. The synergistic effect of these three agents makes it easier for the plate and frame filter press to retain impurities in the fermentation broth (such as bacterial fragments and colloidal substances), resulting in a significantly reduced impurity content in the filtrate. The plate and frame filter press has high filtration precision, effectively removing large particulate impurities formed after pretreatment, preventing them from clogging the membrane pores of the subsequent ceramic membrane device, extending the service life of the ceramic membrane, reducing the filtration burden on the ceramic membrane, and ensuring the retention effect of the subsequent ceramic membrane on small molecule impurities. The polyaluminum chloride and diatomaceous earth used in the pretreatment process are easily degradable, and the filter residue produced by plate and frame filter press can be used as raw material for organic fertilizer or subjected to harmless treatment, with no toxic or harmful substances emitted. The filtrate after pretreatment is purer, laying the foundation for subsequent purification steps. The quality problems caused by residual impurities in the early stage are greatly reduced in the final product, and the product quality is more stable.

[0020] The outlet of the filtrate tank is connected to a purification tank via a pipeline. The inlet of the purification tank is connected to an ammonium sulfate tank and a third acid tank via pipelines. The outlet of the purification tank is connected to the ceramic membrane device via a pipeline. Adding ammonium sulfate to the purification tank utilizes the salting-out effect to precipitate small amounts of large-molecule proteins, polysaccharides, and other impurities remaining in the filtrate. The third acid, adjusting the pH, further enhances the precipitation effect without damaging the structure of pyrroloquinoline quinone. After subsequent treatment to remove the precipitated impurities, the filtrate entering the ceramic membrane device has higher purity. The ceramic membrane can then focus more intently on retaining small particulate impurities, preventing impurities from competing with pyrroloquinoline quinone for adsorption sites or affecting subsequent ion exchange. Ammonium sulfate is readily soluble in water and can be removed in subsequent steps, leaving no residue in the product and generating no difficult-to-treat waste. The third acid is a mild acid, used in small quantities and easily neutralized, making it environmentally friendly.

[0021] The clarified liquid outlet of the ceramic membrane device is connected to an ultrafiltration membrane device via a pipeline, and the clarified liquid outlet of the ultrafiltration membrane device is connected to the first regulating tank via a pipeline. The molecular weight cutoff of the ultrafiltration membrane device is 5000-10000 Da. The ultrafiltration membrane device can accurately retain large molecular impurities that are not completely removed by the ceramic membrane device, allowing pyrroloquinoline quinone to pass through smoothly and further purify the solution. This avoids large molecular impurities entering the first regulating tank and reacting with the acid to generate new impurities or affecting the adsorption efficiency of the ion exchange resin column for pyrroloquinoline quinone. The ultrafiltration membrane filtration process does not require the addition of chemical reagents; impurities are separated solely through physical retention. The resulting retentate mainly contains large molecular organic matter, which can be biodegraded without environmental pollution. The solution after ultrafiltration has extremely low impurity content, allowing the subsequent ion exchange resin column to adsorb pyrroloquinoline quinone more efficiently, reducing interference from impurities on adsorption. The final product purity is greatly improved, and there are no large molecular impurities remaining in the product, resulting in superior quality.

[0022] The ceramic membrane device, with a filtration pore size of 50-100 nm, effectively retains bacterial cells and large particulate impurities in the fermentation broth while avoiding the retention of excessive small-molecule active ingredients, thus reducing the loss of active ingredients. Simultaneously, this pore size is not easily clogged, resulting in high filtration efficiency and long-term stable operation, ensuring the continuity of the purification process. The nanofiltration membrane device, with a molecular weight cutoff of 150-300 Da, precisely retains small-molecule impurities in the solution, while pyrroloquinoline quinone can enter subsequent steps with the concentrated liquid outlet, achieving efficient separation of active ingredients and small-molecule impurities.

[0023] The outlet of the first effluent tank is connected to the inlet of the first regulating tank via a pipeline. The inlet of the ion exchange resin column is connected to an acid water tank via a pipeline, and the outlet of the ion exchange resin column is connected to a washing liquid tank via a pipeline. The outlet of the washing liquid tank is connected to the inlet of the first regulating tank via a pipeline. The inlet of the ion exchange resin column is connected to a phosphate buffer solution tank via a pipeline, and the outlet of the ion exchange resin column is connected to an eluent tank via a pipeline. The outlet of the eluent tank is connected to the inlet of the first regulating tank via a pipeline. The liquid in the first effluent tank, combined with the acid water washing and phosphate buffer elution operations, fully elutes the pyrroloquinoline quinone adsorbed on the resin column. The washing liquid and eluent are combined with the liquid in the first effluent tank and reused for the next batch of ultrafiltration liquid treatment, forming a "dynamic recovery-recycling" mechanism. This avoids pyrroloquinoline quinone residue in a single treatment and greatly improves the yield in the intermediate stage. Attached Figure Description

[0024] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0025] Figure 1 This is a structural schematic diagram of an embodiment of the present utility model;

[0026] The components include: 1. Fermentation broth tank; 2. Ceramic membrane device; 3. First regulating tank; 4. First acid tank; 5. Ion exchange resin column; 6. First effluent tank; 7. Nanofiltration membrane device; 8. Second regulating tank; 9. Disodium bisulfate buffer solution tank (sodium chloride); 10. Second acid tank; 11. First filter; 12. Product tank; 13. Third regulating tank; 14. First purified water tank; 15. Sodium hydroxide tank; 16. Activated carbon tank; 17. Second filter; 18. Crystallization tank. Tanks; 19. First dilute sulfuric acid solution tank; 20. Third filter; 21. Dryer; 22. Pretreatment tank; 23. Second dilute sulfuric acid solution tank; 24. Polyaluminum chloride tank; 25. Diatomaceous earth tank; 26. Plate and frame filter press; 27. Filtrate tank; 28. Impurity removal tank; 29. ​​Ammonium sulfate tank; 30. Third acid tank; 31. Ultrafiltration membrane device; 32. Second effluent tank; 33. Acid water tank; 34. Washing solution tank; 35. Phosphate buffer solution tank; 36. Eluent. Detailed Implementation

[0027] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0028] like Figure 1As shown, a purification device for pyrroloquinoline quinone includes a fermentation broth tank 1. The outlet of the fermentation broth tank 1 is connected to a ceramic membrane device 2 via a pipeline. The clear liquid outlet of the ceramic membrane device 2 is connected to a first regulating tank 3 via a pipeline. The inlet of the regulating tank is connected to a first acid tank 4 via a pipeline. The outlet of the first regulating tank 3 is connected to an ion exchange resin column 5 (model LS-1808, manufacturer: Shaanxi Lanshen Special Resin Co., Ltd.) via a pipeline. The outlet of the ion exchange resin column 5 is connected to a first effluent tank 6 and a second effluent tank 32 via a pipeline. The outlet of the second effluent tank 32 is connected to a nanofiltration membrane device 7 via a pipeline. The concentrated liquid outlet of the nanofiltration membrane device 7 is connected to a second regulating tank 8 via a pipeline. The inlet of the second regulating tank 8 is connected to a sodium chloride-disodium bisulfate buffer solution tank 9 and a second acid tank 10 via pipelines. The outlet of the second regulating tank 8 is connected to a first filter 11 via a pipeline. The solid phase outlet of the first filter 11 is connected to a product tank 12 via a pipeline. The fermentation broth is first filtered using a ceramic membrane device 2, which efficiently removes impurities such as bacterial cells and large protein molecules, preventing interference from impurities in subsequent purification steps. The LS-1808 resin column has a strong adsorption capacity for impurities, but a relatively weak adsorption capacity for pyrroloquinoline quinone. The purity of pyrroloquinoline quinone in the second effluent reaches >90%, eliminating the need for gradient elution, simplifying the process, saving costs, and improving product yield and purity. The nanofiltration membrane device 7 further removes small molecule impurities and allows only the pyrroloquinoline quinone-related components that meet the requirements to enter subsequent steps through the concentrate outlet, reducing the loss of effective components. The second conditioning tank 8 uses a sodium chloride-disodium bisulfate buffer solution to increase the precipitation of pyrroloquinoline quinone. The buffer solution maintains a stable pH, preventing fluctuations and ensuring product quality stability. The entire process does not require the use of highly toxic or recalcitrant chemical reagents, and the waste generated during filtration and adsorption is easy to handle, causing no serious environmental pollution, thus balancing product quality and environmental protection requirements.

[0029] The solid phase outlet of the first filter 11 is connected to a third regulating tank 13 via a pipeline. The inlet of the third regulating tank 13 is connected to a first purified water tank 14, a sodium hydroxide tank 15, and an activated carbon tank 16 via pipelines. The outlet of the third regulating tank 13 is connected to a second filter 17 via a pipeline. The liquid phase outlet of the second filter 17 is connected to a crystallization tank 18 via a pipeline. The inlet of the crystallization tank 18 is connected to a first dilute sulfuric acid solution tank 19 via a pipeline. The outlet of the crystallization tank 18 is connected to a third filter 20 via a pipeline. The solid phase outlet of the third filter 20 is connected to a dryer 21 via a pipeline. The outlet of the dryer 21 is connected to the product tank 12 via a pipeline. After initial separation by the first filter 11, the remaining impurities are diluted by adding purified water through the third regulating tank 13. Activated carbon adsorbs pigments and small organic molecules (such as residual fermentation byproducts) in the solution, further purifying the pyrroloquinoline quinone solution. The second filter 17 retains precipitates and activated carbon, preventing them from entering the crystallization process and affecting product purity. A first dilute sulfuric acid solution is added to the crystallization tank 18 to adjust the system to a suitable crystallization pH, promoting the precipitation of pyrroloquinoline quinone in crystalline form. The crystalline product not only has higher purity but is also easier to separate and dry. The dryer 21 uses a gentle drying method to avoid high-temperature damage to the pyrroloquinoline quinone structure, ensuring stable product quality. During this process, the activated carbon can be reused through regeneration, reducing solid waste generation. The amounts of purified water and dilute sulfuric acid are controllable, with no large amounts of harmful wastewater discharged, thus improving product purity and quality while reducing environmental pressure.

[0030] The outlet of the fermentation broth tank 1 is connected to a pretreatment tank 22 via a pipeline. The inlet of the pretreatment tank 22 is connected to a second dilute sulfuric acid solution tank 23, a polyaluminum chloride tank 24, and a diatomaceous earth tank 25 via pipelines. The outlet of the pretreatment tank 22 is connected to a plate and frame filter press 26 via a pipeline. The liquid phase outlet of the plate and frame filter press 26 is connected to a filtrate tank 27 via a pipeline. The outlet of the filtrate tank 27 is connected to the ceramic membrane device 2 via a pipeline. Adding a second dilute sulfuric acid solution to the pretreatment tank 22 adjusts the pH of the fermentation broth, causing some proteins in the broth to denature and coagulate. Polyaluminum chloride, acting as a flocculant, adsorbs dispersed small impurity particles to form large flocs. Diatomaceous earth acts as a filter aid, improving subsequent filtration efficiency. The synergistic effect of these three agents makes it easier for impurities in the fermentation broth (such as bacterial fragments and colloidal substances) to be retained by the plate and frame filter press 26, resulting in a significantly reduced impurity content in the filtrate. The plate and frame filter press 26 has high filtration precision, effectively removing large particulate impurities formed after pretreatment, preventing them from clogging the membrane pores of the subsequent ceramic membrane device 2, extending the lifespan of the ceramic membrane, reducing the filtration burden on the ceramic membrane, and ensuring the subsequent ceramic membrane's retention effect on small molecule impurities. The polyaluminum chloride and diatomaceous earth used in the pretreatment process are easily degradable, and the filter residue produced by the plate and frame filter press can be used as raw material for organic fertilizer or undergo harmless treatment, with no toxic or harmful substances emitted. The pretreated filtrate is purer, laying the foundation for subsequent purification steps. This significantly reduces quality problems caused by residual impurities in the final product, resulting in more stable product quality.

[0031] The outlet of the filtrate tank 27 is connected to a purification tank 28 via a pipeline. The inlet of the purification tank 28 is connected to an ammonium sulfate tank 29 and a third acid tank 30 via pipelines. The outlet of the purification tank 28 is connected to the ceramic membrane device 2 via a pipeline. Adding ammonium sulfate to the purification tank 28 utilizes the salting-out effect to precipitate small amounts of large-molecule proteins, polysaccharides, and other impurities remaining in the filtrate. The third acid adjusts the pH, further enhancing the precipitation effect without damaging the structure of pyrroloquinoline quinone. After subsequent treatment to remove the precipitated impurities, the filtrate entering the ceramic membrane device 2 has higher purity. The ceramic membrane can then focus more intently on retaining small particulate impurities, preventing impurities from competing with pyrroloquinoline quinone for adsorption sites or affecting subsequent ion exchange. Ammonium sulfate is readily soluble in water and can be removed through subsequent steps, leaving no residue in the product and generating no difficult-to-treat waste. The third acid is a mild acid, used in small quantities and easily neutralized, making it environmentally friendly.

[0032] The clarified liquid outlet of the ceramic membrane device 2 is connected to an ultrafiltration membrane device 31 via a pipeline, and the clarified liquid outlet of the ultrafiltration membrane device 31 is connected to the first regulating tank 3 via a pipeline. The molecular weight cutoff of the ultrafiltration membrane device 31 is 5000-10000 Da. The ultrafiltration membrane device 31 can accurately retain large molecular impurities that are not completely removed by the ceramic membrane device 2, while allowing pyrroloquinoline quinone to pass through smoothly, further purifying the solution. This avoids large molecular impurities entering the first regulating tank 3 and reacting with the acid to generate new impurities or affecting the adsorption efficiency of pyrroloquinoline quinone by the ion exchange resin column 5. The ultrafiltration membrane filtration process does not require the addition of chemical reagents; impurities are separated only through physical retention. The resulting retentate mainly contains large molecular organic matter, which can be biodegraded and is environmentally friendly. The solution after ultrafiltration has extremely low impurity content, allowing the subsequent ion exchange resin column 5 to adsorb pyrroloquinoline quinone more efficiently, reducing interference from impurities on adsorption. The final product purity is greatly improved, and there are no large molecular impurities remaining in the product, resulting in superior quality.

[0033] The ceramic membrane device 2, with a filtration pore size of 50-100 nm, effectively retains bacterial cells and large particulate impurities in the fermentation broth while avoiding the retention of excessive small-molecule active ingredients, thus reducing the loss of active ingredients. Simultaneously, this pore size is not easily clogged, resulting in high filtration efficiency and long-term stable operation, ensuring the continuity of the purification process. The nanofiltration membrane device 7, with a molecular weight cutoff of 150-300 Da, precisely retains small-molecule impurities in the solution, while pyrroloquinoline quinone can enter subsequent steps with the concentrated liquid outlet, achieving efficient separation of active ingredients and small-molecule impurities.

[0034] The outlet of the first effluent tank 6 is connected to the inlet of the first regulating tank 3 via a pipeline. The inlet of the ion exchange resin column 5 is connected to an acid water tank 33 via a pipeline, and the outlet of the ion exchange resin column 5 is connected to a washing liquid tank 34 via a pipeline. The outlet of the washing liquid tank 34 is connected to the inlet of the first regulating tank 3 via a pipeline. The inlet of the ion exchange resin column 5 is connected to a phosphate buffer solution tank 35 via a pipeline, and the outlet of the ion exchange resin column 5 is connected to an eluent tank 36 via a pipeline. The outlet of the eluent tank 36 is connected to the inlet of the first regulating tank 3 via a pipeline. When the effluent turns light red, the collection of the effluent is switched to the second effluent tank 32. The liquid in the first effluent tank 6, combined with the acid washing and phosphate buffer elution, fully elutes the pyrroloquinoline quinone adsorbed by the resin column. The washing solution and eluent 36 are combined with the liquid in the first effluent tank 6 and reused for the next batch of ultrafiltration liquid treatment, forming a "dynamic recovery-recycling" mechanism. This avoids the residue of pyrroloquinoline quinone in a single treatment and greatly improves the yield in the intermediate stage.

[0035] It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

Claims

1. A purification apparatus for pyrroloquinoline quinone, comprising a fermentation broth tank, characterized in that: The outlet of the fermentation broth tank is connected to a ceramic membrane device via a pipeline. The clear liquid outlet of the ceramic membrane device is connected to a first regulating tank via a pipeline. The inlet of the regulating tank is connected to a first acid tank via a pipeline. The outlet of the first regulating tank is connected to an ion exchange resin column via a pipeline. The outlet of the ion exchange resin column is connected to a first effluent tank and a second effluent tank via pipelines. The outlet of the second effluent tank is connected to a nanofiltration membrane device via a pipeline. The concentrated liquid outlet of the nanofiltration membrane device is connected to a second regulating tank via a pipeline. The inlet of the second regulating tank is connected to a sodium chloride-disodium bisulfate buffer solution tank and a second acid tank via pipelines. The outlet of the second regulating tank is connected to a first filter via a pipeline. The solid phase outlet of the first filter is connected to a product tank via a pipeline.

2. The purification apparatus for pyrroloquinoline quinone as described in claim 1, characterized in that: The solid phase outlet of the first filter is connected to a third regulating tank via a pipeline. The inlet of the third regulating tank is connected to a first purified water tank, a sodium hydroxide tank, and an activated carbon tank via pipelines. The outlet of the third regulating tank is connected to a second filter via a pipeline. The liquid phase outlet of the second filter is connected to a crystallization tank via a pipeline. The inlet of the crystallization tank is connected to a first dilute sulfuric acid solution tank via a pipeline. The outlet of the crystallization tank is connected to the third filter via a pipeline. The solid phase outlet of the third filter is connected to a dryer via a pipeline. The outlet of the dryer is connected to the product tank via a pipeline.

3. The purification apparatus for pyrroloquinoline quinone as described in claim 1, characterized in that: The outlet of the fermentation broth tank is connected to a pretreatment tank via a pipeline. The inlet of the pretreatment tank is connected to a second dilute sulfuric acid solution tank, a polyaluminum chloride tank, and a diatomaceous earth tank via pipelines. The outlet of the pretreatment tank is connected to a plate and frame filter press via a pipeline. The liquid phase outlet of the plate and frame filter press is connected to a filtrate tank via a pipeline. The outlet of the filtrate tank is connected to the ceramic membrane device via a pipeline.

4. The purification apparatus for pyrroloquinoline quinone as described in claim 3, characterized in that: The outlet of the filtrate tank is connected to a purification tank via a pipeline. The inlet of the purification tank is connected to an ammonium sulfate tank and a third acid tank via pipelines. The outlet of the purification tank is connected to the ceramic membrane device via a pipeline.

5. The purification apparatus for pyrroloquinoline quinone as described in claim 1, characterized in that: The clear liquid outlet of the ceramic membrane device is connected to an ultrafiltration membrane device via a pipeline, and the clear liquid outlet of the ultrafiltration membrane device is connected to the first regulating tank via a pipeline. The ultrafiltration membrane device has a molecular weight cutoff of 5000-10000 Da.

6. The purification apparatus for pyrroloquinoline quinone as described in claim 1, characterized in that: The ceramic membrane device has a filtration pore size of 50-100 nm, and the nanofiltration membrane device has a molecular weight cutoff of 150-300 Da.

7. The purification apparatus for pyrroloquinoline quinone as described in claim 1, characterized in that: The outlet of the first outflow tank is connected to the inlet of the first regulating tank via a pipeline.

8. The purification apparatus for pyrroloquinoline quinone as described in claim 1, characterized in that: The inlet of the ion exchange resin column is connected to an acid water tank via a pipe, and the outlet of the ion exchange resin column is connected to a washing liquid tank via a pipe. The outlet of the washing liquid tank is connected to the inlet of the first regulating tank via a pipe.

9. The purification apparatus for pyrroloquinoline quinone as described in claim 1, characterized in that: The inlet of the ion exchange resin column is connected to a phosphate buffer solution tank via a pipe, and the outlet of the ion exchange resin column is connected to an eluent tank via a pipe. The outlet of the eluent tank is connected to the inlet of the first regulating tank via a pipe.

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