Production system for solvent-free extraction of pentamethylene diamine in fermentation liquor
By using the decarbonization tank, alkalization tank, filtration equipment and multi-effect evaporator in the solvent-free extraction system, combined with a scraper evaporator and distillation tower, the problems of high energy consumption and low purity in the pentamethylenediamine extraction process were solved, the production of high-purity pentamethylenediamine was achieved, energy consumption was reduced and the stability of the device was improved.
Patent Information
- Application Number
- CN202422677957.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-04
- Publication Date
- 2025-09-30
- Estimated Expiration
- 2034-11-04
AI Technical Summary
The existing technology has problems in the extraction process of pentamethylenediamine, such as high energy consumption and difficulty in obtaining high-purity pentamethylenediamine. In particular, the presence of metal ions in salt-containing fermentation broth leads to increased energy consumption in the evaporation process and difficulty in achieving high purity.
A solvent-free extraction system is used, including a decarbonization tank, an alkalization tank, a filtration device and a multi-effect evaporator, combined with a scraper evaporator and a distillation tower. Pentamethylenediamine and salt are separated through distillation and rectification processes, reducing the amount of alkalization materials used and lowering energy consumption.
High-purity extraction of pentamethylenediamine (99.7%) was achieved, energy consumption was reduced, and the operating stability of the device was improved, avoiding solvent loss and cost increases caused by redundant equipment.
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Figure CN223393427U_ABST
Abstract
Description
Technical Field
[0001] The utility model belongs to the technical field of biochemical separation, and relates to a production system for solvent-free extraction of pentamethylenediamine in fermentation liquid. Background Art
[0002] Pentamethylenediamine is an important chemical raw material and a bio-polyamide derived from renewable raw materials. It is widely used in various polyamides, polyurethanes, chelating agents and additives. It can replace the traditional biogenic amine hexamethylenediamine produced by chemical methods. It can be polymerized with dibasic acids to synthesize high-quality polymer materials - new nylon. It is an environmentally friendly, sustainable and high-temperature resistant bioplastic with broad application prospects.
[0003]
[0004] Lysine hydrochloride, catalyzed by enzymes, produces pentamethylenediamine, with carbon dioxide as a byproduct. The chemical reaction equation is shown above. Pentamethylenediamine is alkaline when dissolved in water. Hydrochloric acid or other acids are added during the catalytic process to adjust the fermentation broth to a neutral or weakly alkaline pH, which is suitable for the growth of engineered bacteria and produces pentamethylenediamine hydrochloride (carbonate, sulfate, phosphate, etc.). Furthermore, the fermentation broth contains bacteria, proteins, pigments, raw materials, metabolites, and fermentation products, resulting in a complex composition and considerable separation challenges. Adding an alkali can liberate pentamethylenediamine from the salt, producing a salt. However, direct distillation of a salt-containing pentamethylenediamine aqueous solution requires overcoming the intermolecular forces between water and the metal ions during the evaporation process. This not only increases energy consumption but also makes it difficult to obtain pentamethylenediamine with a purity exceeding 99.5%. Summary of the Invention
[0005] The utility model provides a production system for extracting pentamethylenediamine from fermentation liquid without solvent, which can reduce the amount of alkalizing materials used, has low energy consumption and high device operation stability.
[0006] The technical solution of the utility model is a production system for solvent-free extraction of pentamethylenediamine from fermentation broth, comprising at least one decarbonization tank, an alkalization tank, a filtration device and a multiple-effect evaporator connected in sequence, wherein the discharge pipe at the bottom of the multiple-effect evaporator is connected to the scraper evaporator, the gas phase pipeline of the scraper evaporator is connected to the first distillation device; and the gas phase pipeline at the top of the multiple-effect evaporator is connected to the second distillation tower.
[0007] In an optional solution, the decarbonization tank is provided with a jacket heating device and a stirring structure, an exhaust hole and an exhaust duct are provided on the top, a one-way valve is installed on the exhaust hole, and the other end of the exhaust duct is connected to the CO2 gas absorption tower.
[0008] In the optional solution, there are multiple sets of decarbonization tanks, which are connected in series or in parallel in the production system.
[0009] In an optional solution, the alkalization tank is provided with a jacket heating device and a stirring structure, and an alkali solution feeding system is provided on the upper part.
[0010] In an optional solution, the filtering equipment is a plate filter; the liquid phase outlet of the plate filter is connected to the multiple-effect evaporator.
[0011] In an optional solution, a cooling buffer tank is provided between the alkalization tank and the filtration equipment.
[0012] In an optional solution, a first buffer tank is provided at the front end of the first distillation device, and a second buffer tank is provided at the front end of the second distillation device.
[0013] In an optional solution, the scraper evaporator shell is equipped with a heating jacket on the outside and a stirring blade on the inside.
[0014] In an alternative solution, the pipes of the multiple-effect evaporator are fed through the upper part of the scraped-surface evaporator.
[0015] The utility model has the following beneficial effects:
[0016] The pentamethylenediamine fermentation broth of the present invention is obtained by fermentation of genetically modified Escherichia coli using lysine hydrochloride as raw material. The catalytic process adopts self-pressure suppression, and the pH is adjusted to 7.1-8.5 using carbon dioxide generated by the system. However, the material used to adjust the acidity is not limited to the carbon dioxide generated by the system itself, and other acids such as hydrochloric acid, sulfuric acid, and phosphoric acid can also be used. The concentration of pentamethylenediamine in the fermentation broth is 180-250g / L. When using this system for production, the addition of organic solvents is not required, avoiding solvent loss and the cost increase caused by redundant equipment. A scraper evaporator is added between the multiple-effect evaporator and the first distillation tower to prevent salt from entering the distillation tower, which makes it difficult to obtain high-purity pentamethylenediamine. The mixed vapor of pentamethylenediamine and water from the top of the scraper evaporator is not condensed and directly enters the first distillation tower. The mixed vapor of water and pentamethylenediamine from the top of the triple-effect evaporator is not condensed and directly enters the second distillation tower, reducing the energy consumption of the distillation process.
[0017] The present invention first separates the salt A in the alkalized solution from fluid B (pentanediamine and water) through distillation. Fluid B is then rectified to separate the pentamethylenediamine and water, producing high-purity pentamethylenediamine. Concentration in a multi-effect evaporator prior to the scraper evaporator reduces the load on the scraper evaporator. BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Figure 1 It is a schematic diagram of the structure of the utility model; in the figure, 1-decarbonization tank, 2-alkalization tank, 3-filtration equipment, 4-multi-effect evaporator, 5-scraper evaporator, 6-first buffer tank, 7-first distillation tower, 8-second buffer tank, 9-second distillation tower. DETAILED DESCRIPTION
[0019] The embodiments of the present invention will be described in detail below with reference to the examples and drawings. However, those skilled in the art will understand that the following examples are only used to illustrate the present invention and should not be construed as limiting the scope of the present invention.
[0020] Example 1
[0021] like Figure 1 As shown, a production system for solvent-free extraction of pentamethylenediamine from fermentation broth includes at least one decarbonization tank 1, an alkalization tank 2, a filtration device 3 and a multiple-effect evaporator 4 connected in sequence, the discharge pipe at the bottom of the multiple-effect evaporator 4 is connected to a scraper evaporator 5, the gas phase pipeline of the scraper evaporator 5 is connected to a first distillation device 7; the gas phase pipeline at the top of the multiple-effect evaporator is connected to a second distillation tower 9.
[0022] In a preferred embodiment, the decarbonization tank is equipped with a jacketed heating device and a stirring mechanism. A vent and an exhaust conduit are located on the top. The vent is equipped with a one-way valve, and the other end of the exhaust conduit is connected to a CO2 gas absorption tower. The fermentation broth flows from the fermentation tank via a pipeline into the decarbonization tank, where it is stirred and heated at 70-90°C for 4-20 hours. As the temperature rises, the bicarbonate of pentamethylenediamine decomposes. As the bicarbonate decomposes, carbon dioxide escapes from the fermentation broth, causing the pH of the broth to rise.
[0023] In a preferred embodiment, there are multiple sets of decarbonization tanks connected in series or in parallel in the production system.
[0024] In another preferred embodiment, the alkalization tank is equipped with a jacketed heating device and a stirring mechanism, and an alkali solution feeding system is located on top. The decarbonized fermentation broth is pumped from the decarbonization tank via a pipeline into the alkalization tank. While stirring, a certain proportion of sodium hydroxide solution and calcium oxide or other alkali is added to liberate pentamethylenediamine from its salts. Calcium carbonate and other saturated salts are also precipitated from the system.
[0025] In a preferred embodiment, the filtering device 3 is a plate filter; the liquid phase outlet of the plate filter is connected to the multi-effect evaporator 4. The alkalized liquid is filtered through the plate-type closed filter to remove calcium carbonate and other saturated salts.
[0026] In a preferred embodiment, a cooling buffer tank is provided between the alkalization tank 2 and the filtering equipment 3 .
[0027] In some embodiments, a first buffer tank 6 is provided at the front end of the first rectification unit 7, and a second buffer tank 8 is provided at the front end of the second rectification unit 9. The feed liquid is evaporated and concentrated in the multiple-effect evaporator, with most of the water and a small amount of pentamethylenediamine gas distilled out from the top. The distilled gas A (mostly water vapor and a small amount of gaseous pentamethylenediamine) does not enter the condenser, but instead enters the second buffer tank and then the second rectification column. The concentrated slurry B at the bottom, which consists of pentamethylenediamine, a small amount of water, and carbonates and other salts precipitated as the water content decreases, enters the scraped-surface evaporator for processing.
[0028] In a preferred embodiment, the scraper evaporator shell is equipped with a heating jacket on the outside and a stirring blade inside. The pipes from the multiple-effect evaporator 4 feed the scraper evaporator 5 through the top. The concentrated slurry B from the bottom of the triple-effect evaporator is pumped into the scraper evaporator from the top. Driven by gravity and the rotating blades, the solution forms a downward-spinning thin film on the inner wall of the shell, continuously evaporating and concentrating as it descends. Gas C (pentamethylenediamine and a small amount of water) evaporates from the top of the scraper evaporator, and carbonate exits from the bottom outlet.
[0029] Gas A (mostly water vapor and a small amount of gaseous pentamethylenediamine) exiting the top of the multiple-effect evaporator enters the second distillation tower for distillation. Water evaporates from the top, while the high-boiling-point pentamethylenediamine evaporates from the bottom tray of the second distillation tower. After condensation, it enters the storage tank. Gas C (pentamethylenediamine and a small amount of water) exiting the top of the scraped-plane evaporator passes through the first buffer tank and enters the first distillation tower for distillation. Water evaporates from the top, while the high-boiling-point pentamethylenediamine evaporates from the bottom tray. After condensation, it enters the storage tank.
[0030] When the production system provided by the utility model is used for production, the fermentation liquid obtained by self-pressure fermentation contains pentamethylenediamine bicarbonate and pentamethylenediamine hydrochloride, wherein the fermentation liquid density is 1.08g / cm 3 The fermentation broth flows from the fermenter into a sealed decarbonization tank at 90°C. As bicarbonate decomposes, CO2 escapes from the top of the tank, gradually raising the pH of the fermentation broth to 10.1. The decarbonized fermentation broth is then pumped into an alkalization tank, where 50% sodium hydroxide solution and a small amount of CaO powder are added. The pH of the solution rises to 13.5, and the temperature is maintained at 90°C. Pentylenediamine is released, and carbonates precipitate at saturation. After cooling, the solid-liquid mixture passes through a plate-type sealed filter to separate the carbonates from the liquid. The liquid enters a triple-effect evaporator. 43 wt% of the stream entering the triple-effect evaporator (40 wt% water, 3 wt% pentylenediamine) is distilled out of the top of the third stage of the triple-effect evaporator as steam. Without condensation, it enters a second buffer tank connected to the second distillation column, where it continues to be distilled. 99.7% pentylenediamine is collected at the bottom of the distillation column. The liquid flowing out of the bottom of the triple-effect reactor (30% water, 20% pentamethylenediamine, 7% salt) is pumped into a scraper evaporator. Inside the scraper evaporator, the liquid flows in from the top, where it continuously concentrates. Pentamethylenediamine and water evaporate from the upper portion of the evaporator, while salt exits through the lower outlet. The gaseous pentamethylenediamine and water flow directly into the first buffer tank connected to the first distillation column, and then into the first distillation column. After distillation, 99.7% pentamethylenediamine is collected at the bottom.
[0031] The above embodiments are merely illustrative of the technical concepts and features of the present invention. The contents described are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Within the technical scope disclosed by the present invention, equivalent changes or improvements based on the technical solutions and the concepts of the present invention are also encompassed within the scope of protection of the present invention.
Claims
1. A production system for solvent-free extraction of pentamethylenediamine from fermentation broth, characterized by: The invention comprises at least one decarbonization tank (1), an alkalization tank (2), a filtering device (3) and a multiple-effect evaporator (4) connected in sequence, wherein the discharge pipe at the bottom of the multiple-effect evaporator (4) is connected to a scraper evaporator (5), the gas phase pipeline of the scraper evaporator (5) is connected to a first distillation device (7); and the gas phase pipeline at the top of the multiple-effect evaporator is connected to a second distillation device (9).
2. The production system according to claim 1, characterized in that: The decarbonization tank is provided with a jacket heating device and a stirring structure, an exhaust hole and an exhaust conduit are provided on the top, a one-way valve is installed on the exhaust hole, and the other end of the exhaust conduit is connected to the CO2 gas absorption tower.
3. The production system according to claim 2, characterized in that: There are multiple sets of decarbonization tanks, which are connected in series or in parallel in the production system.
4. The production system according to claim 1, wherein: The alkalization tank is provided with a jacket heating device and a stirring structure, and an alkali solution feeding system is provided on the upper part.
5. The production system according to any one of claims 1 to 4, characterized in that: The filtering device (3) is a plate filter; the liquid phase outlet of the plate filter is connected to the multi-effect evaporator (4).
6. The production system according to claim 5, characterized in that: A cooling buffer tank is provided between the alkalization tank (2) and the filtering equipment (3).
7. The production system according to claim 1, characterized in that: A first buffer tank (6) is provided at the front end of the first distillation device (7), and a second buffer tank (8) is provided at the front end of the second distillation device (9).
8. The production system according to claim 1, characterized in that: The scraper evaporator shell is equipped with a heating jacket on the outside and a stirring blade on the inside.
9. The production system according to claim 8, characterized in that: The pipe of the multi-effect evaporator (4) is fed through the upper part of the scraper evaporator (5).