Extraction method of pentamethylene diamine

Abstract

The invention provides an extraction method of pentamethylene diamine, which comprises the following steps: reacting pentamethylene diamine fermentation liquor and / or treating fluid thereof through a rectifying tower, and discharging obtained feed liquid from the bottom of the rectifying tower; the temperature of the bottom of the rectifying tower is higher than that of the top of the rectifying tower. The method directly aims at the fermentation liquid and / or the treatment liquid of the fermentation liquid needing alkalization extraction of pentamethylene diamine, operation is easy, the decomposition rate of pentamethylene diamine carbonate can be increased, the dosage of alkaline substances in the alkalization process is reduced, accordingly, the probability of occurrence of abnormal working conditions such as tank overflowing and tank spraying is reduced, and efficient and smooth production is guaranteed.

Description

Technical Field

[0001] The invention relates to pentamethylenediamine, in particular to a method for extracting pentamethylenediamine from a fermentation broth. Background Art

[0002] 1,5-Pentanediamine (Diaminopentane; DN5, hereinafter referred to as pentamethylenediamine), also known as cadaverine, has a wide range of applications in agriculture, medicine and industry. In agriculture, exogenous application of pentamethylenediamine can improve fruit setting and promote fruit ripening; in medicine, pentamethylenediamine can be used as an effective drug for treating dysentery; in industry, pentamethylenediamine prepared by biological fermentation can replace diamines from petrochemical products and undergo polymerization reactions to generate various polymers with different properties, thereby avoiding the high cost of petrochemical products and the adverse effects of production on the environment. It can also be widely used in aerospace, automotive parts, mechanical parts, electronic appliances, packaging materials and other fields.

[0003] Regarding the prior art of separating and extracting pentamethylenediamine from pentamethylenediamine fermentation broth, the following reports can be cited. Patent US7189543B2 discloses a method for preparing pentamethylenediamine adipate crystals directly from pentamethylenediamine fermentation broth, specifically using adipic acid to neutralize pentamethylenediamine produced in the whole cell catalytic process, cooling to obtain pentamethylenediamine adipate crystals. Patent applications (US2010 / 0292429A1, CN101981202A and EP1482055A1) disclose the use of butanol extraction to separate and extract pentamethylenediamine from fermentation broth, specifically adding sodium hydroxide to pentamethylenediamine fermentation broth, high temperature reflux cracking byproducts in the fermentation broth, using butanol to extract multiple times to obtain an organic phase containing pentamethylenediamine, distilling out the low boiling point solvent in the organic phase to obtain high boiling point pentamethylenediamine, and further distilling to obtain high-purity pentamethylenediamine.

[0004] In the prior art of separating and extracting pentamethylenediamine disclosed at present, the yield of pentamethylenediamine carboxylate obtained by crystallization method is low, and impurities such as lysine remain, which makes it difficult to further purify (CN101578256A). The organic solvent of the extraction method has a strong odor, high toxicity, and is flammable and explosive, which increases the difficulty of practical application; and the organic solvent needs to be recovered, which increases the process flow and energy consumption. Summary of the invention

[0005] The present invention provides a method for extracting pentamethylenediamine, which comprises the following steps: allowing pentamethylenediamine fermentation liquid and / or a treated liquid thereof to enter a distillation tower body through the middle and upper part of the distillation tower body, and then spreading the liquid to the first-layer distillation tower plate through a downcomer to the second-layer distillation tower plate, and then sequentially downward to the bottom of the distillation tower, and the obtained liquid is discharged from the bottom of the distillation tower for alkalization treatment to release pentamethylenediamine;

[0006] Wherein, the pentamethylenediamine in the pentamethylenediamine fermentation liquid and / or its treated liquid exists in the form of carbonate and / or bicarbonate, and pentamethylenediamine sulfate;

[0007] The temperature of the top of the distillation tower is 30-80°C, and the temperature of the bottom of the distillation tower is 70-120°C;

[0008] The temperature at the bottom of the distillation tower is greater than the temperature at the top of the distillation tower;

[0009] The temperature increase rate of the pentamethylenediamine fermentation liquid and / or its treated liquid when flowing from an adjacent lower temperature zone to a higher temperature zone is 1 to 3°C / min.

[0010] In a specific embodiment, the temperature of the bottom of the distillation tower is 85-100°C.

[0011] In a specific embodiment, the distillation tower has 5 to 50 stages, and further 10 to 30 stages.

[0012] In one specific embodiment, the distillation tower is a plate tower or a packed tower.

[0013] In a specific embodiment, the distillation tower is provided with a condenser and a reflux tank; wherein, a first reflux passage is formed outside the distillation tower body near the top, the condenser and the reflux tank are both arranged on the first reflux passage, the condenser is connected to the tower top, and the reflux tank is connected to the side wall near the tower top.

[0014] In a specific embodiment, the distillation tower is provided with a reboiler, which is arranged outside the distillation tower body and near the bottom. The reboiler is connected to the bottom of the distillation tower body and the side wall near the bottom through two pipelines respectively to form a second reflux passage between the distillation tower body and the reboiler.

[0015] The method of one embodiment of the present invention treats pentamethylenediamine fermentation liquid and / or treated liquid, wherein pentamethylenediamine exists in the form of carbonate and / or bicarbonate and pentamethylenediamine sulfate. The method improves the decomposition rate of pentamethylenediamine carbonate, reduces the amount of alkaline substances used in the alkalization process, thereby reducing alkaline solid residue, and reduces the probability of abnormal working conditions such as tank overflow and tank spray, thereby ensuring efficient and smooth production. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1a This is a schematic structural diagram of a device for extracting pentamethylenediamine according to one embodiment of the present invention;

[0017] Figure 1b This is a schematic structural diagram of a device for extracting pentamethylenediamine according to another embodiment of the present invention;

[0018] Figure 1cThis is a schematic structural diagram of a device for extracting pentamethylenediamine according to another embodiment of the present invention;

[0019] Figure 2 The figure is a schematic diagram of the structure of a distillation tower for extracting pentamethylenediamine according to one embodiment of the present invention. DETAILED DESCRIPTION

[0020] Typical embodiments that embody the features and advantages of the present invention will be described in detail in the following description. It should be understood that the present invention can have various changes in different embodiments without departing from the scope of the present invention, and the descriptions and illustrations therein are essentially used for illustrative purposes rather than for limiting the present invention. Among them, "first", "second", "third", "fourth", "fifth", etc. are used to distinguish multiple processes or products with the same name, and do not limit their order.

[0021] An embodiment of the present invention provides a method for extracting pentamethylenediamine, comprising obtaining pentamethylenediamine by sequentially passing a material selected from a pentamethylenediamine fermentation broth and / or a treated broth thereof through multiple temperature zones for heating treatment; the multiple temperature zones include a first temperature zone, a second temperature zone and a discharge temperature zone.

[0022] The temperature zone refers to the temperature interval of the heating treatment.

[0023] In one embodiment, the raw material liquid enters into a plurality of temperature zones from the first temperature zone and is discharged from the discharge temperature zone.

[0024] In one embodiment, the pentamethylenediamine fermentation broth can be prepared by a fermentation method, or by a fermentation method and an enzyme conversion method.

[0025] In the pentamethylenediamine fermentation broth (or its treated liquid) of one embodiment of the present invention, pentamethylenediamine mainly exists in the form of carbonate and / or bicarbonate, and partially exists in the form of pentamethylenediamine sulfate, for example, the pentamethylenediamine fermentation broth (or its treated liquid) prepared according to the schemes described in CN105164101B, CN110468167A or CN104762336A.

[0026] In one embodiment of the present invention, pentamethylenediamine fermentation liquid is continuously heated in multiple temperature zones, so that carbonate and / or bicarbonate of pentamethylenediamine is decomposed and converted into pentamethylenediamine. By adopting the method of graded heating in multiple temperature zones, the generated carbon dioxide gas is easier to be discharged from the system, which is beneficial for the decomposition reaction equilibrium to proceed in the positive reaction direction.

[0027] The method of one embodiment of the present invention alleviates the problem of high alkalization cost and difficult solid waste treatment caused by excessive solid residue during alkalization of pentamethylenediamine fermentation broth in the prior art. The alkalization mainly refers to increasing the pH value of the fermentation broth by adding alkaline substances such as sodium hydroxide and calcium oxide to the pentamethylenediamine fermentation broth to fully release pentamethylenediamine in the fermentation broth.

[0028] In one embodiment, the total residence time of the liquid material in multiple temperature zones is 0.3 to 24 hours, for example, 0.5 hours, 0.8 hours, 1 hour, 1.2 hours, 1.5 hours, 1.8 hours, 5 hours, 10 hours, 15 hours, 18 hours, and 20 hours; more preferably, the total residence time of the liquid material in multiple temperature zones can be 1 to 12 hours.

[0029] In one embodiment, the average flow rate of the liquid material in multiple temperature zones is 0.001 to 50 tons / hour, and the preferred average flow rate is 0.005 to 20 tons / hour, for example, 0.01 tons / hour, 0.05 tons / hour, 0.1 tons / hour, 0.5 tons / hour, 1 ton / hour, 2 tons / hour, 5 tons / hour, 8 tons / hour, 10 tons / hour, 12 tons / hour, 15 tons / hour, 18 tons / hour, 20 tons / hour, 25 tons / hour, 30 tons / hour, 35 tons / hour, 40 tons / hour, 45 tons / hour, etc.

[0030] In one embodiment, the time that the pentamethylenediamine fermentation broth stays in each temperature zone can be adjusted to achieve effective decomposition of pentamethylenediamine carbonate and / or bicarbonate.

[0031] In one embodiment, the pentamethylenediamine fermentation broth can be introduced into the first temperature zone for reaction for 0.1 to 6 hours, preferably for 0.1 to 2 hours, and more preferably for 0.5 to 1 hour, for example, 0.2 hours, 0.5 hours, 0.6 hours, 0.8 hours, 1.2 hours, 1.5 hours, 1.8 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, etc.

[0032] In one embodiment, the liquid discharged from the first temperature zone enters the second temperature zone and reacts in the second temperature zone for 0.1 to 6 hours, preferably 0.1 to 2 hours, and further preferably 0.5 to 1 hour, for example, 0.2 hours, 0.5 hours, 0.6 hours, 0.8 hours, 1.2 hours, 1.5 hours, 1.8 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, etc.

[0033] In one embodiment, the pentamethylenediamine fermentation broth is heated in multiple stages through multiple temperature zones connected in series, so that the product gas can be discharged in time, the reaction is more thorough, and the decomposed liquid is discharged from the discharge temperature zone.

[0034] In the present invention, there is no particular requirement for the concentration of the pentamethylenediamine fermentation broth. In one embodiment, the content of pentamethylenediamine in the pentamethylenediamine fermentation broth may be 1-15%, preferably 5-10%, where the above percentages are the mass percentages of pentamethylenediamine in the pentamethylenediamine fermentation broth. For example, the content of pentamethylenediamine may be 2%, 6%, 8%, 12%, etc.

[0035] In one embodiment, the pentamethylenediamine fermentation broth is a fermentation broth of pentamethylenediamine obtained by lysine fermentation and decarboxylation and / or its treated liquid, and / or a fermentation broth of amine obtained by fermentation and / or its treated liquid, or a solution obtained by mixing the fermentation broth of amine and its treated liquid. For example, the pentamethylenediamine fermentation broth is prepared by the preparation method of 1,5-pentamethylenediamine in patent applications CN105164101B, CN110468167A or CN104762336A.

[0036] In one embodiment, the pH of the pentamethylenediamine fermentation broth may be 6-10, and further may be 7-9.

[0037] In one embodiment, the temperature in the rear temperature zone is greater than the temperature in the front temperature zone, for example, the temperature in the second temperature zone is greater than the temperature in the first temperature zone, and the temperature in the discharge temperature zone is the highest among the multiple temperature zones.

[0038] In one embodiment, the temperature in the rear temperature zone is lower than the temperature in the front temperature zone, for example, the temperature in the second temperature zone is lower than the temperature in the first temperature zone, and the temperature in the discharge temperature zone is the lowest among the multiple temperature zones.

[0039] In one embodiment, the temperature of the plurality of temperature zones is above room temperature, preferably 25 to 120°C, for example, 50°C, 60°C, 70°C, 80°C, 90°C, 95°C, or 110°C.

[0040] In one embodiment, the temperature of the first temperature zone is 60-85°C, for example 62°C, 65°C, 66°C, 68°C, 70°C, 72°C, 74°C, 75°C, 76°C, 78°C, 80°C, 81°C, 82°C.

[0041] In one embodiment, the temperature of the second temperature zone is 80-95°C, for example, 82°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C.

[0042] In one embodiment, the pressure of multiple temperature zones is 0 to 100 kPa, and can further be 5 to 20 kPa, for example, 1 kPa, 2 kPa, 10 kPa, 12 kPa, 15 kPa, 180 kPa, 25 kPa, 30 kPa, 35 kPa, 40 kPa, 50 kPa, 60 kPa, 70 kPa, and 80 kPa.

[0043] In one embodiment, the temperature difference ΔT between the temperature of the second temperature zone and the temperature of the first temperature zone is 0≤ΔT≤10°C, such as 2°C, 5°C, 6°C, or 8°C.

[0044] In one embodiment, the plurality of temperature zones include a first temperature zone, a second temperature zone and a third temperature zone connected in sequence. During operation, the liquid material passes through the first temperature zone, the second temperature zone and the third temperature zone in sequence.

[0045] In one embodiment, the temperature of the third temperature zone is 90-120°C, for example, 92°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C, 110°C, 115°C, and more preferably 93-97°C.

[0046] In another embodiment, the plurality of temperature zones include a first temperature zone, a second temperature zone, a third temperature zone and a fourth temperature zone connected in sequence. During operation, the liquid material passes through the first temperature zone, the second temperature zone, the third temperature zone and the fourth temperature zone in sequence.

[0047] In another embodiment, the plurality of temperature zones include a first temperature zone, a second temperature zone, a third temperature zone, a fourth temperature zone and a fifth temperature zone connected in sequence. During operation, the liquid material passes through the first temperature zone, the second temperature zone, the third temperature zone, the fourth temperature zone and the fifth temperature zone in sequence.

[0048] In one embodiment, when the liquid material flows from an adjacent lower temperature zone to a higher temperature zone, it can quickly reach the temperature of the higher temperature zone. For example, the heating rate of the liquid material from the first temperature zone to the second temperature zone is 0 to 5°C / min, preferably 1 to 3°C / min, for example, 0.5°C / min, 1°C / min, 1.5°C / min, 2°C / min, 2.5°C / min, 3°C / min, 3.5°C / min, 4°C / min, and 4.5°C / min.

[0049] In the present invention, the discharge temperature zone is a temperature zone for discharging the pentamethylenediamine conversion liquid, and it can be the third temperature zone, the fourth temperature zone or the fifth temperature zone in sequence.

[0050] In one embodiment, the multiple temperature zones may be located in multiple reaction containers respectively, or may be located in the same reaction container.

[0051] like Figure 1a As shown, one embodiment of the present invention provides a device for extracting pentamethylenediamine for implementing the above method, including a plurality of reactors connected in sequence, the plurality of reactors including at least one first reactor 21, at least one second reactor 22 and a discharge reactor 29, and the first reactor 21 is connected to the second reactor 22.

[0052] In one embodiment, the extraction device includes a fermentation tank 10 and at least one preheating kettle 11, and the preheating kettle 11 is respectively connected to the fermentation tank 10 and multiple reactors; wherein the fermentation tank 10 is used to hold the raw material pentamethylenediamine fermentation liquid or its treated liquid, and the preheating kettle 11 is used to preheat the raw material so that it can enter the subsequent reactor for heating reaction.

[0053] In one embodiment, the preheating kettle 11 is connected to the first reactor 21, the first reactor 21 is connected to the second reactor 22, and the second reactor 22 is connected to the discharge reactor 29. During operation, the raw material pentamethylenediamine fermentation liquid enters the preheating kettle 11 from the fermentation tank 10 for preheating, and then enters the first reactor 21, the second reactor 22, and the discharge reactor 29 in sequence for reaction. After the decomposition reaction of pentamethylenediamine carbonate and / or bicarbonate is completed, the remaining liquid material (including the conversion liquid of pentamethylenediamine) is discharged from the discharge reactor 29 and alkalized by an alkaline substance such as sodium hydroxide, potassium hydroxide or calcium oxide to fully release pentamethylenediamine.

[0054] In one embodiment, the extraction device includes an exhaust pipeline, a liquid inlet pipeline, a heat exchanger 30 and a steam compressor 40 .

[0055] In one embodiment, multiple reactors are connected via exhaust pipes and liquid inlet pipes, respectively. The liquid inlet pipes are used to circulate pentamethylenediamine fermentation liquid or its treated liquid among multiple reactors, and the exhaust pipes are used to circulate the gas generated by the raw material liquid during the reaction process.

[0056] In one embodiment, the liquid inlet pipeline may be composed of multiple sections of pipelines. For example, the first reactor 21 is connected to the second reactor 22 via a first liquid inlet pipeline, and the second reactor 22 is connected to subsequent reactors via a second liquid inlet pipeline.

[0057] In one embodiment, the steam compressor 40 is connected to the exhaust pipeline, and the heat exchanger 30 is disposed in the preheating kettle 11 and is connected to the fermentation tank 10 and the steam compressor 40, respectively.

[0058] In one embodiment, during the decomposition process of pentamethylenediamine carbonate and / or pentamethylenediamine bicarbonate, water vapor and a small amount of pentamethylenediamine will enter the steam compressor 40 through the exhaust pipe together with the carbon dioxide generated by the decomposition to improve the quality of the steam; after the temperature and pressure reach a certain value, the steam is discharged from the steam compressor 40 and enters the heat exchanger 30 for heat exchange; on the one hand, the steam releases its own heat into the preheating kettle 11 through the heat exchanger 30 to preheat the to-be-treated liquid in the preheating kettle 11 to reduce energy consumption; on the other hand, a part of the gas material after heat exchange in the heat exchanger 30 still exists in the form of gas, and the other part is condensed into liquid to form a condensate; at the same time, part of the carbon dioxide in the gas reacts with pentamethylenediamine to generate pentamethylenediamine carbonate and / or bicarbonate again, which exists in the condensate. The gas and condensate in the preheating kettle 11 can be transported to the fermentation tank 10, and the condensate is mixed with the liquid material in the fermentation tank 10 and recycled to reduce the loss of pentamethylenediamine; part of the carbon dioxide gas acts on the liquid material to adjust the pH of the liquid material in the fermentation tank, and the remaining carbon dioxide is discharged from the device.

[0059] In one embodiment, the temperature of the steam discharged from the steam compressor 40 may be 120-140° C., and the pressure may be 0.1-0.3 MPa.

[0060] In one embodiment, if Figure 1a As shown, the exhaust pipeline is a section of pipeline 201, and multiple reactors are connected to the pipeline 201, so that the gas generated in each reactor can directly enter the pipeline 201 and further enter the steam compressor 40 for temperature and pressure increase.

[0061] In another embodiment, if Figure 1b As shown, the exhaust pipeline is composed of multiple sections of pipelines, including a pipeline 201a arranged between the first reactor 21 and the second reactor 22, and a pipeline 201b arranged between the second reactor 22 and the next reactor, wherein the first reactor 21 is connected to the steam compressor 40, so that the gas generated by each stage of the reactor can enter the first reactor 21 through the exhaust pipeline, and then enter the steam compressor 40 from the first reactor 21 to increase the temperature and pressure.

[0062] In another embodiment, if Figure 1c As shown, the exhaust pipeline is composed of multiple sections of pipelines, including a pipeline 201a arranged between the first reactor 21 and the second reactor 22, and a pipeline 201b arranged between the second reactor 22 and the next reactor, wherein the discharge reactor 29 is connected to the steam compressor 40, so that the gas generated by each stage of the reactor can enter the discharge reactor 29 through the exhaust pipeline, and then enter the steam compressor 40 from the discharge reactor 29 to increase the temperature and pressure.

[0063] In one embodiment, the extraction device includes a gas flow meter 202, which can be Figure 1a As shown, it is arranged on the exhaust pipeline 201 and located between the discharge reactor 29 and the steam compressor 40.

[0064] In one embodiment, if Figure 1b As shown, the gas flow meter 202 may be disposed between the heat exchanger 30 and the fermenter 10 .

[0065] In one embodiment, if Figure 1c As shown, the gas flow meter 202 may be disposed between the heat exchanger 30 and the steam compressor 40 .

[0066] In one embodiment, after being compressed by the steam compressor 40, the temperature of the steam (heat exchange medium) is higher than the temperature of the material in the preheating kettle 11, and the temperature difference between the two is 50-110°C, and can further be 60-90°C.

[0067] In one embodiment, the temperature increase rate of the liquid material from the preheating kettle 11 to the first temperature zone is 0-5° C. / min.

[0068] In one embodiment, the plurality of reactors may include a first reactor 21 , a second reactor 22 , and a third reactor which are sequentially connected.

[0069] In one embodiment, the plurality of reactors may include a first reactor 21 , a second reactor 22 , a third reactor, and a fourth reactor which are sequentially connected.

[0070] In one embodiment, the plurality of reactors may include a first reactor 21 , a second reactor 22 , a third reactor, a fourth reactor, and a fifth reactor which are sequentially connected.

[0071] In the present invention, the discharge reactor is a reactor for discharging the pentamethylenediamine conversion liquid, and it can be the third reactor, the fourth reactor or the fifth reactor in sequence.

[0072] In one embodiment, the plurality of reaction kettles may include a plurality of first reaction kettles 21 , such as 2, 3, 4 or 5, and the plurality of first reaction kettles 21 may be connected to the second reaction kettles 22 , respectively.

[0073] In one embodiment, the plurality of reaction kettles may include a plurality of second reaction kettles 22 , such as 2, 3, 4 or 5, and the first reaction kettle 21 may be connected to the plurality of second reaction kettles 22 , respectively.

[0074] In one embodiment, the multiple reactors may include multiple first reactors 21 and multiple second reactors 22. The number of the first reactors 21 and the second reactors 22 may be the same. For example, the number of the first reactors 21 and the second reactors 22 may be 2, 3, 4 or 5 respectively. Each first reactor 21 is connected to a second reactor 22.

[0075] In one embodiment, the extraction device includes a plurality of first reaction kettles 21 and a second reaction kettle 22 , and the plurality of first reaction kettles 21 are directly connected to a second reaction kettle 22 .

[0076] In one embodiment, the extraction device includes a first reaction kettle 21 and a plurality of second reaction kettles 22 , and the plurality of second reaction kettles 22 are directly connected to the first reaction kettle 21 .

[0077] In one embodiment, the number of the first reaction kettles 21 and the number of the second reaction kettles 22 are the same, and each first reaction kettle 21 is directly connected to a second reaction kettle 22 , so that the first reaction kettles 21 and the second reaction kettles 22 can be connected in pairs.

[0078] In one embodiment, multiple first reaction kettles 21 and / or multiple second reaction kettles 22 are provided to realize the combined use of multiple reaction kettles in series or in parallel, which can further improve the conversion efficiency of pentamethylenediamine carbonate and / or pentamethylenediamine bicarbonate.

[0079] In one embodiment, each stage of the reaction kettle may be cylindrical, and its aspect ratio may be (0.1-10.0):1, preferably (1.0-2.0):1.

[0080] In one embodiment, the stirring speed of the materials in the reactor may be 10 to 1000 rpm, and further may be 50 to 200 rpm.

[0081] In one embodiment, each stage of the reaction kettle corresponds to the aforementioned temperature zones, and is applicable to the limitations of its temperature and pressure. For example, the temperature, pressure and other process conditions of the first reaction kettle 21 are applicable to the limitations for the first temperature zone, the temperature, pressure and other process conditions of the second reaction kettle 22 are applicable to the limitations for the second temperature zone, and the temperature, pressure and other process conditions of the discharge reaction kettle 29 are applicable to the limitations for the discharge temperature zone.

[0082] In one embodiment, the process conditions such as temperature and pressure of each stage of the reaction kettle may be the same as or different from those of other reaction kettles.

[0083] Another embodiment of the present invention provides an extraction device for pentamethylenediamine for implementing the above method, which is used for multi-stage decomposition of pentamethylenediamine carbonate and / or pentamethylenediamine bicarbonate. The extraction device includes a distillation tower, such as a plate tower or a packed tower. The plate tower can be Figure 2The sieve plate column shown.

[0084] In one embodiment, the distillation tower includes a distillation tower body 110 , a condenser 120 , a reflux tank 130 and a reboiler 140 .

[0085] In one embodiment, a first reflux passage is formed outside the distillation tower body 110 near the top, and the condenser 120 and the reflux tank 130 are both arranged on the first reflux passage. The condenser 120 is connected to the tower top, and the reflux tank 130 is connected to the side wall near the tower top.

[0086] In one embodiment, the reboiler 140 is disposed outside the distillation tower body 110 and adjacent to the bottom. The reboiler 140 is connected to the bottom and the side wall adjacent to the bottom of the distillation tower body 110 through two pipelines, respectively, to form a second reflux passage between the distillation tower body 110 and the reboiler 140.

[0087] In one embodiment, a plurality of temperature zones may be formed by setting different heating temperatures in the distillation tower body 110 . A downcomer 111 is disposed in the distillation tower body 110 , and raw materials may enter from the middle of the distillation tower body 110 .

[0088] In one embodiment, the pentamethylenediamine fermentation liquid and / or its treated liquid enters the distillation tower body 110 from the middle and upper part of the distillation tower body 110. The pentamethylenediamine fermentation liquid and / or its treated liquid spreads over the first tray and then passes through the downcomer to the second tray, and then sequentially goes down to the bottom of the distillation tower. The liquid after the decomposition of pentamethylenediamine carbonate and / or pentamethylenediamine bicarbonate is discharged from the bottom of the tower and subjected to alkalization treatment to release pentamethylenediamine.

[0089] In one embodiment, by controlling the heating of the reboiler 140, the gas phase is heated from bottom to top and the liquid phase is heated from top to bottom, thereby establishing a vapor-liquid mass transfer and heat transfer process.

[0090] In one embodiment, the number of trays of the distillation tower is 5 to 50, further 10 to 30, for example 10.

[0091] In one embodiment, the temperature of the bottom of the distillation tower may be 70-120°C, and may further be 85-100°C, for example, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, or 110°C.

[0092] In one embodiment, the temperature at the top of the distillation tower is 30-80°C, for example, 10°C, 20°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 90°C.

[0093] In one embodiment, the temperature at the bottom of the distillation tower is greater than the temperature at the top of the distillation tower.

[0094] In one embodiment, the reflux ratio in the distillation tower may be 0.1 to 1.0, and may further be 0.8 to 1.0, such as 0.2, 0.5, 0.6, 0.8, or 0.9.

[0095] In one embodiment of the present invention, the decomposition rate of pentamethylenediamine carbonate and / or pentamethylenediamine bicarbonate is controlled by a plurality of continuous heating temperature zones, thereby reducing the content of carbonate and bicarbonate in the pentamethylenediamine fermentation broth, so that more pentamethylenediamine exists in a free form rather than in a salt form, and the subsequent alkalization process of converting pentamethylenediamine salt into free pentamethylenediamine by adding alkaline substances (such as sodium hydroxide, potassium hydroxide or calcium oxide, etc.) is greatly reduced, thereby shortening the process flow and saving costs. On the other hand, the multi-stage decomposition of pentamethylenediamine carbonate and / or pentamethylenediamine bicarbonate reduces the amount of salt generated during the extraction of pentamethylenediamine, thereby protecting the environment and saving the cost of the enterprise.

[0096] In the method of one embodiment of the present invention, the degassing rate and the foam height in the reaction container reflect the decomposition speed of pentamethylenediamine carbonate and / or pentamethylenediamine bicarbonate. The temperature rise rate of the liquid material (e.g., pentamethylenediamine fermentation liquid and / or its treated liquid) when flowing from an adjacent lower temperature zone to a higher temperature zone can be 0.1 to 5°C / min, preferably 1 to 3°C / min, so that the degassing rate reaches 0 to 800 m / min. 3 / h, and then 400-600m 3 / h. The degassing speed can be adjusted by controlling the heating speed, thereby controlling the lower foam height required in the production of the enterprise to prevent spraying and overflowing the tank. On the basis of ensuring the quality of the final product, the safety of the production process is improved, the generation of alkalized solid slag is significantly reduced, and resources, labor and costs are saved.

[0097] The following is a further description of the method and device for extracting pentamethylenediamine according to one embodiment of the present invention through specific examples. The raw materials used are commercially available unless otherwise specified. The detection methods of the performance parameters involved in each example are as follows:

[0098] 1. Pentamethylenediamine detection method:

[0099] Pentamethylenediamine was detected with dimethyl sulfoxide as the internal standard. M1 dimethyl sulfoxide was dissolved in m2 heavy water to make a concentration of C 内 dimethyl sulfoxide internal standard solution.

[0100] Take dimethyl sulfoxide internal standard solution m 内 , add pentamethylenediamine fermentation broth or pentamethylenediamine conversion broth m 样 , NMR detection of hydrogen spectrum. The peak area ratio of pentamethylenediamine to dimethyl sulfoxide in hydrogen spectrum analysis is A, and the concentration of pentamethylenediamine is calculated.

[0101]

[0102]

[0103] m1 is the mass of dimethyl sulfoxide, g; m2 is the mass of heavy water, g; c 内 is the mass concentration of dimethyl sulfoxide;

[0104] m 内 is the internal standard mass of dimethyl sulfoxide, g; M is the molar mass of pentamethylenediamine, mol / L;

[0105] A is the peak area ratio of pentamethylenediamine to dimethyl sulfoxide internal standard; m 样 is the mass of pentamethylenediamine sample, g.

[0106] 2. Detection method of the decomposition rate of pentamethylenediamine carbonate and / or pentamethylenediamine bicarbonate in the material:

[0107] Take 100 mL of pentamethylenediamine fermentation broth, add excess sulfuric acid, heat to 80°C, collect carbon dioxide gas by drainage method, and measure the volume of carbon dioxide V1;

[0108] Take 100 mL of the pentamethylenediamine fermentation liquid heated in a continuous graded reactor, add excess sulfuric acid, heat to 80°C, collect carbon dioxide gas by drainage method, and measure the volume of carbon dioxide V2;

[0109] At the same time, a blank experiment was performed and the measured volume was V0;

[0110] 3. Maximum foam height:

[0111] After the pentamethylenediamine fermentation liquid is added to the reactor, stirring is started and the liquid level H1 is measured; during the heating process of the pentamethylenediamine fermentation liquid, the highest foam height H2 is recorded;

[0112]

[0113] 4. Reduction of alkaline substances: Take 100 mL of pentamethylenediamine fermentation liquid, add excess sulfuric acid, heat to 80°C, collect carbon dioxide gas in the raw material by water displacement method, and measure the volume of carbon dioxide V1; take 100 mL of pentamethylenediamine fermentation liquid heated by the discharge reactor, add excess sulfuric acid, heat to 80°C, collect carbon dioxide gas by water displacement method, and measure the volume of carbon dioxide V2. Then, calculate the reduction of alkaline substances based on the reduction of carbon dioxide volume converted into the reduction of sodium hydroxide.

[0114] Comparative Example 1 0-2℃ / min heating to 80℃

[0115] The single-stage decomposition method of pentamethylenediamine fermentation liquid comprises the following steps:

[0116] (1) According to the method disclosed in Example 1 of patent application CN104762336A, pentamethylenediamine fermentation broth was prepared by decarboxylating lysine fermentation broth with lysine decarboxylase, wherein the concentration of pentamethylenediamine was 7.8% (mass percentage) and the pH value was 7.76. 1500 g of pentamethylenediamine fermentation broth was added to a 5 L glass reactor with an aspect ratio of 2.0 and stirred at 80 rpm.

[0117] (2) The vacuum degree in the glass reactor was controlled to be 10 kPa, and the temperature was raised to 80°C at a rate of 0-2°C / min. The temperature of the pentamethylenediamine fermentation liquid, the carbon dioxide gas emission rate after the decomposition of pentamethylenediamine carbonate and / or bicarbonate, and the maximum foam height were recorded per minute. After the gas emission was completed, the decomposition rate of pentamethylenediamine carbonate and / or bicarbonate, the pH of the pentamethylenediamine conversion liquid, and the amount of alkaline substances reduced were measured, as shown in Table 1.

[0118] Comparative Example 2 0-2℃ / min heating to 99℃

[0119] The single-stage decomposition method of pentamethylenediamine fermentation liquid comprises the following steps:

[0120] (1) According to the method disclosed in Example 1 of patent application CN104762336A, pentamethylenediamine fermentation broth was prepared by decarboxylating lysine fermentation broth with lysine decarboxylase. 1500 g of pentamethylenediamine fermentation broth, wherein the concentration of pentamethylenediamine was 7.8% (mass percentage) and the pH value was 7.76, was added into a 5 L glass reactor with an aspect ratio of 2.0, and stirred at 80 rpm.

[0121] (2) The vacuum degree in the glass reactor was controlled to be 10 kPa, and the temperature was raised to 99° C. at a rate of 0-2° C. / min. The temperature of the pentamethylenediamine fermentation liquid, the carbon dioxide outgassing rate after the decomposition of pentamethylenediamine carbonate and / or bicarbonate, and the maximum foam height were recorded per minute. After the outgassing was completed, the decomposition rate of pentamethylenediamine carbonate and / or bicarbonate, the pH of the pentamethylenediamine conversion liquid, and the amount of alkaline substances reduced were measured, as shown in Table 1.

[0122] Comparative Example 3 0-3℃ / min heating to 95℃

[0123] The single-stage decomposition method of pentamethylenediamine fermentation liquid comprises the following steps:

[0124] (1) According to the method disclosed in Example 1 of patent application CN104762336A, pentamethylenediamine fermentation broth was prepared by decarboxylating lysine fermentation broth with lysine decarboxylase. 1500 g of pentamethylenediamine fermentation broth, wherein the concentration of pentamethylenediamine was 7.8% (mass percentage) and the pH value was 7.76, was added into a 5 L glass reactor with an aspect ratio of 2.0, and stirred at 80 rpm.

[0125] (2) The vacuum degree in the glass reactor was controlled to be 10 kPa, and the temperature was raised to 95°C at a rate of 0-3°C / min. The temperature of the pentamethylenediamine fermentation liquid, the carbon dioxide outgassing rate after the decomposition of pentamethylenediamine carbonate and / or bicarbonate, and the maximum foam height were recorded per minute. After the outgassing was completed, the decomposition rate of pentamethylenediamine carbonate and / or bicarbonate, the pH of the pentamethylenediamine conversion liquid, and the amount of alkaline substances reduced were measured, as shown in Table 1.

[0126] Comparative Example 4 0-2℃ / min heating to 95℃

[0127] Comparative Example 4 was obtained by using the same raw materials and operations as in Comparative Example 3, except that the heating rate was adjusted to 0-2°C / min. The experimental results are shown in Table 1.

[0128] Comparative Example 5 0-5℃ / min heating to 95℃

[0129] Comparative Example 5 was obtained by using the same raw materials and operations as in Comparative Example 3, except that the heating rate was adjusted to 0-5°C / min. The experimental results are shown in Table 1.

[0130] Table 1

[0131]

[0132] The experimental results of Comparative Examples 1 to 3 show that at 80°C, the system heats up slowly, with a maximum temperature rise of 2°C / min, and a maximum carbon dioxide release rate of 0.55 L / min; at 99°C, the system heats up slowly, with a maximum temperature rise of 2°C / min, and a maximum carbon dioxide release rate of 0.60 L / min; at 95°C, when the maximum temperature rise is 3°C / min, the maximum carbon dioxide release rate is 0.80 L / min; at 95°C, when the maximum temperature rise is 2°C / min, the maximum carbon dioxide release rate is 0.55 L / min; at 95°C, when the maximum temperature rise is 5°C / min, the maximum carbon dioxide release rate is 1.52 L / min.

[0133] As shown in the comparative examples and Table 1, the pentamethylenediamine fermentation liquid of comparative example 1 was heated to 80°C, the pH of the conversion liquid after the reaction was 8.60, the decomposition rate of pentamethylenediamine carbonate and / or pentamethylenediamine bicarbonate was 31.4%, and 100g of the conversion liquid reduced 1.488g of alkaline substances; the pentamethylenediamine fermentation liquid of comparative example 2 was heated to 99°C, the pH of the conversion liquid after the reaction was 9.59, the decomposition rate of pentamethylenediamine carbonate and / or pentamethylenediamine bicarbonate was 63.4%, and 100g of the conversion liquid reduced 2.992g of alkaline substances. The pentamethylenediamine fermentation liquid of comparative example 3 was heated to 95°C, the pH of the conversion liquid after the reaction was 9.25, the decomposition rate of pentamethylenediamine carbonate and / or pentamethylenediamine bicarbonate was 49.4%, and 100g of the conversion liquid reduced 2.336g of alkaline substances. The pentamethylenediamine fermentation liquid of Comparative Example 4 was heated to 95° C., the pH of the conversion liquid after the reaction was 9.27, the decomposition rate of pentamethylenediamine carbonate and / or pentamethylenediamine bicarbonate was 49.9%, and 100 g of the conversion liquid reduced 2.360 g of alkaline substances. The pentamethylenediamine fermentation liquid of Comparative Example 5 was heated to 95° C., the pH of the conversion liquid after the reaction was 9.02, the decomposition rate of pentamethylenediamine carbonate and / or pentamethylenediamine bicarbonate was 47.6%, and 100 g of the conversion liquid reduced 2.248 g of alkaline substances.

[0134] The results of Comparative Examples 1 to 5 show that the maximum foam height is 13.3% of the liquid level at 80°C; 47.3% of the liquid level at 95°C (maximum temperature rise of 2°C / min); 100.1% of the liquid level at 95°C (maximum temperature rise of 3°C / min); 154.8% of the liquid level at 95°C (maximum temperature rise of 5°C / min); and 167% of the liquid level when the liquid boils at 99°C. It can be seen that in the comparative example, when the decomposition temperature is too high during the single-stage decomposition, and the temperature rise rate when the liquid material flows from the adjacent lower temperature zone to the higher temperature zone is too fast, it has a significant adverse effect on the maximum foam height, which is easy to cause abnormal conditions such as foam accumulation and spray cans.

[0135] Example 1

[0136] The three-stage continuous decomposition of pentamethylenediamine fermentation broth was tested in a small test. The specific steps are as follows:

[0137] (1) According to the method disclosed in Example 1 of patent application CN104762336A, pentamethylenediamine fermentation broth was prepared by decarboxylating lysine fermentation broth with lysine decarboxylase, wherein the concentration of pentamethylenediamine was 7.8% (mass percentage) and the pH value was 7.76.

[0138] The extraction device used is composed of a fermentation tank, a preheating kettle and three reactors connected in sequence. The fermentation liquid is passed from the fermentation tank to the preheating kettle at a rate of 1500g / h for preheating, and then enters three 5L glass reactors (length-to-diameter ratio 2.0) connected in series in sequence, which are the first reactor, the second reactor, and the discharge reactor. The feeding coefficient of each reactor is 0.3, and the stirring is at 80rpm.

[0139] (2) The vacuum degree in the three glass reactors was controlled to be 10 kPa, the temperature of the first reactor was 80° C., the temperature of the second reactor was 90° C., and the temperature of the discharge reactor was 95° C. The maximum foam height was recorded, and the decomposition rate of pentamethylenediamine carbonate and / or pentamethylenediamine bicarbonate, the pH of the pentamethylenediamine conversion liquid, and the amount of alkaline substance reduction after the discharge reactor was heated were measured, as shown in Table 2.

[0140] Example 2

[0141] use Figure 1a The device shown in the figure performs industrial three-stage continuous decomposition of pentamethylenediamine fermentation liquid, and the specific steps are as follows:

[0142] (1) According to the method disclosed in Example 1 of patent application CN104762336A, the lysine fermentation broth is decarboxylated by lysine decarboxylase to obtain pentamethylenediamine fermentation broth, wherein the concentration of pentamethylenediamine is 7.8% (mass percentage) and the pH value is 7.76. The fermentation broth is heated to 25 m 3 / h from the fermentation tank 10 to the preheating kettle 11 for preheating, and then enters three 50m 3 In the stainless steel reactor (length-to-diameter ratio 2.0, with a steam tube heat exchanger), the three stainless steel reactors are respectively the first reactor 21, the second reactor 22, and the discharge reactor 29. The pentamethylenediamine fermentation liquid enters the first reactor 21 to react and generate carbon dioxide gas. After the liquid material is discharged from the discharge port of the first reactor 21, it enters the second reactor 22 through the liquid inlet pipeline to continue the reaction, and then enters the discharge reactor 29 for reaction. The liquid material including the conversion liquid of pentamethylenediamine remaining after the decomposition of pentamethylenediamine carbonate and / or bicarbonate is discharged from the discharge reactor 29, and then the pentamethylenediamine is fully freed by alkalization treatment. The feeding coefficient of each reactor is 0.5, and it is stirred at 80rpm. The pentamethylenediamine conversion liquid discharged from the discharge reactor 29 is used for subsequent production.

[0143] During the reaction process, the gases in the first reactor 21, the second reactor 22, and the discharge reactor 29 all enter the exhaust pipeline, and after being heated and pressurized by the steam compressor 40, enter the heat exchanger 30 for heat exchange. The heat obtained by the heat exchanger 30 is transferred to the preheating kettle 11 for preheating the fermentation liquid. After the heat exchange, part of the gas is condensed into liquid to form a condensate, and the other part forms a gas containing carbon dioxide. The condensate and the gas are introduced into the fermentation tank 10 together. The condensate is reused to participate in the next round of decomposition reaction. Part of the carbon dioxide gas is dissolved in the fermentation liquid for pH adjustment, and the other part of the carbon dioxide gas is discharged from the device.

[0144] (2) The three stainless steel reactors were all connected to a vacuum pump, and the vacuum degree in the stainless steel reactors was controlled to be 10 kPa. The reactors at each level were heated by a steam tube heat exchanger, and the temperature of the first reactor 21 was 79-81° C., the temperature of the second reactor 22 was 89-91° C., and the temperature of the discharge reactor 29 was 94-96° C. The maximum foam height in each reactor was recorded, and the decomposition rate of pentamethylenediamine carbonate and / or pentamethylenediamine bicarbonate, the pH of the pentamethylenediamine conversion liquid, and the amount of alkaline substances reduced in the discharge reactor 29 after heating were measured, as shown in Table 2.

[0145] Example 3

[0146] use Figure 1b The device shown in the figure performs industrial three-stage continuous decomposition of pentamethylenediamine fermentation liquid, and the specific steps are as follows:

[0147] (1) According to the method disclosed in Example 1 of patent application CN104762336A, pentamethylenediamine fermentation broth is prepared by decarboxylating lysine fermentation broth with lysine decarboxylase.

[0148] The concentration of pentamethylenediamine was 7.8% (mass percentage) and the pH value was 7.76. 3 / h from the fermentation tank 10 to the preheating kettle 11 for preheating, and then enters three 50m 3 In the stainless steel reactor (length-to-diameter ratio 2.0, with a steam tube heat exchanger), the three stainless steel reactors are respectively the first reactor 21, the second reactor 22, and the discharge reactor 29. The pentamethylenediamine fermentation liquid enters the first reactor 21 to react and generate carbon dioxide gas. After the liquid material is discharged from the discharge port of the first reactor 21, it enters the second reactor 22 through the liquid inlet pipeline to continue the reaction, and then enters the discharge reactor 29 for reaction. The liquid material including the conversion liquid of pentamethylenediamine remaining after the decomposition of pentamethylenediamine carbonate and / or bicarbonate is discharged from the discharge reactor 29, and then the pentamethylenediamine is fully freed by alkalization treatment. The feeding coefficient of each reactor is 0.5, and it is stirred at 80rpm. The pentamethylenediamine conversion liquid discharged from the discharge reactor 29 is used for subsequent production.

[0149] During the reaction process, the gases in the first reactor 21, the second reactor 22, and the discharge reactor 29 all enter the exhaust pipeline, and after being heated and pressurized by the steam compressor 40, enter the heat exchanger 30 for heat exchange. The heat obtained by the heat exchanger 30 is transferred to the preheating kettle 11 for preheating the fermentation liquid. After the heat exchange, part of the gas is condensed into liquid to form a condensate, and the other part forms a gas containing carbon dioxide. The condensate and the gas are introduced into the fermentation tank 10 together. The condensate is reused to participate in the next round of decomposition reaction. Part of the carbon dioxide gas is dissolved in the fermentation liquid for pH adjustment, and the other part of the carbon dioxide gas is discharged from the device.

[0150] (2) The vacuum pump is connected to the first reactor 21. The mixed steam in the discharge reactor 29 enters the second reactor 22 through the pipeline 201b. The mixed steam in the second reactor 22 enters the first reactor 21 through the pipeline 201a. The mixed steam in the first reactor 21 is discharged from the reactor system through the vacuum pump. The vacuum degree in the stainless steel reactor is controlled to be 10 kPa. The reactors of each stage are heated by the steam tube heat exchanger. The temperature of the first reactor 21 is 79-81°C, the temperature of the second reactor 22 is 89-91°C, and the temperature of the discharge reactor 29 is 94-96°C. The maximum foam height in each stage of the reactor is recorded, and the decomposition rate of pentamethylenediamine carbonate and / or pentamethylenediamine bicarbonate, the pH of the pentamethylenediamine conversion liquid and the amount of alkaline substances reduced after the discharge reactor 29 is heated are measured. See Table 2 for details.

[0151] Example 4

[0152] Pentamethylenediamine fermentation broth Figure 2 The device shown adopts a continuous multi-stage decomposition method, comprising the following steps:

[0153] (1) According to the method disclosed in Example 1 of patent application CN104762336A, a lysine fermentation broth is decarboxylated by lysine decarboxylase to obtain a pentamethylenediamine fermentation broth, wherein the pentamethylenediamine concentration is 7.8% (mass percentage) and the pH value is 7.76, and the 1000 g / h pentamethylenediamine fermentation broth is distilled from a distillation tower ( Figure 2 The pentamethylenediamine fermentation liquid is added from the top (as shown), and the lower 10-stage tower plates are gradually covered with the pentamethylenediamine fermentation liquid.

[0154] (2) Heating by reboiler 140, controlling the top temperature of the distillation tower to 80°C, the bottom temperature to 95°C, and the vacuum degree to 10 kPa. Full reflux is performed to establish a vapor-liquid phase mass transfer and heat transfer process. After the decomposition of pentamethylenediamine carbonate and / or bicarbonate, the pentamethylenediamine conversion liquid is discharged from the bottom of the tower.

[0155] The maximum foam height of the pentamethylenediamine fermentation liquid in the distillation tower was recorded, and the decomposition rate of pentamethylenediamine carbonate and / or pentamethylenediamine bicarbonate, the pH of the pentamethylenediamine conversion liquid and the reduction of alkaline substances were determined, as shown in Table 2.

[0156] Table 2

[0157]

[0158] As shown in Table 2, the pH of the solution of the pentamethylenediamine fermentation broth of Example 1 after three-stage continuous decomposition is 9.55, and the decomposition rate of pentamethylenediamine carbonate and bicarbonate is 62.3%. 2.944g of alkaline substances are reduced for every 100mL of conversion liquid, and the alkaline substances are reduced by 24.7% compared with Comparative Example 4 (single-stage heating). The maximum temperature rise is 2°C / min, and the maximum foam height is 15%, and the foam height is reduced by 68.3% compared with Comparative Example 4. In the gas release rate and temperature curve of the discharge reactor 29, the flow rate and temperature reach a steady-state equilibrium. The pentamethylenediamine fermentation broth is continuously stirred and decomposed in three stages, and the feed liquid is mixed more evenly, and the carbon dioxide gas is released more fully, resulting in the three-stage continuous decomposition effect being improved than the single-stage decomposition effect.

[0159] After the pentamethylenediamine fermentation liquid of Example 2 was passed through the industrial three-stage continuous decomposition device, the solution pH was 9.53, and the decomposition rate of pentamethylenediamine carbonate and bicarbonate was 61.9%. The maximum temperature rise was 2°C / min, and the maximum foam height was 18%, which was 61.9% lower than that of Comparative Example 4. In the gas release rate and temperature curve of the discharge reactor 29, the gas flow rate and temperature balance were stable within 18 hours, and the gas flow rate was stable.

[0160] Every 100 mL of conversion liquid reduces 2.928 g of alkaline substances, which is 24.1% less than that of comparative example 4. The annual processing capacity of pentamethylenediamine fermentation liquid in the factory is 900,000 tons. After treatment by the industrial three-stage continuous decomposition device, 33,000 tons of alkaline solid waste can be reduced, which is 6,000 tons more than the single-stage decomposition, which has significant economic benefits in industrial production.

[0161] The mixed steam generated by the three-stage continuous decomposition of the industry is heated and pressurized by the steam compressor 40 and then preheated to the preheating kettle 11, which saves 1.8×10 6 kJ, which can save 3.6×10 6 kW·h. After heat exchange, the mixed steam is cooled to condensate, and the content of pentamethylenediamine in the condensate accounts for 1.1% of the output. After recycling, 720 tons of pentamethylenediamine finished products can be added each year. The utilization of waste heat of mixed steam and the recovery of pentamethylenediamine in condensate have significant economic benefits in industrial production.

[0162] After the pentamethylenediamine fermentation liquid of Example 3 was passed through the industrial three-stage continuous decomposition device, the solution pH was 9.51, and the decomposition rate of pentamethylenediamine carbonate and bicarbonate was 61.5%. The maximum temperature rise was 3°C / min, and the maximum foam height was 36%, which was 64.0% lower than that of Comparative Example 3. In the gas release rate and temperature curve of the discharge reactor 29, the gas flow rate and temperature balance were stable within 18 hours.

[0163] Every 100 mL of conversion liquid reduces 2.904 g of alkaline substances, which is 24.3% less than that of comparative example 3. The annual processing capacity of pentamethylenediamine fermentation liquid in the factory is 900,000 tons. After treatment by the industrial three-stage continuous decomposition device, 33,000 tons of alkaline solid waste can be reduced, which is 6,000 tons more than the single-stage decomposition, which has significant economic benefits in industrial production.

[0164] The mixed steam generated by the three-stage continuous decomposition of the industry is heated and pressurized by the steam compressor 40 and then preheated to the preheating kettle 11, which saves 1.7×10 6 kJ, which can save 3.4×10 6 kW·h. After heat exchange, the mixed steam is cooled to condensate, and the content of pentamethylenediamine in the condensate accounts for 1.2% of the output. After recycling, 785 tons of pentamethylenediamine finished products can be added each year. The utilization of waste heat of mixed steam and the recovery of pentamethylenediamine in condensate have significant economic benefits in industrial production.

[0165] The pH of the solution of the pentamethylenediamine fermentation liquid of Example 4 after multi-stage continuous decomposition was 9.64, and the decomposition rate of pentamethylenediamine carbonate and bicarbonate was 64.1%. 3.032 g of alkaline substances were reduced per 100 mL of conversion liquid, and the alkaline substances were reduced by 28.5% compared with Comparative Example 4. The maximum foam height was 10%, and the foam height decreased by 78.8% compared with Comparative Example 4.

[0166] Compared with the three-stage continuous reactor, since the distillation tower has 10 tower plates, the pentamethylenediamine fermentation liquid can be more evenly distributed on the tower plates to form a thinner liquid layer. At the same time, due to the countercurrent flow of the gas phase and the liquid phase in the distillation tower, the surface area of ​​the pentamethylenediamine fermentation liquid is greatly increased, so that the carbon dioxide gas is released quickly and fully, and the decomposition efficiency is higher while ensuring less foam.

[0167] It can be seen from the above embodiments that the continuous multi-stage decomposition device has a stable gas flow rate and less foam volume compared to the single-stage decomposition, and can withstand a larger temperature rise. Considering the decomposition rate of pentamethylenediamine carbonate and / or pentamethylenediamine bicarbonate and the maximum foam height, it is preferred that the maximum temperature rise of the fermentation liquid between adjacent temperature zones is 1-3°C / min, and the degassing speed is 400-600m / min. 3 / h. This is very important for production, as it can prevent abnormal conditions such as overflowing and spraying, and ensure smooth production.

[0168] Unless otherwise defined, the terms used in the present invention have the meanings commonly understood by those skilled in the art.

[0169] The embodiments described in the present invention are for illustrative purposes only and are not intended to limit the scope of protection of the present invention. Those skilled in the art may make various other substitutions, changes and improvements within the scope of the present invention. Therefore, the present invention is not limited to the above embodiments, but is only limited by the claims.

Claims

1. A method for extracting pentamethylenediamine, characterized in that: The method comprises the following steps: allowing the pentamethylenediamine fermentation liquid and / or its treated liquid to enter the distillation tower body through the middle and upper part of the distillation tower body, and then spreading over the first layer of distillation tower plates through a downcomer to the second layer of distillation tower plates, and then sequentially downward to the bottom of the distillation tower, and the obtained feed liquid is discharged from the bottom of the distillation tower for alkalization treatment to release pentamethylenediamine; Wherein, the pentamethylenediamine in the pentamethylenediamine fermentation liquid and / or its treated liquid exists in the form of carbonate and / or bicarbonate, and pentamethylenediamine sulfate; The temperature of the top of the distillation tower is 30-80°C, and the temperature of the bottom of the distillation tower is 70-120°C; The temperature at the bottom of the distillation tower is greater than the temperature at the top of the distillation tower; The temperature increase rate of the pentamethylenediamine fermentation liquid and / or its treated liquid when flowing from an adjacent lower temperature zone to a higher temperature zone is 1 to 3°C / min.

2. The method according to claim 1, characterized in that: The temperature of the bottom of the distillation tower is 85-100°C.

3. The method according to claim 1, characterized in that The distillation tower has 5 to 50 stages of plates.

4. The method according to claim 3, characterized in that The distillation tower has 10 to 30 stages of plates.

5. The method according to claim 1, characterized in that The distillation tower is a plate tower or a packed tower.

6. The method according to claim 1, characterized in that The distillation tower is provided with a condenser and a reflux tank; wherein a first reflux passage is formed outside the distillation tower body near the top, the condenser and the reflux tank are both arranged on the first reflux passage, the condenser is connected to the tower top, and the reflux tank is connected to the side wall near the tower top.

7. The method according to claim 1 or 6, characterized in that: The distillation tower is provided with a reboiler, which is arranged outside the distillation tower body and near the bottom. The reboiler is connected to the bottom of the distillation tower body and the side wall near the bottom through two pipelines respectively to form a second reflux passage between the distillation tower body and the reboiler.

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