A method for the extraction of 1,5-pentanediamine, the resulting 1,5-pentanediamine product and polyamides

Abstract

The application provides a method for extracting 1,5-pentanediamine, a resultant 1,5-pentanediamine product and a polyamide, the method comprising the following steps: providing a first solution, the first solution comprising 1,5-pentanediamine, metal ions and water; performing extraction treatment on the first solution by using an organic solvent to obtain a first aqueous solution and a first organic solution, so that at least part of the metal ions in the first solution are extracted into the first organic solution; recovering 1,5-pentanediamine from the first aqueous solution; wherein the organic solvent comprises a complexing extractant. The complexing extraction separates pentanediamine and metal ions and other impurities from the first solution system efficiently, and further purifies the 1,5-pentanediamine product.

Description

TECHNICAL FIELD

[0001] The present application relates to 1,5-pentanediamine, in particular to a method for extracting 1,5-pentanediamine from an aqueous solution. BACKGROUND

[0002] 1,5-pentanediamine (referred to as pentanediamine) is an important 5-carbon platform compound in the chemical industry, which can be used to manufacture polyamide, polyurethane, etc., and can also be used as an important chemical raw material to manufacture isocyanate, pyridine, piperidine, etc.

[0003] It has been reported in the literature that pentanediamine can be synthesized by microbial transformation, i.e., prepared by a biological fermentation method. For the preparation of pentanediamine by the biological fermentation method, it is necessary to introduce acid ions by adjusting the pH during the fermentation process, and there are also acid ions in the culture medium. As a result, a large amount of sulfate, carbonate, etc. of pentanediamine is formed in the fermentation broth.

[0004] In the existing production process, an alkaline substance such as caustic soda (NaOH), Ca(OH)2, Mg(OH)2, etc. is added to the fermentation broth to perform alkalization, to generate free pentanediamine and salts (such as Na2SO4 salt / MgSO4 salt / CaSO4 precipitate), etc., and then the pentanediamine is distilled out by filtration and distillation to obtain pure pentanediamine. When alkalization is performed with alkali metal-based alkaline substances such as caustic soda, etc., the molecular weight of NaOH, etc. is low but the price is high, and only one OH - anion is provided for alkalization, resulting in a substantial increase in production cost, and the soluble salt generated will enter the water body to cause pollution. When alkalization is performed with alkaline earth metal-based alkaline substances such as Ca(OH)2, Mg(OH)2, etc., two OH - anions per unit are provided, and the precipitate product formed during the reaction process can be reused by recovery and calcination, substantially reducing the entry of metal ions and anions into the water body. However, if the composition of the system is complex during the subsequent distillation and recovery of pentanediamine, the distillation conditions are strict, the equipment requirements are high, and the effect of distillation and purification is limited. Therefore, how to effectively purify 1,5-pentanediamine and separate it from impurities is still a challenging problem. SUMMARY

[0005] To solve the above technical problems, the present application provides a method for extracting 1,5-pentanediamine, comprising the following steps: providing a first solution comprising 1,5-pentanediamine, metal ions and water; performing extraction treatment on the first solution by using an organic solvent to obtain a first aqueous solution and a first organic solution, so that at least a part of the metal ions in the first solution is extracted into the first organic solution; and recovering 1,5-pentanediamine from the first aqueous solution; wherein the organic solvent comprises a complexing extractant.

[0006] The 1,5-pentanediamine product prepared by the method has a purity of 98 wt% or more.

[0007] The polyamide is prepared from the 1,5-pentanediamine product.

[0008] In some embodiments of the present application, the metal ions and other impurities can be efficiently extracted from the first solution system by complex extraction, thereby further purifying the 1,5-pentanediamine product. DETAILED DESCRIPTION

[0009] The embodiments embodying the features and advantages of the present application will be described in detail in the following description. It should be understood that the present application can have various changes on different embodiments, which do not deviate from the scope of the present application, and the description and essence are used as an illustration, not to limit the present application. Among them, "first", "second", etc. are used to distinguish between multiple processes or products with the same name, and are not limited.

[0010] The method for extracting 1,5-pentanediamine provided by an embodiment of the present application comprises the following steps:

[0011] A first solution is provided, which comprises 1,5-pentanediamine, metal ions and water;

[0012] The first solution is subjected to extraction treatment by an organic solvent containing a complexing extractant, so that at least a part of the metal ions in the first solution are extracted into a first organic solution, and after separation, a first aqueous solution (water phase) and a first organic solution (organic phase) are obtained; and

[0013] 1,5-pentanediamine is recovered from the first aqueous solution.

[0014] The metal ions include, but are not limited to, any one or more of calcium ions, magnesium ions, iron ions and barium ions; and the complexing extractant includes one or more of neutral phosphorus oxygen type extractants, acidic phosphorus oxygen type extractants, double coordination phosphorus oxygen type extractants, acidic complexing extractants containing carboxyl, sulfonic acid groups or hydroxyl groups, and tertiary amine type extractants.

[0015] In an embodiment, the hydroxyl groups in the acidic complexing extractant can be phenolic hydroxyl groups and / or other hydroxyl groups.

[0016] In the method of an embodiment of the present application, the metal ions in the first solution are subjected to complex extraction by the complexing extractant, so that the metal ions are transferred from the water phase to the organic phase, thereby removing the metal ions in the first aqueous solution, reducing the subsequent solid residue, and improving the process efficiency; at the same time, most of the 1,5-pentanediamine can be retained in the first aqueous solution, thereby playing a role in separating and purifying the pentanediamine.

[0017] In one embodiment, the neutral phosphine oxide extractant has a general formula of XYZPO (Z is a group different from X or Y); the acidic phosphine oxide extractant has a general formula of XYP(O)OH; the bidentate phosphine oxide extractant has a general formula of XYP(O)(CH2) n A(B)W, n is 1-6, for example, 2, 3, 4 or 5, and W is an alkyl group, an alkoxy group, an alkylamino group, etc. with a carbon atom number of 1-10; the tertiary amine extractant can be a trialkylamine compound with a general formula of R3N, wherein R is C m H 2m+1 , and m is 8, 9 or 10.

[0018] In one embodiment, X and Y in the neutral phosphine oxide extractant, the acidic phosphine oxide extractant and the bidentate phosphine oxide extractant are each independently selected from an alkoxy group or an alkyl group with a linear or branched structure and a carbon atom number of 2-10; further, X and Y are each independently selected from an alkoxy group or an alkyl group with a linear or branched structure and a carbon atom number of 5-10; for example, the carbon atom number of X and Y can be 3, 4, 5, 6, 7, 8 or 9, respectively.

[0019] In one embodiment, Z can be an alkyl group or an alkoxy group with 1-5 carbon atoms, and further, the carbon atom number of Z can be 2, 3 or 4.

[0020] In one embodiment, A is selected from N or P.

[0021] In one embodiment, B is selected from an alkyl group, an alkoxy group or oxygen with a carbon atom number of 1-5.

[0022] In one embodiment, the complexing extractant is an acidic phosphine oxide extractant, for example, 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (P507), methylphosphonic acid dimethylheptyl ester (P350), di(2-ethylhexyl) phosphonic acid (P204), di(2-ethylhexyl) monothiophosphonic acid (D2EHMTPA), etc.

[0023] In one embodiment, the complexing extractant is a neutral phosphine oxide extractant, for example, tributyl phosphate, trialkyloxyphosphine (Chinese alias: dihexyl(octyl)oxyphosphine).

[0024] In one embodiment, the complexing extractant is a bidentate phosphine oxide extractant, for example, dibutyl α-acylmethylphosphonate, ethylene bisphosphonic acid tetrabutyl ester.

[0025] In one embodiment, the complexing extractant is a combination of two or more compounds, which at least includes an acidic phosphine oxide extractant. In the complexing extractant, the proportion of the acidic phosphine oxide extractant is 20% or more, and further, 50% or more. For example, 30wt%, 60wt%, 80wt%.

[0026] In one embodiment, the complexing extractant includes one or more of a combination of 2-ethylhexyl phosphoric acid mono 2-ethylhexyl ester (P507), di(2-ethylhexyl)phosphoric acid ester (P204), dibutyl alpha-acyl methyl phosphonate, ethylenediphosphonic acid tetrabutyl ester, tributyl phosphate, trialkyl phosphine oxide, tri-octyl amine.

[0027] In one embodiment, the molar ratio of the complexing extractant to the metal ion in the first solution can be (0.1-50):1, further can be (0.5-50):1, further can be (1-30):1, further can be (2-20):1, for example 0.3:1, 0.6:1, 0.9:1, 1.5:1, 3:1, 5:1, 6:1, 9:1, 10:1, 12:1, 15:1, 18:1, 25:1.

[0028] In one embodiment, the molar ratio of the complexing extractant to the pentanediamine in the first solution can be 1:(0.5-40), further can be 1:(1-40), further can be 1:(1.5-40), further can be 1:(3-40), further can be 1:(3-20), further can be 1:(5-20), for example 0.3:5, 0.6:5, 0.9:5, 1.5:5, 3:5, 6:5, 1:10, 1:15, 1:18, etc.

[0029] In one embodiment, the extraction process is a single stage extraction or more than two stages of extraction. In one embodiment, A concentration step can be performed between any two stages of extraction.

[0030] The present application does not make specific restrictions on the concentration of 1,5-pentanediamine in the first solution, which can be 50wt% or less, further can be 30wt% or less, further can be 10wt% or less.

[0031] The present application does not make specific restrictions on the concentration of the metal ion in the first solution, which can be 2wt% or less, further can be 1wt% or less.

[0032] In one embodiment, the content of the residual complexing extractant in the first aqueous solution is 2500ppm or less, further is 1500ppm or less.

[0033] In one embodiment, the organic solvent includes the complexing extractant and the diluent.

[0034] In one embodiment, the complexing extractant and the diluent are mixed, and then mixed with the first solution to realize the contact of the first solution with the complexing extractant.

[0035] In one embodiment, the content of the residual diluent in the first aqueous solution is 7000ppm or less, further is 3000ppm or less.

[0036] In one embodiment, the diluent comprises one or more of an ether compound, an ester compound, a linear, branched and cyclic alcohol compound, a linear and cyclic alkane compound, a halogenated alkane, an aromatic compound.

[0037] In one embodiment, the diluent comprises one or more of an ether compound having a carbon number of 4 to 10, an ester compound having a carbon number of 2 to 10, a linear, branched and cyclic alcohol compound having at least four carbon atoms, a linear and cyclic alkane compound having at least five carbon atoms and mixtures thereof, a halogenated alkane having a carbon number of 1 to 3, an aromatic compound.

[0038] In one embodiment, the linear, branched and cyclic alcohol compound has a carbon number of 4 to 18. For example, 5, 6, 7, 8, 10, 12, 14, 16.

[0039] In one embodiment, the ether compound can have a carbon number of 4, 5, 6, 7, 8, 9 or 10, including but not limited to isopropyl ether, diethyl ether, n-butyl ether, etc.

[0040] In one embodiment, the halogenated alkane can have a carbon number of 1, 2 or 3, which can be a chlorinated and / or brominated alkane.

[0041] In one embodiment, the halogenated alkane can be a mono-halogenated alkane, a di-halogenated alkane, a tri-halogenated alkane, a tetra-halogenated alkane, for example, including but not limited to carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, etc.

[0042] In one embodiment, the linear and cyclic alkane compound can have a carbon number of 5 to 12, for example, 6, 7, 8, 9, 10, 11, 12, for example, the linear and cyclic alkane compound can include but not limited to n-pentane, n-hexane, cyclohexane, dodecane, etc.

[0043] In one embodiment, the aromatic compound includes but not limited to benzene, toluene, ethylbenzene, chlorobenzene, xylene, etc.

[0044] In one embodiment, the diluent comprises one, two or more of kerosene, n-hexane, cyclohexane, dichloromethane, carbon tetrachloride, xylene, ethyl acetate, butyl acetate, isopropyl ether.

[0045] In one embodiment, the organic solvent comprises a complexing extractant and a diluent, the concentration of the complexing extractant in the organic solvent is 0.003 to 2.5 mol / kg, further 0.03 to 1.5 mol / kg.

[0046] In one embodiment, the mass ratio of the organic solvent to the first solution is (0.3-15):1, further (0.5-12):1, further (0.5-8):1, for example 1:1, 2:1, 3:1, 4:1, 6:1, 8:1.

[0047] In one embodiment, the first solution (also referred to as 1,5-pentanediamine alkali liquor) is prepared by alkali treatment of an aqueous solution containing 1,5-pentanediamine salt, i.e. adding a basic substance to react with the 1,5-pentanediamine salt in the aqueous solution to form 1,5-pentanediamine.

[0048] In one embodiment, the aqueous solution containing 1,5-pentanediamine salt can be a fermentation broth or an enzymatic conversion broth containing 1,5-pentanediamine salt, or an aqueous solution of 1,5-pentanediamine salt.

[0049] In one embodiment, the 1,5-pentanediamine salt includes any one or a combination of two or more of sulfate, hydrochloride, carbonate, and phosphate of 1,5-pentanediamine.

[0050] In one embodiment, the basic substance added to the aqueous solution containing 1,5-pentanediamine salt can be water-insoluble, including but not limited to one or more of calcium hydroxide, magnesium hydroxide, calcium oxide, and magnesium oxide.

[0051] In the present application, the way of adding the basic substance to the aqueous solution containing 1,5-pentanediamine salt is not particularly limited, which can be one-time input, batch input, or inputting multiple basic substances separately, or mixing all components and then adding at once.

[0052] In one embodiment, the reaction time of the aqueous solution containing 1,5-pentanediamine salt with the basic substance is ≥1 hour, further ≥1.5 hours.

[0053] In one embodiment, the temperature of the extraction treatment can be 10-95℃, further 20-60℃, further 20-40℃, for example 10℃, 22℃, 25℃, 28℃, 30℃, 32℃, 35℃, 38℃, 50℃, 60℃, 70℃, 80℃, 90℃, etc.

[0054] In one embodiment, the extraction rate of metal ions in the extraction treatment is ≥10%, further ≥50%, further ≥85%, further ≥90%, which refers to the percentage of metal ions entering the first organic solution in the metal ions in the first solution.

[0055] In one embodiment, the extraction rate of 1,5-pentanediamine in the extraction process is 50% or less, further 35% or less, further 30% or less, further 20% or less, which is the percentage of 1,5-pentanediamine in the first solution that enters the first organic solution.

[0056] In one embodiment, the pH of the first solution can be 7 or more, further 10-14, further 11-12.5, for example 10.5, 11.5, 12, 13, 13.5, etc.

[0057] In one embodiment, the pH of the first aqueous solution is 12 or less, further 11.5 or less, further 11 or less, further 10.5 or less.

[0058] In one embodiment, the pH of the first aqueous solution is 10-12.

[0059] In one embodiment, the difference between the pH of the first solution and the pH of the first aqueous solution is equal to ΔpH, and the absolute value of ΔpH is ≤2.5, further ≤2, for example ≤2.2, 1.8, 1.5, 1.3, 1.0, 0.8, 0.5. The lower the absolute value of ΔpH, the more metal ions are extracted, and the less 1,5-pentanediamine is extracted.

[0060] In one embodiment, the pH of the first solution is greater than the pH of the first aqueous solution.

[0061] The method of one embodiment of the present application further comprises the following steps:

[0062] The first organic solution is stripped by a second extractant, and after separation, a second aqueous solution (water phase) and a second organic solution (organic phase) are obtained; and

[0063] 1,5-pentanediamine is recovered from the first aqueous solution and the second aqueous solution;

[0064] The type of second extractant (stripping agent) includes water, basic aqueous solution.

[0065] In one embodiment of the present application, the second extractant is contacted with the first organic solution to perform stripping, so that the 1,5-pentanediamine remaining in the organic phase is transferred to the water phase, and is recovered through the water phase, further improving the yield of 1,5-pentanediamine. By controlling the stripping process conditions, as little metal ions as possible are extracted into the water phase, and as much 1,5-pentanediamine as possible is extracted into the water phase.

[0066] In one embodiment, the stripping rate of the metal ions during the stripping process is 5% or less, and further 1% or less. The stripping rate refers to the percentage of the metal ions in the first organic solution that enters the second aqueous solution.

[0067] In one embodiment, the stripping rate of the 1,5-pentanediamine during the stripping process is 20% or more, and further 50% or more. The stripping rate refers to the percentage of the 1,5-pentanediamine in the first organic solution that enters the second aqueous solution.

[0068] In one embodiment, the second extractant is water.

[0069] In one embodiment, the second extractant is an aqueous alkaline solution, which can be prepared by dissolving any one or a combination of two or more of alkaline substances, such as sodium hydroxide, potassium hydroxide, sodium oxide, and potassium oxide, in water. The purity of the alkaline substance is related to the source of the raw material, and as long as the impurities do not contain components that affect the quality of the 1,5-pentanediamine product, they can be used in the present application.

[0070] In one embodiment, the second extractant is an aqueous alkaline solution. The aqueous alkaline solution includes, but is not limited to, sodium hydroxide solution, potassium hydroxide solution, and combinations thereof.

[0071] The present application does not have a particular limitation on the addition method of the alkaline substance, which can be one-time input, batch input, or multiple alkaline substances can be added separately, or all components can be mixed and then added at once. The concentration of the aqueous alkaline solution can be 0.01 mol / L to 10 mol / L, further 0.05 to 5 mol / L, further 0.1 to 5 mol / L, for example, 0.5 mol / L, 1 mol / L, 1.5 mol / L, 2.5 mol / L, 3 mol / L, 4 mol / L.

[0072] In one embodiment, the temperature of the stripping process can be 10 to 120°C.

[0073] In one embodiment, the temperature of the stripping process can be 20 to 120°C, further 50 to 120°C, and further 80 to 100°C, for example, 60°C, 70°C, 90°C, etc.

[0074] In another embodiment, the temperature of the stripping process can be 10 to 100°C, further 20 to 40°C, for example, 25°C, 30°C, 35°C, etc.

[0075] In one embodiment, the volume ratio of the first organic solution to the second extractant (volume ratio of oil to water in the stripping stage) can be (0.5-10): 1, further (0.5-5): 1, for example 2: 1, 3: 1, 4: 1, 6: 1.

[0076] In one embodiment, the mass ratio of the second extractant to the complexing extractant can be (0.5-100): 1, further (1-50): 1; further (1-20): 1, for example 5: 1, 10: 1, 15: 1, 18: 1, 30: 1, 50: 1, 80: 1, 90: 1, etc.

[0077] In one embodiment, after stripping, the complexing extractant is reused in the primary reaction.

[0078] In one embodiment, the back-extraction is a single stage extraction or more than two stages of extraction. In one embodiment, A concentration step can be performed between any two stages of back-extraction. In one embodiment, a concentration step can be performed between any two stages of stripping.

[0079] In one embodiment, the method for recovering 1,5-pentanediamine from the first aqueous solution and / or the second aqueous solution can be a rectification process and / or a distillation process. The rectification and / or distillation can be performed in conventional equipment in the art.

[0080] In one embodiment, the method for recovering 1,5-pentanediamine from the first aqueous solution and / or the second aqueous solution comprises heating the first aqueous solution and / or the second aqueous solution to obtain a vapor containing 1,5-pentanediamine; collecting the vapor containing 1,5-pentanediamine and cooling to obtain a 1,5-pentanediamine product. By heating the first aqueous solution and / or the second aqueous solution, low-boiling-point substances such as solvent water can be removed, and other low-boiling-point impurities can also be further removed if present.

[0081] In one embodiment, the distillation process is performed at a pressure of -0.08 to -0.1 MPa (gauge) and a temperature of 150-185°C.

[0082] In one embodiment, after stripping, the solvent in the first aqueous solution and / or the second aqueous solution can be removed separately to recover the pentanediamine; or the first aqueous solution and / or the second aqueous solution can be removed together with the first solution that has not been treated by complexing extraction to remove water and obtain a pentanediamine product.

[0083] In one embodiment, 1,5-pentanediamine can be recovered from the first aqueous solution and / or the second aqueous solution to obtain a 1,5-pentanediamine product. The 1,5-pentanediamine product can then be used to participate in downstream reactions such as polymerization reactions, etc.; or the first aqueous solution and / or the second aqueous solution can be used as a raw material to participate in downstream reactions such as polymerization reactions, etc.

[0084] In one embodiment, the aqueous solution containing 1,5-pentanediamine salt can be a fermentation broth containing 1,5-pentanediamine salt produced by biological method, or an enzyme conversion solution; or can be an enzyme conversion solution of lysine salt reacted under the action of lysine decarboxylase (LDC); or can be an aqueous solution containing only 1,5-pentanediamine salt and metal ions.

[0085] The present application does not particularly limit the specific preparation method of the enzyme conversion solution containing 1,5-pentanediamine salt or the direct fermentation method for preparing 1,5-pentanediamine, and those skilled in the art can determine the specific raw materials and the process parameters of the specific enzyme conversion process according to the prior art, so as to obtain the aqueous solution containing 1,5-pentanediamine salt.

[0086] In one embodiment, the aqueous solution containing 1,5-pentanediamine salt is an enzyme conversion solution, which can be obtained by reacting lysine salt solution under the action of lysine decarboxylase (LDC). The lysine salt can be an inorganic salt or an organic salt of lysine, such as lysine hydrochloride and lysine sulfate commercially available on the market.

[0087] In one embodiment, the aqueous solution containing 1,5-pentanediamine salt is a fermentation broth containing 1,5-pentanediamine salt, which can be obtained by the following method: up-regulating the expression of lysine decarboxylase in a strain capable of producing lysine by genetic technology, or recombinantly expressing lysine decarboxylase, so that the produced lysine is simultaneously converted into pentanediamine during fermentation, thereby directly obtaining the fermentation broth containing 1,5-pentanediamine salt.

[0088] The present application does not particularly limit the specific preparation method of the enzyme conversion solution containing 1,5-pentanediamine salt or the direct fermentation method for preparing 1,5-pentanediamine, and those skilled in the art can determine the specific raw materials and the process parameters of the specific enzyme conversion process according to the prior art, so as to obtain the aqueous solution containing 1,5-pentanediamine salt.

[0089] In one embodiment, the enzyme conversion solution or the fermentation broth can be an original solution containing bacteria without any treatment, or a solution system (collectively referred to as treated solution) obtained after further treatment, such as a clear solution obtained after filtering bacteria and macromolecular substances such as proteins by ceramic membrane or ultrafiltration membrane, a solution obtained after simple filtration, a supernatant obtained after centrifugation, or a solution obtained after decolorization and impurity removal by activated carbon. In these processes, insoluble impurities or soluble impurities can be removed, and 1,5-pentanediamine salt can be retained in the solution system. In addition, the enzyme conversion solution or the fermentation broth, or the treated solution after treatment can be further concentrated. The concentration method can use any applicable prior art, such as evaporation, atmospheric distillation, reduced pressure distillation, reverse osmosis, etc.

[0090] In one embodiment, the aqueous solution containing 1,5-pentanediamine salt can be a pure solution system of an aqueous solution containing inorganic salt or organic salt of 1,5-pentanediamine, or can coexist with solid microbial or compound impurities, etc.

[0091] The embodiment of the present application can efficiently extract metal ions from the first solution system by complex extraction, and can reduce subsequent distillation solid residue. Meanwhile, the extraction method can be continuously operated, and has the advantages of large processing capacity, strong selectivity, low cost, high extraction rate, recyclable extractant, etc.

[0092] The embodiment of the present application can separate the entire 1,5-pentanediamine system from the metal ions by stripping the small amount of 1,5-pentanediamine extracted together with the metal ions in the complex extraction process, and recycling the 1,5-pentanediamine, so as to obtain a relatively pure 1,5-pentanediamine aqueous solution; and then obtaining a high-purity and high-yield 1,5-pentanediamine product by distillation or rectification process.

[0093] The embodiment of the present application also provides a 1,5-pentanediamine product prepared by any one of the above methods. The purity of the 1,5-pentanediamine product is more than 98%, further more than 98.5wt%, and still further more than 99%.

[0094] In an embodiment, the P content in the 1,5-pentanediamine product is less than or equal to 200ppm, and further less than or equal to 80ppm.

[0095] In an embodiment, the residual diluent content in the 1,5-pentanediamine product is less than or equal to 200ppm, and further less than or equal to 80ppm.

[0096] The embodiment of the present application further provides a polyamide, and the production raw material of the polyamide comprises the above 1,5-pentanediamine product.

[0097] In an embodiment, the yellow index of the polyamide is less than or equal to 8, and further less than or equal to 3.

[0098] In an embodiment, the P content in the polyamide is less than or equal to 100ppm, and further less than or equal to 60ppm.

[0099] Hereinafter, the extraction method of the 1,5-pentanediamine in the embodiment of the present application will be further described in combination with specific examples. In the examples and comparative examples, the raw material 1,5-pentanediamine alkalization liquid (first solution) is not otherwise specified, and is as follows:

[0100] In the examples 1-21 and comparative examples, the 1,5-pentanediamine alkalization liquid (provided by Kaisai (Wusu) Biological Material Co., Ltd.) is obtained by using CaO and / or Ca(OH)2 to alkalize the fermentation liquid containing 1,5-pentanediamine sulfate and / or 1,5-pentanediamine carbonate. The concentration of 1,5-pentanediamine in the 1,5-pentanediamine alkalization liquid is 8.87% (0.8696mol / L), and contains Ca 2+Concentration: 6959 ppm, pH of the alkalized liquor = 12.1; initial absorbance of the 1,5-pentanediamine alkalized liquor was 1.13.

[0101] In Example 22, 1,5-pentanediamine alkalized liquor (provided by Kaisai (Wusu) Biological Material Co., Ltd.): obtained by using MgO and / or Mg(OH)2to alkalize the fermentation liquor containing 1,5-pentanediamine sulfate and / or 1,5-pentanediamine carbonate. Among them, the concentration of 1,5-pentanediamine in the 1,5-pentanediamine alkalized liquor was 8.76%, the pH of the alkalized liquor was 12.0, and the initial absorbance of the 1,5-pentanediamine alkalized liquor was 1.18. 2+ Concentration: 6959 ppm, pH of the alkalized liquor = 12.1; initial absorbance of the 1,5-pentanediamine alkalized liquor was 1.13.

[0102] The detection methods of the performance parameters involved in each example are as follows:

[0103] 1. Detection method of pentanediamine purity:

[0104] Determined by gas chromatography normalization method.

[0105] 2. Absorbance detection method: measured by ultraviolet spectrophotometer.

[0106] 3. Determination method of pentanediamine concentration in aqueous phase:

[0107] By internal standard method, the sample was analyzed by nuclear magnetic resonance with dimethyl sulfoxide DMSO heavy water solution as internal standard. The integral area ratio of the methylene peak of the pentanediamine ortho amine group at 2.5 ppm to the methyl peak of dimethyl sulfoxide DMSO at 2.65 ppm, the corresponding internal standard concentration and the number of hydrogens were calculated.

[0108] Pentanediamine concentration = (internal standard concentration x internal standard mass x pentanediamine integral peak area x pentanediamine molecular weight x hydrogen number in pentanediamine integral peak (4) / (DMSO integral peak area x DMSO molecular weight x hydrogen number in DMSO integral peak (6)) x 100%

[0109] 4. Calculation method of total yield of pentanediamine:

[0110] Total yield = (pentanediamine product mass x pentanediamine product purity) / (pentanediamine alkalized liquor mass x pentanediamine concentration in pentanediamine alkalized liquor) x 100%.

[0111] 5. Calcium ion concentration determination method: EDTA titration method; magnesium ion concentration test method: tested by inductively coupled plasma atomic emission spectrometry (ICP).

[0112] 6. Polyamide 56 was prepared using the method set forth in Example 3 of published CN103980486B. And the properties of the polyamides involved were tested using the following methods, unless otherwise specified:

[0113] a) Viscosity number

[0114] Ubbelohde viscometer concentrated sulfuric acid method: accurately weigh the dried nylon sample 0.25±0.0002g, add 50mL concentrated sulfuric acid (96%) to dissolve, measure and record the concentrated sulfuric acid flow time t0and the nylon solution flow time t in a 25℃ constant temperature water bath.

[0115] Viscosity number calculation formula: viscosity number VN=(t / t0-1) / C

[0116] T—solution flow time, t0—solvent flow time, C—concentration of polymer (g / mL).

[0117] b) Yellow index: sample preparation and testing according to GB-T 2409-1980 method.

[0118] c) Tensile strength, elongation at break: sample preparation and testing according to ASTM D638 method.

[0119] d) Bending strength: sample preparation and testing according to ASTM D790 method.

[0120] e) Izod impact strength: sample preparation and testing according to ASTM D256 method.

[0121] 7. Detection of the content (ppm) of complexing extractant in the first aqueous solution: measured by gas chromatography normalization method, calculated according to the ratio of the peak area of complexing extractant to the peak area of pentanediamine in gas phase.

[0122] 8. Detection of the content (ppm) of diluent in the first aqueous solution: measured by gas chromatography normalization method, calculated according to the ratio of the peak area of diluent to the peak area of pentanediamine in gas phase.

[0123] 9. Detection of the content (ppm) of P (phosphorus) in 1,5-pentanediamine product: tested by inductively coupled plasma emission spectroscopy (ICP-OES).

[0124] 10. Detection of the content (ppm) of diluent in 1,5-pentanediamine product: measured by gas chromatography normalization method, calculated according to the ratio of the peak area of diluent to the peak area of pentanediamine in gas phase.

[0125] 11. Detection of the content (ppm) of P (phosphorus) in polyamide product: tested by inductively coupled plasma emission spectroscopy (ICP-OES).

[0126] Complexation extraction of Example 1

[0127] The organic solvent configured for complexation extraction includes extractant P507 and diluent carbon tetrachloride, wherein the concentration of P507 is 0.0522 mol / kg. The mass ratio of the organic solvent used in the complexation extraction process to the 1,5-pentanediamine alkaline solution is 1:1 (oil-water mass ratio).

[0128] Take the above-mentioned 1,5-pentanediamine alkaline solution 1 kg and the corresponding amount of the above-mentioned organic solvent, place it in a reactor, stir at 30°C and 300 rpm for 1 h, then stand for 30 min, and then separate after the two phases are completely layered to obtain a first organic solution and a first aqueous solution.

[0129] Subsequently, the first aqueous solution is distilled under a pressure of -0.09 MPa and heated to 180°C to obtain a pentanediamine product. The purity test results of the pentanediamine product are shown in Table 1.

[0130] The concentrations of pentanediamine and calcium ions in the aqueous phase before and after extraction are calculated, and the relevant experimental parameters are shown in Table 1.

[0131] Complexation extraction of Example 2

[0132] The organic solvent configured for complexation extraction includes extractant P507 and diluent carbon tetrachloride, wherein the concentration of P507 is 0.00522 mol / kg. The mass ratio of the organic solvent used in the complexation extraction process to the 1,5-pentanediamine alkaline solution is 1:1 (oil-water mass ratio).

[0133] Take the above-mentioned 1,5-pentanediamine alkaline solution 1 kg and the corresponding amount of the above-mentioned organic solvent, place it in a reactor, stir at 30°C and 300 rpm for 1 h, then stand for 30 min, and then separate after the two phases are completely layered to obtain a first organic solution and a first aqueous solution.

[0134] Subsequently, the first aqueous solution is distilled under a pressure of -0.09 MPa and heated to 180°C to obtain a pentanediamine product. The purity test results of the pentanediamine product are shown in Table 1.

[0135] The concentrations of pentanediamine and calcium ions in the aqueous phase before and after extraction are calculated, and the relevant experimental parameters are shown in Table 1.

[0136] Complexation extraction of Example 3

[0137] The organic solvent configured for complexation extraction includes extractant P507 and diluent carbon tetrachloride, wherein the concentration of P507 is 1.044 mol / kg. The mass ratio of the organic solvent used in the complexation extraction process to the 1,5-pentanediamine alkaline solution is 1:1 (oil-water mass ratio).

[0138] Take the above 1,5-pentanediamine alkaline solution 1 kg and the corresponding amount of the above organic solvent, placed in the reactor, stirring at 30 ℃, 300 rpm for 1 h, and then standing for 30 min, after the two phases are completely separated, the first organic solution and the first aqueous solution are obtained.

[0139] The first aqueous solution is then distilled under-0.09 MPa pressure and heated to 180 ℃. The distilled pentanediamine product is obtained. The purity test results of the pentanediamine product are shown in Table 1.

[0140] The concentrations of pentanediamine and calcium ions in the aqueous phase before and after extraction are calculated. The relevant experimental parameters are shown in Table 1.

[0141] Example 4 Complex extraction

[0142] The organic solvent used for complex extraction includes complexing agent P507 and diluent carbon tetrachloride, wherein the concentration of P507 is 0.0522 mol / kg. The mass ratio of the organic solvent used in the complex extraction process to the 1,5-pentanediamine alkaline solution is 2:1 (oil-water mass ratio).

[0143] Take the above 1,5-pentanediamine alkaline solution 1 kg and the corresponding amount of the above organic solvent, placed in the reactor, stirring at 30 ℃, 300 rpm for 1 h, and then standing for 30 min, after the two phases are completely separated, the first organic solution and the first aqueous solution are obtained.

[0144] The first aqueous solution is then distilled under-0.09 MPa pressure and heated to 180 ℃. The distilled pentanediamine product is obtained. The purity test results of the pentanediamine product are shown in Table 1.

[0145] The concentrations of pentanediamine and calcium ions in the aqueous phase before and after extraction are calculated. The relevant experimental parameters are shown in Table 1.

[0146] Example 5 Complex extraction

[0147] The organic solvent used for complex extraction includes complexing agent P507 and diluent carbon tetrachloride, wherein the concentration of P507 is 0.0522 mol / kg. The mass ratio of the organic solvent used in the complex extraction process to the 1,5-pentanediamine alkaline solution is 3:1 (oil-water mass ratio).

[0148] Take the above 1,5-pentanediamine alkaline solution 1 kg and the corresponding amount of the above organic solvent, placed in the reactor, stirring at 30 ℃, 300 rpm for 1 h, and then standing for 30 min, after the two phases are completely separated, the first organic solution and the first aqueous solution are obtained.

[0149] The first aqueous solution is then distilled, heated to 180°C under a pressure of -0.09 MPa, and pentanediamine product is distilled. The purity of the pentanediamine product is shown in Table 1.

[0150] The concentrations of pentanediamine and calcium ions in the aqueous phase before and after extraction are calculated, and the relevant experimental parameters are shown in Table 1.

[0151] Example 6 Complex extraction

[0152] The organic solvent used for complex extraction is prepared, including complexing agent P507 and diluent carbon tetrachloride, wherein the concentration of P507 is 0.0522 mol / kg. The mass ratio of the organic solvent used in the complex extraction process to the 1,5-pentanediamine alkaline solution is 5:1 (oil-water mass ratio).

[0153] The above-mentioned 1 kg of 1,5-pentanediamine alkaline solution and the corresponding amount of the above-mentioned organic solvent are placed in a reactor, stirred at 30°C and a rotation speed of 300 rpm for 1 h, and then left to stand for 30 min. After the two phases are completely separated, a first organic solution and a first aqueous solution are obtained.

[0154] The first aqueous solution is then distilled, heated to 180°C under a pressure of -0.09 MPa, and pentanediamine product is distilled. The purity of the pentanediamine product is shown in Table 1.

[0155] The concentrations of pentanediamine and calcium ions in the aqueous phase before and after extraction are calculated, and the relevant experimental parameters are shown in Table 1.

[0156] Example 7 Complex extraction

[0157] The organic solvent used for complex extraction is prepared, including complexing agent P507 and diluent carbon tetrachloride, wherein the concentration of P507 is 0.0522 mol / kg. The mass ratio of the organic solvent used in the complex extraction process to the 1,5-pentanediamine alkaline solution is 10:1 (oil-water mass ratio).

[0158] The above-mentioned 1 kg of 1,5-pentanediamine alkaline solution and the corresponding amount of the above-mentioned organic solvent are placed in a reactor, stirred at 30°C and a rotation speed of 300 rpm for 1 h, and then left to stand for 30 min. After the two phases are completely separated, a first organic solution and a first aqueous solution are obtained.

[0159] The first aqueous solution is then distilled, heated to 180°C under a pressure of -0.09 MPa, and pentanediamine product is distilled. The purity of the pentanediamine product is shown in Table 1.

[0160] The concentrations of pentanediamine and calcium ions in the aqueous phase before and after extraction are calculated, and the relevant experimental parameters are shown in Table 1.

[0161] Example 8 Complex extraction

[0162] The organic solvent used for complex extraction includes complexing agent P507 and diluent carbon tetrachloride, wherein the concentration of P507 is 0.0522 mol / kg. The mass ratio of the organic solvent used in the complex extraction process to the 1,5-pentanediamine alkaline solution is 5:1 (oil-water mass ratio).

[0163] The above 1 kg of 1,5-pentanediamine alkaline solution and the corresponding amount of the above organic solvent are placed in a reactor, stirred at 90°C and a rotation speed of 300 rpm for 1 h, and then left to stand for 30 min. After the two phases are completely separated, the first organic solution and the first aqueous solution are separated.

[0164] The first aqueous solution is then distilled. The distillation is performed under a pressure of -0.09 MPa and at a temperature of 180°C. The purity of the pentanediamine product is shown in Table 1.

[0165] The concentrations of pentanediamine and calcium ions in the aqueous phase before and after extraction are calculated, and the related experimental parameters are shown in Table 1.

[0166] Example 9 Complex extraction

[0167] The organic solvent used for complex extraction includes complexing agent P507 and diluent carbon tetrachloride, wherein the concentration of P507 is 0.0522 mol / kg. The mass ratio of the organic solvent used in the complex extraction process to the 1,5-pentanediamine alkaline solution is 5:1 (oil-water mass ratio).

[0168] The above 1 kg of 1,5-pentanediamine alkaline solution and the corresponding amount of the above organic solvent are placed in a reactor, stirred at 90°C and a rotation speed of 300 rpm for 1 h, and then left to stand for 30 min. After the two phases are completely separated, the first organic solution and the first aqueous solution are separated.

[0169] The first aqueous solution is then distilled. The distillation is performed under a pressure of -0.09 MPa and at a temperature of 180°C. The purity of the pentanediamine product is shown in Table 1.

[0170] The concentrations of pentanediamine and calcium ions in the aqueous phase before and after extraction are calculated, and the related experimental parameters are shown in Table 1.

[0171] Example 10 Complex extraction

[0172] The organic solvent used for complex extraction includes complexing agent P507 and diluent carbon tetrachloride, wherein the concentration of P507 is 0.0522 mol / kg. The mass ratio of the organic solvent used in the complex extraction process to the 1,5-pentanediamine alkaline solution is 5:1 (oil-water mass ratio).

[0173] Take the above-mentioned 1,5-pentanediamine alkaline solution 1 kg and the corresponding amount of the above-mentioned organic solvent, placed in the reactor, stirring at 30℃, 300 rpm for 1h, then stand for 30min, after the two phases are completely separated, the first organic solution and the first aqueous solution are obtained.

[0174] The first aqueous solution is then distilled, heated to 180℃ under-0.09MPa pressure, and the pentanediamine product is distilled. The purity of the pentanediamine product is shown in Table 1.

[0175] The concentrations of pentanediamine and calcium ions in the aqueous phase before and after extraction are calculated, and the relevant experimental parameters are shown in Table 1.

[0176] Example 11 Complex extraction

[0177] The organic solvent used for complex extraction is configured to include complexing agent P507 and diluent butyl acetate, wherein the concentration of P507 is 0.0522 mol / kg. The mass ratio of the organic solvent used in the complex extraction process to the 1,5-pentanediamine alkaline solution is 5:1 (oil-water mass ratio).

[0178] Take the above-mentioned 1,5-pentanediamine alkaline solution 1 kg and the corresponding amount of the above-mentioned organic solvent, placed in the reactor, stirring at 30℃, 300 rpm for 1h, then stand for 30min, after the two phases are completely separated, the first organic solution and the first aqueous solution are obtained.

[0179] The first aqueous solution is then distilled, heated to 180℃ under-0.09MPa pressure, and the pentanediamine product is distilled. The purity of the pentanediamine product is shown in Table 1.

[0180] The concentrations of pentanediamine and calcium ions in the aqueous phase before and after extraction are calculated, and the relevant experimental parameters are shown in Table 1.

[0181] Example 12 Complex extraction

[0182] The organic solvent used for complex extraction is configured to include complexing agent P507 and diluent isopropyl ether, wherein the concentration of P507 is 0.0522 mol / kg. The mass ratio of the organic solvent used in the complex extraction process to the 1,5-pentanediamine alkaline solution is 5:1 (oil-water mass ratio).

[0183] Take the above-mentioned 1,5-pentanediamine alkaline solution 1 kg and the corresponding amount of the above-mentioned organic solvent, placed in the reactor, stirring at 30℃, 300 rpm for 1h, then stand for 30min, after the two phases are completely separated, the first organic solution and the first aqueous solution are obtained.

[0184] The first aqueous solution is then distilled, heated to 180°C under a pressure of -0.09 MPa, and pentanediamine product is distilled. The purity of the pentanediamine product is shown in Table 1.

[0185] The concentrations of pentanediamine and calcium ions in the aqueous phase before and after extraction are calculated, and the relevant experimental parameters are shown in Table 1.

[0186] Example 13 Complex extraction

[0187] The organic solvent used for complex extraction is prepared, including complexing agent P204 and diluent carbon tetrachloride, wherein the concentration of P204 is 0.0522 mol / kg. The mass ratio of the organic solvent used in the complex extraction process to the 1,5-pentanediamine alkaline solution is 5:1 (oil-water mass ratio).

[0188] The above-mentioned 1 kg of 1,5-pentanediamine alkaline solution and the corresponding amount of the above-mentioned organic solvent are placed in a reactor, stirred at 30°C and a rotation speed of 300 rpm for 1 h, and then left to stand for 30 min. After the two phases are completely separated, the first organic solution and the first aqueous solution are obtained.

[0189] The first aqueous solution is then distilled, heated to 180°C under a pressure of -0.09 MPa, and pentanediamine product is distilled. The purity of the pentanediamine product is shown in Table 1.

[0190] The concentrations of pentanediamine and calcium ions in the aqueous phase before and after extraction are calculated, and the relevant experimental parameters are shown in Table 1.

[0191] Example 14 Complex extraction

[0192] The organic solvent used for complex extraction is prepared, including complexing agent P204 and diluent carbon tetrachloride, wherein the concentration of P204 is 0.0522 mol / kg. The mass ratio of the organic solvent used in the complex extraction process to the 1,5-pentanediamine alkaline solution is 5:1 (oil-water mass ratio).

[0193] The above-mentioned 1 kg of 1,5-pentanediamine alkaline solution and the corresponding amount of the above-mentioned organic solvent are placed in a reactor, stirred at 30°C and a rotation speed of 300 rpm for 1 h, and then left to stand for 30 min. After the two phases are completely separated, the first organic solution and the first aqueous solution are obtained.

[0194] The first aqueous solution is then distilled, heated to 180°C under a pressure of -0.09 MPa, and pentanediamine product is distilled. The purity of the pentanediamine product is shown in Table 1.

[0195] The concentrations of pentanediamine and calcium ions in the aqueous phase before and after extraction are calculated, and the relevant experimental parameters are shown in Table 1.

[0196] Example 15 Complexation extraction

[0197] The organic solvent configured for complexation extraction includes complexing agent ethylene bisphosphonic acid tetrabutyl ester and diluent carbon tetrachloride, wherein the concentration of the complexing agent is 0.0522 mol / kg. The mass ratio of the organic solvent used in the complexation extraction to the 1,5-pentanediamine alkaline solution is 5:1 (oil-water mass ratio).

[0198] The above 1 kg of 1,5-pentanediamine alkaline solution and the corresponding amount of the above organic solvent are placed in a reactor, stirred at 30°C and a rotation speed of 300 rpm for 1 h, and then left to stand for 30 min. After the two phases are completely separated, a first organic solution and a first aqueous solution are obtained.

[0199] The first aqueous solution is then distilled at a pressure of -0.09 MPa and heated to 180°C to obtain a pentanediamine product. The purity of the pentanediamine product is shown in Table 1.

[0200] The concentrations of pentanediamine and calcium ions in the aqueous phase before and after extraction are calculated, and the relevant experimental parameters are shown in Table 1.

[0201] Example 16 Complexation extraction

[0202] The organic solvent configured for complexation extraction includes complexing agent ethylene bisphosphonic acid tetrabutyl ester and diluent carbon tetrachloride, wherein the concentration of the complexing agent is 0.0522 mol / kg. The mass ratio of the organic solvent used in the complexation extraction to the 1,5-pentanediamine alkaline solution is 5:1 (oil-water mass ratio).

[0203] The above 1 kg of 1,5-pentanediamine alkaline solution and the corresponding amount of the above organic solvent are placed in a reactor, stirred at 30°C and a rotation speed of 300 rpm for 1 h, and then left to stand for 30 min. After the two phases are completely separated, a first organic solution and a first aqueous solution are obtained.

[0204] The first aqueous solution is then distilled at a pressure of -0.09 MPa and heated to 180°C to obtain a pentanediamine product. The purity of the pentanediamine product is shown in Table 1.

[0205] The concentrations of pentanediamine and calcium ions in the aqueous phase before and after extraction are calculated, and the relevant experimental parameters are shown in Table 1.

[0206] Example 17 Complexation extraction

[0207] The organic solvent used for complex extraction is configured to include complexing extractant α-acyl methyl phosphonic acid dibutyl ester, P507 and diluent carbon tetrachloride, wherein the concentration of the complexing extractant is 0.0522 mol / kg, and the molar ratio of α-acyl methyl phosphonic acid dibutyl ester to P507 is 1:5. The mass ratio of the organic solvent used in the complex extraction process to the 1,5-pentanediamine alkaline solution is 5:1 (oil-water mass ratio).

[0208] The above-mentioned 1 kg of 1,5-pentanediamine alkaline solution and the corresponding amount of the above-mentioned organic solvent are placed in a reactor, stirred at 30°C and a rotation speed of 300 rpm for 1 h, and then left to stand for 30 min. After the two phases are completely separated, a first organic solution and a first aqueous solution are obtained.

[0209] Subsequently, the first aqueous solution is distilled at a pressure of -0.09 MPa and heated to 180°C to obtain a pentanediamine product. The purity detection results of the pentanediamine product are shown in Table 1.

[0210] The concentrations of pentanediamine and calcium ions in the aqueous phase before and after extraction are calculated, and the related experimental parameters are shown in Table 1.

[0211] Example 18 Complex extraction

[0212] The organic solvent used for complex extraction is configured to include complexing extractant α-acyl methyl phosphonic acid dibutyl ester, P507 and diluent carbon tetrachloride, wherein the concentration of the complexing extractant is 0.0522 mol / kg, and the molar ratio of α-acyl methyl phosphonic acid dibutyl ester to P507 is 1:5. The mass ratio of the organic solvent used in the complex extraction process to the 1,5-pentanediamine alkaline solution is 5:1 (oil-water mass ratio).

[0213] The above-mentioned 1 kg of 1,5-pentanediamine alkaline solution and the corresponding amount of the above-mentioned organic solvent are placed in a reactor, stirred at 30°C and a rotation speed of 300 rpm for 1 h, and then left to stand for 30 min. After the two phases are completely separated, a first organic solution and a first aqueous solution are obtained.

[0214] Subsequently, the first aqueous solution is distilled at a pressure of -0.09 MPa and heated to 180°C to obtain a pentanediamine product. The purity detection results of the pentanediamine product are shown in Table 1.

[0215] The concentrations of pentanediamine and calcium ions in the aqueous phase before and after extraction are calculated, and the related experimental parameters are shown in Table 1.

[0216] Example 19 Complex extraction

[0217] The organic solvent used for complex extraction includes complexing agent P507 and diluent carbon tetrachloride, chloroform, wherein the concentration of P507 is 0.0522 mol / kg, and the molar ratio of carbon tetrachloride and chloroform is 3:1. The mass ratio of the organic solvent used in the complex extraction process to the 1,5-pentanediamine alkaline solution is 5:1 (oil-water mass ratio).

[0218] The above-mentioned 1 kg of 1,5-pentanediamine alkaline solution and the corresponding amount of the above-mentioned organic solvent are placed in a reactor, stirred at 30°C and a rotation speed of 300 rpm for 1 h, and then left to stand for 30 min. After the two phases are completely separated, a first organic solution and a first aqueous solution are obtained.

[0219] Subsequently, the first aqueous solution is distilled under a pressure of -0.09 MPa and heated to 180°C to obtain a pentanediamine product. The purity of the pentanediamine product is shown in Table 1.

[0220] The concentrations of pentanediamine and calcium ions in the aqueous phase before and after extraction are calculated, and the related experimental parameters are shown in Table 1.

[0221] Example 20 Complex extraction

[0222] The organic solvent used for complex extraction includes complexing agent P507 and diluent carbon tetrachloride, chloroform, wherein the concentration of P507 is 0.0522 mol / kg, and the molar ratio of carbon tetrachloride and chloroform is 3:1. The mass ratio of the organic solvent used in the complex extraction process to the 1,5-pentanediamine alkaline solution is 5:1 (oil-water mass ratio).

[0223] The above-mentioned 1 kg of 1,5-pentanediamine alkaline solution and the corresponding amount of the above-mentioned organic solvent are placed in a reactor, stirred at 30°C and a rotation speed of 300 rpm for 1 h, and then left to stand for 30 min. After the two phases are completely separated, a first organic solution and a first aqueous solution are obtained.

[0224] Subsequently, the first aqueous solution is distilled under a pressure of -0.09 MPa and heated to 180°C to obtain a pentanediamine product. The purity of the pentanediamine product is shown in Table 1.

[0225] The concentrations of pentanediamine and calcium ions in the aqueous phase before and after extraction are calculated, and the related experimental parameters are shown in Table 1.

[0226] Example 20 Complex extraction

[0227] The organic solvent used for complex extraction includes complexing agent P507 and diluent carbon tetrachloride, chloroform, wherein the concentration of P507 is 0.0522 mol / kg, and the molar ratio of carbon tetrachloride and chloroform is 3:1. The mass ratio of the organic solvent used in the complex extraction process to the 1,5-pentanediamine alkaline solution is 5:1 (oil-water mass ratio).

[0228] Take the above-mentioned 1,5-pentanediamine alkaline solution 1 kg and the corresponding amount of the above-mentioned organic solvent, placed in the reactor, stirring at 30℃, 300 rpm for 1h, then stand for 30min, after the two phases are completely separated, the first organic solution and the first aqueous solution are obtained.

[0229] The first aqueous solution is then distilled, heated to 180℃ under-0.09MPa pressure, and the pentanediamine product is distilled. The purity of the pentanediamine product is shown in Table 1.

[0230] The concentrations of pentanediamine and calcium ions in the aqueous phase before and after extraction are calculated, and the relevant experimental parameters are shown in Table 1.

[0231] Example 22 Complex extraction

[0232] The organic solvent for complex extraction is configured, including complexing agent P204 and diluent carbon tetrachloride, wherein the concentration of P204 is 0.0522 mol / kg. The mass ratio of the organic solvent used in the complex extraction process to the 1,5-pentanediamine alkaline solution is 5:1 (oil-water mass ratio).

[0233] Take the above-mentioned 1,5-pentanediamine alkaline solution 1 kg and the corresponding amount of the above-mentioned organic solvent, placed in the reactor, stirring at 30℃, 300 rpm for 1h, then stand for 30min, after the two phases are completely separated, the first organic solution and the first aqueous solution are obtained.

[0234] The first aqueous solution is then distilled, heated to 180℃ under-0.09MPa pressure, and the pentanediamine product is distilled. The purity of the pentanediamine product is shown in Table 1.

[0235] The concentrations of pentanediamine and magnesium ions in the aqueous phase before and after extraction are calculated, and the relevant experimental parameters are shown in Table 1.

[0236] Example 22 Complex extraction

[0237] The extraction agent is configured as carbon tetrachloride, and the oil-water mass ratio of the 1,5-pentanediamine alkaline solution is 1:1.

[0238] Take the above-mentioned 1,5-pentanediamine alkaline solution 1 kg and the corresponding amount of carbon tetrachloride, placed in the reactor, stirring at 30℃, 300 rpm for 1h, then stand for 30min, after the two phases are completely separated, the first organic solution and the first aqueous solution are obtained.

[0239] The first aqueous solution is then distilled, heated to 180℃ under-0.09MPa pressure, and the pentanediamine product is distilled. The purity of the pentanediamine product is shown in Table 1.

[0240] The concentration of piperazine and calcium ion in the water phase before and after extraction was calculated, and the relevant experimental parameters are shown in Table 1.

[0241] Comparative Example 2 Complex extraction

[0242] The extractant was carbon tetrachloride, and the oil-water mass ratio of the alkaline solution was 5:1.

[0243] Take the above-mentioned 1, 5-piperazine alkaline solution 1 kg and the corresponding amount of carbon tetrachloride, place it in a reactor, stir at 30°C and 300 rpm for 1 hour, then stand for 30 minutes, and then separate after the two phases are completely separated. The first organic solution and the first aqueous solution are obtained.

[0244] Subsequently, the first aqueous solution is distilled under a pressure of -0.09 MPa and heated to 180°C to obtain a piperazine product. The purity test results of the piperazine product are shown in Table 1.

[0245] The concentration of piperazine and calcium ion in the water phase before and after extraction was calculated, and the relevant experimental parameters are shown in Table 1.

[0246] Comparative Example 3 Complex extraction

[0247] The extractant was carbon tetrachloride, and the oil-water mass ratio of the 1, 5-piperazine alkaline solution was 10:1.

[0248] Take the above-mentioned 1, 5-piperazine alkaline solution 1 kg and the corresponding amount of carbon tetrachloride, place it in a reactor, stir at 30°C and 300 rpm for 1 hour, then stand for 30 minutes, and then separate after the two phases are completely separated. The first organic solution and the first aqueous solution are obtained.

[0249] Subsequently, the first aqueous solution is distilled under a pressure of -0.09 MPa and heated to 180°C to obtain a piperazine product. The purity test results of the piperazine product are shown in Table 1.

[0250] The concentration of piperazine and calcium ion in the water phase before and after extraction was calculated, and the relevant experimental parameters are shown in Table 1.

[0251] Table 1

[0252]

[0253] Comparing the data in Table 1, it can be seen that, in the presence of the same amount of diluent, the complexing extractant in the examples can well extract metal ions. However, when the diluent is used as the extractant alone, the extraction efficiency of metal ions is very low, and thus the separation and extraction of piperazine and metal ions cannot be achieved. Different complexing extractants have different extraction efficiencies for piperazine and metal ions, and a suitable extraction system should have a lower extraction rate for piperazine and a higher extraction rate for metal ions, thereby improving the separation capacity of metal ions from piperazine.

[0254] In addition, a suitable extractant concentration can further improve the extraction selectivity of the extraction system for piperazine and metal ions, thereby reducing the extraction amount of piperazine and extracting more metal ions. That is, in the presence of a small amount of extractant, as much metal ions as possible are extracted. When the concentration of the complexing extractant is too high, although the extraction efficiency of metal ions is still higher than that of piperazine, the separation degree of the two is low.

[0255] When the same concentration of complexing extractant is used for extraction, as the oil-water ratio increases, the extraction capacity of the extraction system for piperazine and metal ions also increases. A suitable extractant can control the extraction rate of metal ions to be faster than that of piperazine, thereby improving the separation capacity of metal ions from piperazine.

[0256] In the following examples, the stripping efficiency is calculated based on the content of piperazine extracted in the system.

[0257] Example 6-1

[0258] (1) Complex extraction was performed according to the raw materials and process of Example 6 to obtain a first organic solution and a first aqueous solution.

[0259] (2) 1 L of the first organic solution was taken and placed in a reactor, 1 L of water was added as a stripping agent (i.e., the oil-water volume ratio was 1:1), a reflux condenser was installed, and stirring was performed at 100°C and a rotation speed of 300 rpm for 1 h. After standing for 30 min, the two phases were completely separated to obtain a second organic solution and a second aqueous solution. The stripping rate of piperazine was 59.8%, and the stripping rate of calcium ions was 0.68%.

[0260] After the first aqueous solution and the second aqueous solution were combined, it was found that the total yield of piperazine was 94.3%, and the residual calcium ion content was 570 ppm.

[0261] After the first aqueous solution and the second aqueous solution were combined, distillation was performed under a pressure of -0.09 MPa and heating to 180°C to obtain pure piperazine, and the purity was determined by gas chromatography to be 99.3%.

[0262] Example 6-2

[0263] (1) Complexation extraction was carried out according to the raw materials and process of Example 6 to obtain the first organic solution and the first aqueous solution.

[0264] (2) 1 L of the first organic solution was taken and placed in a reactor, 1 L of water was added as a stripping agent (i.e. the oil-water volume ratio was 1:1), and stirring was carried out at 80°C and a rotation speed of 300 rpm for 1 h, then the mixture was allowed to stand for 30 min, after the two phases were completely separated, extraction separation was carried out to obtain the second organic solution and the second aqueous solution. The stripping rate of pentanediamine was calculated to be 51.8%, and the stripping rate of calcium ions was 0.46%.

[0265] After the first aqueous solution and the second aqueous solution were combined, it was detected that the total yield of pentanediamine was 93.2%, and the residual calcium ion content was 560 ppm.

[0266] After the first aqueous solution and the second aqueous solution were combined, distillation was carried out, heated to 180°C under a pressure of -0.09 MPa, and pentanediamine pure product was obtained by distillation, and the purity was determined by gas chromatography to be 99.6%.

[0267] Example 6-3

[0268] (1) Complexation extraction was carried out according to the raw materials and process of Example 6 to obtain the first organic solution and the first aqueous solution.

[0269] (2) 1 L of the first organic solution was taken and placed in a reactor, 1 L of water was added as a stripping agent (i.e. the oil-water volume ratio was 1:1), and stirring was carried out at 50°C and a rotation speed of 300 rpm for 1 h, then the mixture was allowed to stand for 30 min, after the two phases were completely separated, extraction separation was carried out to obtain the second organic solution and the second aqueous solution. The stripping rate of pentanediamine was calculated to be 39.1%, and the stripping rate of calcium ions was 0.41%.

[0270] After the first aqueous solution and the second aqueous solution were combined, it was detected that the total yield of pentanediamine was 91.3%, and the residual calcium ion content was 557 ppm.

[0271] After the first aqueous solution and the second aqueous solution were combined, distillation was carried out, heated to 180°C under a pressure of -0.09 MPa, and pentanediamine pure product was obtained by distillation, and the purity was determined by gas chromatography to be 99.1%.

[0272] Example 6-4

[0273] (1) Complexation extraction was carried out according to the raw materials and process of Example 6 to obtain the first organic solution and the first aqueous solution.

[0274] (2) Take 1 L of the first organic solution, place it in a reactor, add 1 L of water as a stripping agent (i.e. the oil-water volume ratio is 1:1), stir at 300 rpm for 1 h at 30°C, then stand for 30 min, and after the two phases are completely separated, carry out extraction separation to obtain a second organic solution and a second aqueous solution. The stripping rate of pentanediamine is calculated to be 31.6%, and the stripping rate of calcium ions is 0.23%.

[0275] After the first aqueous solution and the second aqueous solution are combined, the total yield of pentanediamine is detected to be 90.2%, and the residual calcium ion content is 546 ppm.

[0276] After the first aqueous solution and the second aqueous solution are combined, distillation is carried out, heated to 180°C under a pressure of -0.09 MPa, and pentanediamine pure product is distilled, and the purity is determined by gas chromatography to be 98.9%.

[0277] Example 6-5

[0278] (1) Complex extraction is carried out according to the raw materials and process of Example 6 to obtain a first organic solution and a first aqueous solution.

[0279] (2) Take 1 L of the first organic solution, place it in a reactor, add 1 L of 2 mol / L NaOH solution as a stripping agent (i.e. the oil-water volume ratio is 1:1), stir at 300 rpm for 1 h at 30°C, then stand for 30 min, and after the two phases are completely separated, carry out extraction separation to obtain a second organic solution and a second aqueous solution. The stripping rate of pentanediamine is calculated to be 64.8%, and the stripping rate of calcium ions is 2.06%.

[0280] After the first aqueous solution and the second aqueous solution are combined, the total yield of pentanediamine is detected to be 95.0%, and the residual calcium ion content is 663 ppm.

[0281] After the first aqueous solution and the second aqueous solution are combined, distillation is carried out, heated to 180°C under a pressure of -0.09 MPa, and pentanediamine pure product is distilled, and the purity is determined by gas chromatography to be 98.9%.

[0282] The obtained pentanediamine product and the polyamide sample obtained by polymerization of adipic acid are further subjected to basic physical and chemical property analysis, and the results are shown in Table 2.

[0283] Table 2

[0284]

[0285] Unless specifically limited, the terms used in the present application have the meanings generally understood by those skilled in the art.

[0286] The embodiments described herein are for illustrative purposes only and are not intended to limit the scope of the present invention, and various other substitutions, changes and improvements can be made by those skilled in the art within the scope of the present invention, and thus the present invention is not limited to the above-described embodiments but is defined only by the claims.

Claims

1. A method for extracting 1,5-pentanediamine, comprising the steps of: providing a first solution comprising 1,5-pentanediamine, metal ions and water; subjecting the first solution to an extraction treatment by an organic solvent to obtain a first aqueous solution and a first organic solution, so that at least a part of the metal ions in the first solution is extracted into the first organic solution; and recovering 1,5-pentanediamine from the first aqueous solution; wherein the concentration of 1,5-pentanediamine in the first solution is 50 wt% or less; the concentration of metal ions in the first solution is 2 wt% or less; the metal ions are selected from any one or more of calcium ions, magnesium ions, iron ions and barium ions; the organic solvent is a complexing extractant and a diluent, wherein the concentration of the complexing extractant in the organic solvent is 0.03-0.0522 mol / kg; the mass ratio of the organic solvent to the first solution is (2-15) : 1; the complexing extractant is selected from neutral phosphorus oxygen type extractants, acidic phosphorus oxygen type extractants and double coordination phosphorus oxygen type extractants; the neutral phosphorus oxygen type extractants are selected from tributyl phosphate and dihexyl(octyl) phosphine oxide; the acidic phosphorus oxygen type extractants are selected from 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester and dimethylheptyl phosphoric acid methylide; the double coordination phosphorus oxygen type extractants are selected from dibutyl α-acyl methyl phosphonate and ethylene bisphosphonic acid tetrabutyl ester; the diluent is selected from one, two or more of isopropyl ether, ethyl ether, n-butyl ether, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, kerosene, n-hexane, xylene, ethyl acetate and butyl acetate; and the pH value of the first solution is 7-14. 2.The method of claim 1, wherein the extraction rate of the metal ions during the extraction treatment is 10% or more. 3.The method of claim 2, wherein the extraction rate of the metal ions during the extraction treatment is 50% or more. 4.The method of claim 2, wherein the extraction rate of the metal ions during the extraction treatment is 85% or more. 5.The method of claim 2, wherein the extraction rate of the metal ions during the extraction treatment is 90% or more. The neutral phosphorus oxygen type extractant is tributyl phosphate. The acidic phosphorus oxygen type extractant is selected from 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester and di(2-ethylhexyl) phosphoric acid. The complexing extractant is selected from a combination of one or more of 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester, di(2-ethylhexyl) phosphoric acid, dibutyl α-acyl methyl phosphonate, ethylene bisphosphonic acid tetrabutyl ester and tributyl phosphate. In the first aqueous solution, the content of the diluent is 7000 ppm or less. In the first aqueous solution, the content of the diluent is 3000 ppm or less. The concentration of 1,5-pentanediamine in the first solution is 10 wt% or less. The concentration of metal ions in the first solution is 1 wt% or less. ​ ​ ​ ​ ​ 6. The method of claim 1, wherein, ​ 7. The method of claim 1, wherein, ​ 8. The method of claim 1, wherein, ​ 9. The method of claim 1, wherein, ​ 10. The method of claim 1, wherein, ​ 11. The method of claim 1, wherein, ​ 12. The method of claim 1, wherein, ​ 13. The method of claim 1, wherein, an absolute value of a difference ΔpH between a pH value of the first solution and a pH value of the first aqueous solution is ≤ 2.5; and / or, a molar ratio of the complexing extractant to the metal ion is (0.1-50):1; and / or, a temperature of the extraction treatment is 10-95°C; and / or, an extraction rate of 1,5-pentanediamine in the extraction treatment is 50% or less.

14. The method of claim 13, wherein, a molar ratio of the complexing extractant to the metal ion is (1-30):

1.

15. The method of claim 13, wherein, an extraction rate of 1,5-pentanediamine in the extraction treatment is 30% or less.

16. The method of claim 13, wherein, an extraction rate of 1,5-pentanediamine in the extraction treatment is 20% or less.

17. The method of claim 1, wherein, further comprising the steps of: back-extracting the first organic solution with a second extractant to obtain a second aqueous solution and a second organic solution; and recovering 1,5-pentanediamine from the first aqueous solution and the second aqueous solution; wherein the second extractant comprises water, an aqueous alkaline solution.

18. The method of claim 17, wherein, a volume ratio of the first organic solution to the second extractant is (0.5-5):1; and / or, a mass ratio of the second extractant to the complexing extractant is (0.5-100):1; and / or, a temperature of the back-extraction is 10-120°C.

19. The method of claim 17, wherein, separating the 1,5-pentanediamine from the first aqueous solution and the second aqueous solution by a rectification process and / or a distillation process.

20. The method of claim 1, wherein, a concentration of 1,5-pentanediamine in the first solution is 30 wt% or less; and / or, a pH value of the first solution is 10-14.

21. The method of any one of claims 1 to 20, wherein, the preparation process of the first solution comprises: providing a second solution comprising a 1,5-pentanediamine salt and water; and adding an alkaline substance to the second solution, the 1,5-pentanediamine salt reacting with the alkaline substance to generate 1,5-pentanediamine.

22. The method of claim 21, wherein, the second solution is an aqueous solution of a 1,5-pentanediamine salt, or a fermentation broth or an enzyme conversion broth produced by a biological method and containing a 1,5-pentanediamine salt.

23. The method of claim 21, wherein, the 1,5-pentanediamine salt is selected from any one or a combination of two or more of a sulfate salt, a hydrochloride salt, a carbonate salt, and a phosphate salt of 1,5-pentanediamine.

24. The method of claim 1, wherein, a content of the complexing extractant in the first aqueous solution is 2500 ppm or less.

25. The method of claim 24, wherein, a content of the complexing extractant in the first aqueous solution is 1500 ppm or less.

26. The method of claim 1, wherein a purity of the obtained 1,5-pentanediamine product is 98 wt% or more.

27. The method of claim 1, wherein a P content of the obtained 1,5-pentanediamine product is 200 ppm or less.

28. The method of claim 27, wherein the P content of the obtained 1,5-pentanediamine product is 80 ppm or less.

29. The method of claim 1, wherein a diluent content of the obtained 1,5-pentanediamine product is 200 ppm or less.

30. The method of claim 29, wherein the diluent content of the obtained 1,5-pentanediamine product is 80 ppm or less.

31. A method of producing a polyamide, comprising carrying out the method of any one of claims 1-30, and producing a polyamide from the obtained 1,5-pentanediamine product.

32. The method of claim 31, wherein the resulting polyamide has a yellowness index of 8 or less.

33. The method of claim 32, wherein the resulting polyamide has a yellowness index of 3 or less.

34. The method of claim 31 or 32, wherein the resulting polyamide has a P content of 60 ppm or less.

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