CN115611748A - Separation method of 1, 5-pentanediamine - Google Patents
Separation method of 1, 5-pentanediamine Download PDFInfo
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- CN115611748A CN115611748A CN202110795397.8A CN202110795397A CN115611748A CN 115611748 A CN115611748 A CN 115611748A CN 202110795397 A CN202110795397 A CN 202110795397A CN 115611748 A CN115611748 A CN 115611748A
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
Abstract
The invention discloses a method for separating 1, 5-pentanediamine. The method comprises the following steps: providing a first solution, wherein the first solution is an alkalizing solution containing 1, 5-pentanediamine and water; extracting 1, 5-pentanediamine in the first solution by using an extracting agent to obtain a mixed solution containing the 1, 5-pentanediamine and the extracting agent; separating 1, 5-pentanediamine from the mixed solution; the extractant is selected from one or two or more of linear chain or branched chain aliphatic alcohol with 2-6 carbon atoms and aromatic alcohol with 7-10 carbon atoms; the temperature of the extraction treatment is 25-50 ℃. The separation method of the 1, 5-pentanediamine has the advantages of high efficiency and simplicity in process, low cost, low pollution, high extraction rate and high selectivity, and is particularly suitable for separating the 1, 5-pentanediamine from biological fermentation liquor, enzyme conversion liquor or treatment liquor of the enzyme conversion liquor.
Description
Technical Field
The invention belongs to the field of compound extraction and purification, relates to a separation method of 1, 5-pentamethylene diamine, and particularly relates to a separation method of 1, 5-pentamethylene diamine in biological fermentation liquid, enzyme conversion liquid or treatment liquid thereof.
Background
1, 5-Pentanediamine, also known as 1, 5-diaminopentane, cadaverine, is an alkane alpha, omega-diamine comprising a straight pentane backbone with amino substitutions at positions 1 and 5. The molecular formula is C 5 H 10 N 2 Melting point 9 deg.C, boiling point 179 deg.C, is readily soluble in water and ethanol, and slightly soluble in diethyl ether. 1, 5-pentanediamine is widely used in agriculture, medicine, physiology, industry and the like. Among them, the most important application value of 1, 5-pentanediamine is embodied in the industrial field. The 1, 5-pentanediamine is an important intermediate in industrial production, can participate in the polymerization of polyamide, polyurethane and the like, and has wide application in the fields of synthetic fibers and synthetic resins. The 1, 5-pentanediamine can replace 1, 6-hexanediamine to participate in the synthesis of polyamide, and the produced nylon 56 has good wear resistance and heat resistance, and meets the requirements of sustainable, green and environment-friendly production. 1, 5-pentanediamine is a natural product and can be produced by a biological fermentation method, so that the petrochemical means can be successfully avoided, and nylon products can be produced by a biological method. Currently, the difficulty in industrially mass-producing 1, 5-pentanediamine using a biological fermentation process is the separation step of 1, 5-pentanediamine. In order to ensure the activity of strains, the concentration of 1, 5-pentanediamine products in mother liquor produced by fermentation is generally not high, and fermentation liquor contains a large amount of inorganic salt, saccharides, protein and other impurities, so that the separation process needs to simultaneously concentrate, enrich, refine and purify, and is a difficult problem in the industrial production step.
From the viewpoint of economic efficiency, in addition to the improvement of fermentation productivity, development of a separation process downstream of the biological production of 1, 5-pentanediamine should be considered. Generally, the downstream separation process accounts for more than 50% of the total production cost. The content of the 1, 5-pentanediamine in the fermentation liquor is about 2-10%, and if the 1, 5-pentanediamine is directly separated from the fermentation liquor by a distillation method, a large amount of water needs to be evaporated, so that the energy consumption is huge. In addition, hydrophilic impurities such as sugar, protein, inorganic salts, etc. in the fermentation liquor can block the tray and corrode the equipment. Currently, the purification methods for preparing 1, 5-pentanediamine by biological methods include an adsorption method and an extraction method. The adsorption method adopts cation exchange resin as adsorbent and utilizes adsorptionThe difference of the adsorption capacity of the adsorbent and the components is that 1, 5-pentanediamine and part of cations are adsorbed, other impurities (such as fermentation metabolites of sugar, pigment and the like, and byproducts of 2,3,4, 5-tetrahydropyridine and the like) do not react with the cationic resin and flow out of the column along with the solution to be separated; adsorbing the 1, 5-pentanediamine solution by cationic resin, eluting the 1, 5-pentanediamine adsorbed by the resin in an alkali washing mode, evaporating, rectifying and concentrating to obtain the 1, 5-pentanediamine. However, the adsorption method has problems of high cost and limited load of adsorption treatment. The extraction method adopts an organic solvent as an extracting agent, the organic solvent is mixed with alkali liquor according to a certain proportion to obtain a saturated organic solvent, and the organic solvent added with alkali is used for extracting the pentamethylene diamine from the fermentation liquor. The extracted extraction phase can be used for purifying the 1, 5-pentanediamine by a simple direct rectification method, or can be used for purifying the extraction phase by a crystallization method and introducing CO into the extraction phase 2 Or SO 2 And (3) reacting the acid gas with 1, 5-pentanediamine to generate carbonate, and carrying out low-temperature reduced pressure distillation, concentration and rectification to obtain the 1, 5-pentanediamine product.
Document 10.1002/jctb.4058 studies on the ability of 4-nonylphenol, 3, 4-bis ((2-ethylhexyl) oxy) phenol, bis (2-ethylhexyl) phosphoric acid, dinonylnaphthalenesulfonic acid, 4-octylbenzaldehyde, and the like to extract diamines. It was found that 4-nonylphenol was almost free from residue in the aqueous phase, and that 1, 5-pentanediamine could be efficiently extracted from the aqueous medium. However, 4-nonylphenol is a substance which is liable to cause environmental pollution, and increases the cost of wastewater treatment.
Reference 10.1039/d0ra08564b uses 1, 5-pentanediamine for CO capture 2 The corresponding carbamate is formed, thereby realizing the crystallization separation of the 1, 5-pentanediamine. After three times of dissolution and crystallization, carbamate with the purity of 99.1 percent is obtained, and the total yield is 57.48 percent. These carbamates consist of mixed crystals of various structural forms, which readily decompose carbon dioxide to give the 1, 5-pentanediamine product. However, this process involves crystallization, requires high equipment and does not give high final yields.
How to select a proper extracting agent to be suitable for the separation of the 1, 5-pentanediamine in a solution system containing the 1, 5-pentanediamine and derived from biological fermentation or enzymatic reaction becomes a technical problem to be solved in the field.
Disclosure of Invention
The invention provides a method for separating 1, 5-pentanediamine, which comprises the following steps:
providing a first solution, wherein the first solution is an alkalizing solution containing 1, 5-pentanediamine and water; extracting 1, 5-pentamethylene diamine in the first solution by an extracting agent to obtain a mixed solution containing the 1, 5-pentamethylene diamine and the extracting agent; separating 1, 5-pentanediamine from the mixed solution;
the extractant is selected from one or two or more of linear chain or branched chain aliphatic alcohol with 2-6 carbon atoms and aromatic alcohol with 7-10 carbon atoms;
the temperature of the extraction treatment is 25-50 ℃, preferably 25-45 ℃.
According to an embodiment of the present invention, the linear or branched aliphatic alcohol having 2 to 6 carbon atoms may be selected from one, two or three of ethanol, n-butanol and isopropanol, and preferably n-butanol.
According to an embodiment of the present invention, the aromatic alcohol having 7 to 10 carbon atoms is preferably benzyl alcohol.
Illustratively, the extractant is selected from benzyl alcohol and/or n-butanol.
According to an embodiment of the present invention, the first solution may be an alkalized solution obtained by alkalizing the second solution;
the second solution is fermentation liquor containing 1, 5-pentanediamine salt produced by a biological method or enzyme conversion liquor containing 1, 5-pentanediamine salt.
Wherein the fermentation liquor containing 1, 5-pentanediamine salt or the enzyme conversion liquor containing 1, 5-pentanediamine salt contains 1, 5-pentanediamine salt and water, and further contains inorganic salt, and/or pigment, and/or protein and other substances optionally. And the fermentation broth or the enzyme conversion broth is a typical polar system. From the research of the prior art, the aromatic substances containing benzene rings have poor extraction and separation effects on polar systems. However, the present inventors have surprisingly found that the extraction of 1, 5-pentanediamine using an alcohol having a benzene ring, such as benzyl alcohol, works well.
According to an embodiment of the present invention, the 1, 5-pentanediamine salt in the second solution is reacted with a first inorganic base to obtain free 1, 5-pentanediamine and a corresponding inorganic salt.
Preferably, the first inorganic base may be selected from one, two or more of the following including, but not limited to: hydroxides, e.g. alkali metal hydroxides (such as NaOH, KOH and mixtures thereof), alkaline earth metal hydroxides (such as Mg (OH) 2 、Ca(OH) 2 And mixtures thereof); oxides, such as alkaline earth metal oxides (e.g., caO, mgO, and mixtures thereof); basic salts such as sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate and mixtures thereof. One, two or more of the first inorganic bases may be added to the second solution containing 1, 5-pentanediamine/1, 5-pentanediamine salt substantially simultaneously or at different times. When at least two first inorganic bases are added, the different bases may be added as one or more mixtures, or separately.
For example, in certain embodiments, the first inorganic base mixture can be a mixture of one, two, or more strong bases and one, two, or more weak bases. Examples of the first inorganic base mixture include, but are not limited to, a mixture of sodium phosphate and sodium hydroxide, or a mixture of sodium carbonate, sodium hydroxide, and potassium hydroxide.
For another example, in certain embodiments, the first inorganic base mixture can be a mixture of one, two, or more strong bases. Examples of the first inorganic base mixture include, but are not limited to, a mixture of sodium hydroxide and potassium hydroxide.
Preferably, at least 85wt% or more of the first inorganic base is an alkaline earth metal hydroxide and/or an alkaline earth metal oxide. Preferably, the alkaline earth metal hydroxide and alkaline earth metal oxide have the selections as indicated above.
Taking 1, 5-pentamethylene diamine salt as 1, 5-pentamethylene diamine hydrochloride and NaOH as an example, the reaction principle is as follows: [ NH ] 3 (CH 2 ) 5 NH 3 ]Cl 2 +2NaOH→NH 2 (CH 2 ) 5 NH 2 +2NaCl+2H 2 O。
According to an embodiment of the invention, the pH of the first solution is 7 or more, for example 10-14, further may be 11-13, exemplary 10.5, 11, 11.03, 11.5, 12, 12.5, 12.65, 13, 13.23, 13.5 or a point value between any two of the aforementioned numerical ranges.
On one hand, the first inorganic base can be added to form insoluble salt (such as calcium sulfate) through reaction to precipitate and promote the alkali dissolution, and the 1, 5-pentanediamine is converted into the 1, 5-pentanediamine after salinization, so that the reaction efficiency is improved; on the other hand, impurities (partial pigments and proteins) with acid radical groups, such as acid radical anions, in the system can be removed simultaneously.
Further, a second inorganic base can be optionally added or not added into the first solution after the alkalization treatment to adjust the pH value of the solution; the second inorganic base has the choice as shown above for the first inorganic base.
In one embodiment, the second inorganic base may be the same as the first inorganic base. When the second inorganic base is the same as the first inorganic base, then the base may be added to the second solution only once. In this case, the addition of the base can simultaneously perform the above-described two functions and the function of adjusting the pH of the first solution.
According to an embodiment of the invention, the pH of the second solution is lower than the pH of the first solution.
According to an embodiment of the present invention, the concentration of 1, 5-pentanediamine in the first solution may be 20wt% or less, still further may be 10wt% or less, 7wt% or less, or 6.5wt% or less, preferably 3 to 6.5wt%; by way of example, the concentration of 1, 5-pentanediamine in the first solution is 1.13wt%, 2wt%, 5wt%, 6.14wt%, 9wt%, 9.05wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, or a point between any two of the foregoing ranges of values.
Preferably, when the concentration of 1, 5-pentanediamine in the first solution is below 7wt%, further below 6.5wt%, it is advantageous to improve the extraction efficiency.
According to an embodiment of the present invention, the mass ratio of the extractant to the first solution is greater than or equal to 0.5, further greater than or equal to 1, for example, (0.5-20): 1, further (1-15): 1, further (1-10): 1, further (1-7): 1, exemplary 1.
According to embodiments of the invention, the temperature of the extraction process may be 25-35 ℃, illustratively 30 ℃, 32 ℃, 34 ℃, 35 ℃, 36 ℃, 38 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ or a value between any two of the foregoing. When the extraction temperature is in the lower temperature condition, the extraction efficiency of the 1, 5-pentanediamine is improved, and the energy consumption is greatly saved.
According to an embodiment of the present invention, the mixed solution is stirred at the time of the extraction treatment; preferably, the stirring time is not particularly limited, and may be 10 to 60 minutes, for example, 20 to 40 minutes.
According to the embodiment of the invention, the mixed solution is stirred and then is kept stand for layering to obtain an extract phase and a raffinate phase; the time for which the mixed solution is allowed to stand is not particularly limited, and may be 1 to 30 minutes, for example, 5 to 15 minutes.
According to an embodiment of the invention, the extraction process comprises n stages of extraction processes, n ≧ 1 and an integer, such as n ≧ 2 and an integer, and further such as n ≧ 3 and an integer.
According to an embodiment of the invention, the mass ratio of extractant and aqueous phase of the second extraction (n = 2) is the same as that of the first extraction (n = 1); preferably, the extraction temperature of the secondary extraction (n = 2) is the same as the primary extraction (n = 1).
According to an embodiment of the invention, the mass ratio of extractant and aqueous phase of the third extraction (n = 3) is the same as that of the first extraction (n = 1); preferably, the extraction temperature of the third stage extraction (n = 3) is the same as the first stage extraction (n = 1).
The standing mixed solution has good phase separation, does not generate the phenomenon of interference extraction such as emulsification, floccule and the like, and is beneficial to the subsequent treatments such as distillation, evaporation, rectification and the like.
According to an embodiment of the invention, the separation method further comprises: and distilling and/or evaporating and/or rectifying the extract phase to obtain the 1, 5-pentanediamine product.
According to an embodiment of the invention, the operating conditions of the rectification comprise: the number of the tower plates is 3-10, and/or the temperature of the reboiler is 80-200 ℃, and/or the reflux ratio is 0.05-0.5.
According to an embodiment of the invention, the purity of the 1, 5-pentanediamine product is above 99wt%, such as above 99.5wt%, above 99.7 wt%.
The invention also provides application of the separation method in preparation of high-purity 1, 5-pentanediamine products. Preferably, the high purity 1, 5-pentanediamine product means that the purity of the 1, 5-pentanediamine product is above 99wt%, such as above 99.5wt%, above 99.7 wt%.
Preferably, the separation method is used to obtain a high-purity 1, 5-pentanediamine product from the alkalized liquor of the fermentation broth containing 1, 5-pentanediamine salt (i.e., the first solution) or the alkalized liquor of the enzyme conversion broth containing 1, 5-pentanediamine salt (i.e., the first solution).
Preferably, the fermentation broth containing 1, 5-pentanediamine and the enzymatic conversion broth containing 1, 5-pentanediamine both have the meanings as indicated above.
The invention has the advantages of
The separation method of the 1, 5-pentanediamine has the advantages of high efficiency and simplicity in process, low cost, low pollution, high extraction rate and high selectivity, and is particularly suitable for separating the 1, 5-pentanediamine from biological fermentation liquid, enzyme conversion liquid or treatment liquid thereof. The used extractants, namely benzyl alcohol and n-butyl alcohol, are cheap and easy to obtain, and a good extraction effect can be obtained.
The 1, 5-pentanediamine obtained by the method has high purity and meets the requirements of downstream polymer production.
Detailed Description
In the method for separating 1, 5-pentanediamine, the enzymatic conversion solution of 1, 5-pentanediamine may be prepared by a Lysine Decarboxylation (LDCN) reaction. For example, it is prepared by the following process: converting a solution of lysine and/or a lysine salt (e.g., a fermentation broth of lysine and/or a lysine salt) into 1, 5-pentanediamine/1, 5-pentanediamine salt in the presence of Lysine Decarboxylase (LDC) to obtain the enzymatic conversion broth of 1, 5-pentanediamine.
Preferably, the lysine salt is a salt formed from lysine and one, two or more inorganic and/or organic acids. For example, the lysine salt is one, two or more lysine/inorganic acid salts. Examples of the lysine/inorganic acid salt include, but are not limited to, lysine hydrochloride, lysine sulfate, or any combination of the two.
Wherein the lysine or lysine salt can be prepared by fermentation preparation methods known in the art or can be purchased commercially. The lysine fermentation liquor obtained by the fermentation preparation method can be used for the enzymatic preparation of the 1, 5-pentanediamine. For example, the lysine fermentation broth comprises an aqueous solution of a lysine salt, preferably an aqueous solution comprising lysine sulfate.
For example, the lysine fermentation broth may be further treated before being used in an enzymatic conversion broth for enzymatically preparing 1, 5-pentanediamine.
For example, the further treatment may be by means of, for example, filtration, centrifugation or membrane filtration to remove impurities (such as microorganisms) from the lysine fermentation broth and to obtain an aqueous lysine salt solution.
As another example, the further treatment may be carried out by decolorizing the lysine fermentation broth with activated carbon, filtering to obtain an aqueous lysine salt solution, preferably an aqueous lysine sulfate solution.
According to an embodiment of the present invention, the fermentative preparation method may use microorganisms known in the art to be suitable for lysine fermentation. Examples of such microorganisms include, but are not limited to, wild-type strains, mutagenized strains, and/or recombinant strains. For example, strains include, but are not limited to, strains of Corynebacterium (Corynebacterium) such as Corynebacterium glutamicum (c.glutamicum), corynebacterium beijing (c.pekinense) or Corynebacterium crenatum (c.crenatum), brevibacterium (brevibacterium) strains such as brevibacterium lactofermentum (b.lactofermentum) and brevibacterium flavum (b.flavum).
According to an embodiment of the invention, the lysine fermentation process is carried out in a culture medium. The medium may be a medium known in the art to be suitable for lysine fermentation. For example, the medium may comprise a carbon source and a non-carbon nutrient source.
According to an embodiment of the present invention, the Lysine Decarboxylase (LDC) is an enzyme that can convert lysine into 1, 5-pentanediamine. The LDCs can be prepared by suitable fermentation methods known in the art, and the LDC fermentation broth thus obtained can be directly used for the enzymatic preparation of 1, 5-pentanediamine. For example, the LDC fermentation broth may be further processed prior to use in the enzymatic preparation of 1, 5-pentanediamine. For example, the LDC fermentation broth may be centrifuged, filtered and/or otherwise treated, optionally further purified, to provide a treated or purified LDC composition.
According to an embodiment of the invention, in said Lysine Decarboxylation (LDCN) reaction, the substrate is lysine/lysine salt as described above and the enzyme is said LDC. Wherein the reaction temperature of the LDCN may be about 20 ℃ to about 60 ℃. The reaction pH of the LDCN is a pH suitable for enzymatic conversion and depends on the LDC used in the LDCN reaction. For example, the pH of the LDCN reaction can be from about 5 to about 8.
In one embodiment, an acid is added to the LDCN reaction to maintain the pH of the reaction in a suitable range. In one embodiment, acid is added to the lysine/lysine salt solution prior to the addition of LDC to adjust the pH to a suitable pH, and then LDC is added to facilitate the conversion of lysine to the 1, 5-pentanediamine salt. In another embodiment, the acid is added after mixing the LDC with the lysine/lysine salt solution. Wherein the acid is selected from the group consisting of, but not limited to, inorganic acids (e.g., HCl, sulfuric acid, and any combination thereof) and acid gases (e.g., CO) 2 ) One, two or more.
In another embodiment, a buffer is used in the LDCN reaction to maintain the pH in a suitable range to optimize conversion. Wherein, the buffer solution can be selected from common buffer solutions including but not limited to those used in the effective range of LDC, such as buffer solution prepared by 7 parts of 0.2mol/L acetic acid and 3 parts of 0.2mol/L sodium acetate solution.
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The partition coefficients (. Beta.1 and. Beta.2) and selectivity (. Beta.2) were used to evaluate the extraction performance of the extractant, which is defined as follows:
in the formula, w 1 And w 2 The mass fractions of 1, 5-pentanediamine and water are respectively, and the superscript E and R are respectively an extract phase and a residual liquid phase.
pH value test method: measured using a pH meter.
In the following examples, the extraction rate of total 1, 5-pentanediamine = (mass sum of pentanediamine in extraction phase of three extractions/mass of pentanediamine in 1, 5-pentanediamine alkalization liquid) × 100%.
Preparative example 1 preparation of Lysine Decarboxylase (LDC)
(1) Seed and fermentation medium:
seed medium (g/L): tryptone 10, beef extract 5, naCl 5 and corn steep liquor 5 (pH 7.2). Wild type honeycomb Hafnia species expressing LDC (Hafniaalveii 1.1009, available from CGMCC, http:// www.cgmcc.net/index.php/controls/show/id/460) were grown on a slant, transferred into a Erlenmeyer flask containing 30mL of seed medium, and cultured at 35 ℃ for 15 hours with shaking at 170R/min.
(2) Culture conditions
Fermentation medium (g/L): glucose 18.2, yeast extract 20, corn steep liquor 36.6, mgSO 4 0.3、KH 2 PO 4 0.1 percent of NaCl, 3 percent of L-lysine, 5 percent of vitamin B 6 1 and a pH of 6.5 to 7.0.
10% of the seeds were transferred to 250mL flasks containing 100mL fermentation medium. During the growth phase of the cells, the temperature was controlled at 35 ℃ and the cells were cultured for 13 hours on a rotary shaker shaking at 220 r/min; then statically culturing for 5 hours to obtain LDC fermentation liquor. And directly using the obtained LDC fermentation liquor for LDC catalytic conversion of lysine or centrifuging to obtain wet cells.
Preparatory example 2 preparation of 1, 5-Pentanediamine salt solution by enzymatic conversion of lysine sulfate solution
100L of the lysine decarboxylase solution (LDC fermentation broth) obtained in preparation example 1 was charged into a 250L reactor, and acetic acid and sodium acetate were added to the reaction to give final molar concentrations of 0.21mol/L, respectively. Commercially available lysine sulfate was added to the reaction to control the lysine concentration to 3g/L, and Tween-80 (total 0.15 kg) was added to the reaction. The reaction was stirred at 35 ℃. The reaction was complete in about 5 hours with a molar conversion of lysine of about 86.5%. The enzymatic conversion solution was concentrated to give a solution of 1, 5-pentanediamine salt (about 5 wt%).
Example 1
800g of the 1, 5-pentanediamine salt solution obtained in the preliminary example 2 is taken, then alkalization treatment is carried out by calcium oxide, more than 95% of 1, 5-pentanediamine in the 1, 5-pentanediamine salt solution is dissociated, insoluble substances are removed by filtration, and concentration is carried out, so as to obtain 1, 5-pentanediamine alkalized solution, wherein the mass percentage of the 1, 5-pentanediamine in the alkalized solution is 6.14%, and the pH value is 12.65.
500g of n-butyl alcohol serving as an extractant and 500g of alkalized solution of 1, 5-pentanediamine are taken for extraction treatment.
Primary extraction: placing the n-butyl alcohol and the 1, 5-pentanediamine alkalized solution into a 5L reactor, stirring for 30min at 30 ℃ and 600rpm, standing for 10min, and completely layering the two phases to obtain uniform and good phase separation. Separating extract phase and raffinate phase. The partition coefficient beta 1 is 1.68, the selectivity is 5.90, and the single-stage extraction rate is 71.80%.
Secondary-tertiary extraction: the raffinate phase (water phase) separated after the first-stage extraction is used as a raw material, n-butyl alcohol is used as an extracting agent, and the mass ratio of the n-butyl alcohol to the raffinate phase in the second-stage extraction process is the same as that of the first-stage reaction. And performing secondary extraction according to the steps and parameters of the primary extraction. Similarly, the three-stage extraction was continued. The extraction rate of the total 1, 5-pentanediamine after the three-stage extraction is 99.51 percent.
The obtained total extract phase is used for rectification, the number of tower plates is 5, the temperature of a reboiler is 150-200 ℃, the reflux ratio is 0.1, and the purity of 1, 5-pentanediamine at the bottom of the tower reaches 99.6%.
Example 2
800g of the 1, 5-pentanediamine salt solution obtained in the preliminary example 2 is taken, then alkalized by calcium oxide, more than 95% of 1, 5-pentanediamine in the 1, 5-pentanediamine salt solution is dissociated, insoluble substances are removed by filtration, and concentrated to obtain 1, 5-pentanediamine alkalized solution, wherein the mass percentage of the 1, 5-pentanediamine in the alkalized solution is 6.16%, and the pH value is 12.67.
500g of benzyl alcohol as an extractant and 500g of 1, 5-pentanediamine alkalized liquid are taken for extraction treatment.
Primary extraction: placing benzyl alcohol and 1, 5-pentanediamine alkalization liquid into a 5L reactor, stirring for 30min at 30 ℃ and 600rpm, standing for 10min, and completely layering the two phases to obtain uniform and good phase separation. Separating extract phase and raffinate phase. The partition coefficient beta 1 is 0.868, the selectivity is 8.71, and the single-stage extraction rate is 85.08 percent.
Secondary-tertiary extraction: the raffinate phase (water phase) obtained by separation after the first-stage extraction is used as a raw material, n-butanol is used as an extracting agent, and the mass ratio of the n-butanol to the raffinate phase in the second-stage extraction process is the same as that of the first-stage reaction. And performing secondary extraction according to the steps and parameters of the primary extraction. Similarly, the three-stage extraction was continued. The total extraction rate of 1, 5-pentanediamine after three-stage extraction is 99.78 percent.
The obtained total extract phase is used for rectification, the number of tower plates is 5, the temperature of a reboiler is 150-200 ℃, the reflux ratio is 0.1, and the purity of 1, 5-pentanediamine at the bottom of the tower reaches 99.5%.
Example 3
800g of the 1, 5-pentanediamine salt solution obtained in the preliminary example 2 is taken, then alkalized by calcium oxide, more than 95% of 1, 5-pentanediamine in the 1, 5-pentanediamine salt solution is dissociated, insoluble substances are removed by filtration, and concentrated to obtain 1, 5-pentanediamine alkalized solution, wherein the mass percentage of the 1, 5-pentanediamine in the alkalized solution is 6.14%, and the pH value is 12.63.
Extracting 500g of n-butyl alcohol serving as an extracting agent and 500g of alkalized solution of 1, 5-pentanediamine.
Placing n-butanol and 1, 5-pentanediamine alkalization liquid in a 5L reactor, stirring at 40 deg.C and 600rpm for 30min, standing for 10min, and separating two phases completely to obtain uniform and good phase separation. Separating extract phase and raffinate phase. The partition coefficient beta 1 is 1.43, the selectivity is 5.12, and the extraction rate is 66.21%.
The extraction phase is used for rectification, the number of tower plates is 5, the temperature of a reboiler is 150-200 ℃, the reflux ratio is 0.1, and the purity of the 1, 5-pentanediamine at the tower bottom reaches 99.2%.
The temperature in the extraction process is changed from 30 ℃ to 40 ℃, and the extraction effect is reduced.
Example 4
800g of the 1, 5-pentanediamine salt solution obtained in the preliminary example 2 is taken, then alkalization treatment is carried out by calcium oxide, more than 95% of 1, 5-pentanediamine in the 1, 5-pentanediamine salt solution is dissociated, insoluble substances are removed by filtration, and concentration is carried out, so as to obtain 1, 5-pentanediamine alkalized solution, wherein the mass percentage of the 1, 5-pentanediamine in the alkalized solution is 6.15%, and the pH value is 12.65.
500g of n-butyl alcohol serving as an extractant and 500g of alkalized solution of 1, 5-pentanediamine are taken for extraction treatment.
Placing n-butanol and 1, 5-pentanediamine alkalization liquid in a 5L reactor, stirring at 50 deg.C and 600rpm for 30min, standing for 10min, and separating two phases completely to obtain uniform and good phase separation. Separating extract phase and raffinate phase. The partition coefficient β 1 was 1.33, the selectivity 4.88 and the extraction 63.70%.
The extraction phase is used for rectification, the number of tower plates is 5, the temperature of a reboiler is 150-200 ℃, the reflux ratio is 0.1, and the purity of 1, 5-pentanediamine at the tower bottom reaches 99.1%.
The temperature in the extraction process is changed from 30 ℃ to 50 ℃, and the extraction effect is reduced.
Example 5
800g of the 1, 5-pentanediamine salt solution obtained in the preliminary example 2 is taken, then alkalized by calcium oxide, more than 95% of 1, 5-pentanediamine in the 1, 5-pentanediamine salt solution is dissociated, insoluble substances are removed by filtration, and concentrated to obtain 1, 5-pentanediamine alkalized solution, wherein the mass percentage of the 1, 5-pentanediamine in the alkalized solution is 6.16%, and the pH value is 12.66.
Extracting 600g of n-butyl alcohol serving as an extracting agent and 500g of alkalized solution of 1, 5-pentanediamine.
Placing the n-butyl alcohol and the 1, 5-pentanediamine alkalized solution into a 5L reactor, stirring for 30min at 30 ℃ and 600rpm, standing for 10min, and completely layering the two phases to obtain uniform and good phase separation. Separating extract phase and raffinate phase. The partition coefficient beta 1 was 1.88, the selectivity was 5.94 and the extraction was 73.96%.
The extraction phase is used for rectification, the number of tower plates is 5, the temperature of a reboiler is 150-200 ℃, the reflux ratio is 0.1, and the purity of the 1, 5-pentanediamine at the tower bottom reaches 99.3%.
The dosage of the extracting agent is increased from 1 time of the raw materials to 1.2 times of the raw materials, and the extraction effect is improved.
Example 6
800g of the 1, 5-pentanediamine salt solution obtained in the preliminary example 2 is taken, then alkalized by calcium oxide, more than 95% of 1, 5-pentanediamine in the 1, 5-pentanediamine salt solution is dissociated, insoluble substances are removed by filtration, and concentrated to obtain 1, 5-pentanediamine alkalized solution, wherein the mass percentage of the 1, 5-pentanediamine in the alkalized solution is 6.14%, and the pH value is 12.64.
700g of n-butyl alcohol serving as an extractant and 500g of alkalized solution of 1, 5-pentanediamine are taken for extraction treatment.
Placing the n-butyl alcohol and the 1, 5-pentanediamine alkalized solution into a 5L reactor, stirring for 30min at 30 ℃ and 600rpm, standing for 10min, and completely layering the two phases to obtain uniform and good phase separation. Separating extract phase and raffinate phase. The partition coefficient beta 1 is 1.96, the selectivity is 5.97 and the single-stage extraction rate is 82.42 percent.
The extraction phase is used for rectification, the number of tower plates is 5, the temperature of a reboiler is 150-200 ℃, the reflux ratio is 0.1, and the purity of the 1, 5-pentanediamine at the tower bottom reaches 99.4%.
The dosage of the extracting agent is increased from 1 time of the raw material to 1.4 times of the raw material, and the extraction effect is improved.
Example 7
Taking 800g of the 1, 5-pentanediamine salt solution obtained in the preparation example 2, then using a calcium hydroxide solution to carry out alkalization treatment, so that more than 95% of 1, 5-pentanediamine in the 1, 5-pentanediamine salt solution is dissociated, filtering to remove insoluble substances, concentrating, wherein the mass percentage of the 1, 5-pentanediamine in the alkalized solution is 4.95%, and obtaining 1, 5-pentanediamine alkalized solution with the pH value of 12.35.
700g of n-butyl alcohol serving as an extractant and 500g of alkalized solution of 1, 5-pentanediamine are taken for extraction treatment.
Placing n-butanol and 1, 5-pentanediamine alkalization liquid in a 5L reactor, stirring at 30 deg.C and 600rpm for 30min, standing for 10min, and separating two phases completely to obtain uniform and good phase separation. Separating extract phase and raffinate phase. The partition coefficient beta 1 is 1.69, the selectivity is 5.92, and the single-stage extraction rate is 77.65%.
The extraction phase is used for rectification, the number of tower plates is 5, the temperature of a reboiler is 150-200 ℃, the reflux ratio is 0.1, and the purity of the 1, 5-pentanediamine at the tower bottom reaches 99.4%.
The content of 1, 5-pentanediamine in the raw material is reduced, and the extraction effect is improved.
Example 8
800g of the 1, 5-pentanediamine salt solution obtained in the preliminary example 2 is taken, then alkalization treatment is carried out by calcium oxide, more than 95 percent of 1, 5-pentanediamine in the 1, 5-pentanediamine salt solution is dissociated, insoluble substances are removed by filtration, and concentration is carried out, so as to obtain 1, 5-pentanediamine alkalized solution, wherein the mass percentage of the 1, 5-pentanediamine in the alkalized solution is 7.18 percent, and the pH value is 12.92.
700g of n-butyl alcohol serving as an extractant and 500g of alkalized solution of 1, 5-pentanediamine are taken for extraction treatment.
Placing n-butanol and 1, 5-pentanediamine alkalization liquid in a 5L reactor, stirring at 30 deg.C and 600rpm for 30min, standing for 10min, and separating two phases completely to obtain uniform and good phase separation. Separating extract phase and raffinate phase. The partition coefficient β 1 was 1.54, the selectivity 5.33 and the single-stage extraction 67.93%.
The extraction phase is used for rectification, the number of tower plates is 5, the temperature of a reboiler is 150-200 ℃, the reflux ratio is 0.1, and the purity of 1, 5-pentanediamine at the tower bottom reaches 99.3%.
The content of 1, 5-pentanediamine in the raw material is increased, and the extraction effect is reduced.
Comparative example 1
800g of the 1, 5-pentanediamine salt solution obtained in the preliminary example 2 is taken, then alkalized by calcium oxide, more than 95% of 1, 5-pentanediamine in the 1, 5-pentanediamine salt solution is dissociated, insoluble substances are removed by filtration, and concentrated to obtain 1, 5-pentanediamine alkalized solution, wherein the mass percentage of the 1, 5-pentanediamine in the alkalized solution is 6.17%, and the pH value is 12.66.
500g of extractant benzene and 500g of 1, 5-pentanediamine alkalization liquid are taken, the mass percentage content of the 1, 5-pentanediamine in the alkalization liquid is 6.14%, and the pH =12.65.
Placing benzene and 1, 5-pentanediamine alkalization liquid into a 5L reactor, stirring for 30min at 30 ℃ and 600rpm, standing for 10min, and completely layering two phases to obtain uniform and good phase separation. Separating extract phase and raffinate phase. The partition coefficient β 1 was 0.005 and the extraction rate was 0.49%. Benzene-p-pentanediamine has little extraction effect.
Comparative example 2
800g of the 1, 5-pentanediamine salt solution obtained in the preliminary example 2 is taken, then alkalized by calcium oxide, so that more than 95% of 1, 5-pentanediamine in the 1, 5-pentanediamine salt solution is dissociated, insoluble substances are removed by filtration, and concentrated to obtain 1, 5-pentanediamine alkalized solution, wherein the mass percentage of the 1, 5-pentanediamine in the alkalized solution is 6.16%, and the pH value is 12.67.
Taking 500g of extractant p-xylene and 500g of 1, 5-pentanediamine alkalization liquid, wherein the mass percentage of 1, 5-pentanediamine in the alkalization liquid is 6.14 percent, and the pH =12.65.
Placing the p-xylene and 1, 5-pentanediamine alkalized liquid into a 5L reactor, stirring for 30min at the temperature of 30 ℃ and the rotating speed of 600rpm, continuing standing for 10min, and after two phases are completely layered, uniformly and well separating the phases. Separating extract phase and raffinate phase. The partition coefficient beta 1 was 0.01 and the extraction rate was 0.60%. The p-xylene and p-pentamethylene diamine have little extraction effect.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for separating 1, 5-pentanediamine, which is characterized by comprising the following steps:
providing a first solution, wherein the first solution is an alkalizing solution containing 1, 5-pentanediamine and water; extracting 1, 5-pentamethylene diamine in the first solution by an extracting agent to obtain a mixed solution containing the 1, 5-pentamethylene diamine and the extracting agent; separating 1, 5-pentanediamine from the mixed solution;
the extractant is selected from one or two or more of linear chain or branched chain aliphatic alcohol with 2-6 carbon atoms and aromatic alcohol with 7-10 carbon atoms;
the temperature of the extraction treatment is 25-50 ℃, preferably 25-45 ℃.
2. The separation method according to claim 1, wherein the aliphatic alcohol having 2 to 6 carbon atoms and being linear or branched is selected from one, two or three of ethanol, n-butanol and isopropanol, preferably n-butanol;
preferably, the aromatic alcohol with 7 to 10 carbon atoms is benzyl alcohol;
preferably, the extractant is selected from benzyl alcohol and/or n-butanol.
3. The separation process according to claim 1 or 2, characterized in that the first solution is an alkalinized liquor obtained by alkalinization of the second solution;
the second solution is fermentation liquor containing 1, 5-pentamethylene diamine salt produced by a biological method or enzyme conversion liquor containing 1, 5-pentamethylene diamine salt;
preferably, the fermentation liquid containing 1, 5-pentamethylene diamine salt or the enzyme conversion liquid containing 1, 5-pentamethylene diamine salt contains 1, 5-pentamethylene diamine salt and water, and further optionally contains inorganic salt, pigment, protein and the like.
4. A separation process according to claim 3, characterized in that the 1, 5-pentanediamine salt in the second solution is reacted with a first inorganic base capable of obtaining free 1, 5-pentanediamine and the corresponding inorganic salt;
preferably, the first inorganic base is selected from one, two or more of the following, including but not limited to: hydroxides, oxides, basic salts;
preferably, the hydroxide is selected from alkali metal hydroxides and/or alkaline earth metal hydroxides; preferably, the oxide is an alkaline earth metal oxide; preferably, the alkaline salt is selected from the group consisting of sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, and mixtures thereof;
preferably, the pH of the first solution is 7 or more, preferably 10 to 14.
5. The separation method according to claim 3 or 4, wherein at least 85wt% or more of the first inorganic base is an alkaline earth metal hydroxide and/or an alkaline earth metal oxide; preferably, the alkaline earth metal hydroxide and the alkaline earth metal oxide have the selection as indicated in claim 4.
6. A separation process according to any one of claims 1 to 5, characterized in that the concentration of 1, 5-pentanediamine in the first solution is 20wt% or less, preferably 10wt% or less, 7wt% or less or 6.5wt% or less.
7. The separation process according to any one of claims 1 to 6, characterized in that the mass ratio of the extractant to the first solution is greater than or equal to 0.5, preferably greater than or equal to 1, and preferably also (0.5-20): 1;
preferably, the temperature of the extraction treatment is 25-35 ℃;
preferably, the mixed solution is stirred during the extraction treatment;
preferably, the mixed solution is stirred and then is kept stand, and layering is carried out to obtain an extract phase and a raffinate phase;
preferably, the extraction treatment comprises n stages of extraction treatment, wherein n is more than or equal to 1 and is an integer;
preferably, the mass ratio of extractant and aqueous phase of the second extraction (n = 2) is the same as that of the first extraction (n = 1); preferably, the extraction temperature of the secondary extraction (n = 2) is the same as the primary extraction (n = 1).
Preferably, the mass ratio of extractant and aqueous phase of the third extraction (n = 3) is the same as that of the first extraction (n = 1); preferably, the extraction temperature of the third stage extraction (n = 3) is the same as the first stage extraction (n = 1).
8. The separation method according to any one of claims 1 to 7, further comprising: and distilling and/or evaporating and/or rectifying the extract phase to obtain the 1, 5-pentanediamine product.
9. The separation process of claim 8, wherein the operating conditions of the rectification comprise: the number of tower plates is 3-10, and/or the temperature of the reboiler is 80-200 ℃, and/or the reflux ratio is 0.05-0.5; preferably, the purity of the 1, 5-pentanediamine product is above 99 wt%.
10. Use of the separation method according to any one of claims 1 to 9 for the preparation of a high purity 1, 5-pentanediamine product;
preferably, the high-purity 1, 5-pentanediamine product means that the purity of the 1, 5-pentanediamine product is more than 99 wt%;
preferably, the separation method is used for obtaining a high-purity 1, 5-pentanediamine product from an alkalized solution of a fermentation broth containing 1, 5-pentanediamine salt or an alkalized solution of an enzyme conversion broth containing 1, 5-pentanediamine salt.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101981202A (en) * | 2008-01-23 | 2011-02-23 | 巴斯夫欧洲公司 | Method for fermentatively producing 1,5-diaminopentane |
| US20130079486A1 (en) * | 2010-03-01 | 2013-03-28 | Tomonori Hidesaki | Method for producing 1,5-pentamethylenediamine, 1,5-pentamethylenediamine, 1,5-pentamethylene diisocyanate, method for producing 1,5-pentamethylene diisocyanate, polyisocyanate composition, and polyurethane resin |
| WO2013151139A1 (en) * | 2012-04-05 | 2013-10-10 | 三井化学株式会社 | Method for producing 1,5-pentamethylenediamine, method for producing 1,5-pentamethylenediisocyanate, method for producing polyisocyanate composition, and method for storing catalyst cell |
| US20130338330A1 (en) * | 2011-03-09 | 2013-12-19 | Mitsui Chemicals ,Inc. | Pentamethylenediisocyanate, method for producing pentamethylenediisocyanate, polyisocyanate composition, polyurethane resin, and polyurea resin |
| US20170121273A1 (en) * | 2013-01-28 | 2017-05-04 | Cathay R&D Center Co., Ltd. | Preparation of cadaverine |
| CN109704978A (en) * | 2018-12-25 | 2019-05-03 | 天津大学 | A kind of purification process of pentanediamine |
-
2021
- 2021-07-14 CN CN202110795397.8A patent/CN115611748A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101981202A (en) * | 2008-01-23 | 2011-02-23 | 巴斯夫欧洲公司 | Method for fermentatively producing 1,5-diaminopentane |
| US20130079486A1 (en) * | 2010-03-01 | 2013-03-28 | Tomonori Hidesaki | Method for producing 1,5-pentamethylenediamine, 1,5-pentamethylenediamine, 1,5-pentamethylene diisocyanate, method for producing 1,5-pentamethylene diisocyanate, polyisocyanate composition, and polyurethane resin |
| US20130338330A1 (en) * | 2011-03-09 | 2013-12-19 | Mitsui Chemicals ,Inc. | Pentamethylenediisocyanate, method for producing pentamethylenediisocyanate, polyisocyanate composition, polyurethane resin, and polyurea resin |
| WO2013151139A1 (en) * | 2012-04-05 | 2013-10-10 | 三井化学株式会社 | Method for producing 1,5-pentamethylenediamine, method for producing 1,5-pentamethylenediisocyanate, method for producing polyisocyanate composition, and method for storing catalyst cell |
| US20170121273A1 (en) * | 2013-01-28 | 2017-05-04 | Cathay R&D Center Co., Ltd. | Preparation of cadaverine |
| CN109704978A (en) * | 2018-12-25 | 2019-05-03 | 天津大学 | A kind of purification process of pentanediamine |
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