CN105712888B - A kind of preparation method of long-chain nylon salt - Google Patents
A kind of preparation method of long-chain nylon salt Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of long-chain nylon salt.This method includes：Long-chain biatomic acid terminate zymotic fluid it is preprocessed, acidifying, organic solvent purification, then substep into organic phase add binary amine aqueous solution, then it is concentrated, crystallization and dry, obtain long-chain nylon product salt.The preparation process that this method purifies organic solvent long-chain biatomic acid and long-chain nylon salt is coupled, eliminate tediously long the step of preparing polymer grade long-chain biatomic acid product, and resulting long-chain nylon salt disclosure satisfy that polymer grade requirement, and the yield of nylon salt can be improved.
Description
Technical field
The present invention relates to a kind of manufacture method of long-chain nylon salt, more particularly to a kind of long-chain obtained with biological fermentation process
Binary acid is the method that raw material prepares long-chain nylon salt with diamine reaction.
Background technology
Nylon resin scientific name polyamide, there is excellent mechanical mechanics property, be the most widely used engineering in countries in the world
Plastics.Wherein long carbon chain nylon is compared with the nylon of short chain, in flexibility, lower temperature resistance, impact, water resistance, dimensionally stable
Property and processability etc. have significant advantage.With the primary raw material long-chain biatomic acid from petro-jelly fermentation production long carbon chain nylon
Technological industrialization, long carbon chain nylon resin are developed into countries in the world nylon research and development, the emphasis of production.
Nylon is produced by the use of diamine and binary acid as raw material, is the method for industry generally use.First, diamine is made
Nylon salt is made with binary acid reaction, afterwards, resulting nylon salt is obtained into steady quality by processes such as melt polycondensations
High molecular weight nylon product.
At present, the production method of long-chain nylon salt has two kinds.One kind is alcohols solvent crystallisation, both at a certain temperature will
The ethanol solution of diamine is added dropwise in the ethanol solution of equimolar long-chain biatomic acid, is allowed to after neutralizing completely through separating, doing
It is dry to obtain solid nylon salt.Another kind is aqua-solution method, both using water as solvent, is gathered with polymer grade long-chain biatomic acid with equimolar
Close level diamine and neutralization reaction is carried out in water, obtain nylon saline solution, concentrated dehydration, crystallization, dry, you can consolidate
Body nylon salt.
CN00110713.5 is proposed with alcohols solvent dicarboxylic acids crude product of the extracting containing thalline and is obtained colourless length
Chain binary acid organic solution, and diamine solution is prepared with identical alcohols solvent, it is organic that the solution is added into long-chain biatomic acid
Solution, generation nylon salt is neutralized, through crystallisation by cooling, washing and drying, obtain nylon product salt.Subject matter existing for this method
It is：（1）Alcohols solvent is not suitable for refining long-chain biatomic acid, is particularly unsuitable for producing the polymer grade long-chain binary of nylon salt
Acid product.In this method in order to obtain the long-chain biatomic acid of polymer grade, under the conditions of 50~130 DEG C, contained with alcohols extracting
The thick binary acid of thalline, under the conditions of this, alcohol inevitably generates long-chain biatomic acid ester with long-chain biatomic acid, on the one hand reduces
The yield of long-chain biatomic acid product, on the other hand when producing long-chain nylon salt, dibasic acid ester is remained in nylon salt, is being synthesized
During polyamide, the presence of ester serves the effect of polymerization inhibitor, and the molecular weight for limiting polyamide increases, and have impact on the power of polyamide
Learn performance.（2）During synthetic nylon salt, control is not measured to crucial Con trolling index pH, to nylon salt certified products
Production cause larger fluctuation, have impact on the mechanical property of polyamide.（3）This area has all been substituted using the aqueous solution at present
Alcoholic solvent produces nylon salt, and compared to aqueous process, the safety in production requirement of acquisition nylon salt is produced under alcoholic solvent atmosphere more
Height, production equipment need sealing, anti-riot, investment and operating cost height.（4）The crystallization of nylon salt is also needed to substantial amounts of fresh molten
Liquid is washed, and adds the amount that nylon salt dissolves in a solvent, reduces the yield of nylon salt.（5）Nylon containing impurity
Salt recrystallisation solvent mother liquor is, it is necessary to carry out refined recovery so that technological process becomes tediously long, add production equipment and operation into
This.
CN03142127.X proposes the method with water as solvent production long-chain nylon salt, will under the conditions of 60~95 DEG C
Binary amine aqueous solution is gradually added in the long-chain biatomic acid aqueous solution, and reaction mass pH reaches 7.0~7.2, and insulation 0.5~3.0 is small
When, 20~40 DEG C are cooled to, then by centrifugation and dry acquisition long carbon chain nylon product salt.The aqueous solution is the method use to enter
The synthesis of row nylon salt, the shortcomings of changing the safety risks that alcohols solvent method is brought.But the problem of this method is present is：Will
First obtain polymer grade long-chain biatomic acid product, then again with diamine and production polymer grade nylon salt, from polymer grade length
Chain binary acid produces the production for arriving nylon salt again, and technological process is relatively complicated tediously long, and production run cost is higher, have impact on product
Competitiveness.
Nylon salt is the raw material monomer of synthesizing polyamides, it is necessary to is polymer grade, it requires its base stock long-chain two
First acid must reach polymer grade specification requirement.And zymotic fluid is a collection microbial cells, culture medium, alkane, water and other generations
Thank to the heterogeneous system that product coexists, composition is complicated, and medium is sticky, very tired using the separation method Hydrolysis kinetics binary acid of routine
Difficulty, product purity is difficult to reach polymer grade requirement, and yield is low.At present, the general method of long-chain biatomic acid production field is to use
Acetate solvate carries out the product of refined production polymer grade, and then reacts production polymer grade nylon salt with polymer grade diamine, although
The nylon salt that this method obtains meets the requirement of polyamide synthesis, but the problems such as technological process is long, the production cycle is long be present.
It is well known that the fermentation broth contents of Production of Long-chain Dicarboxylic Acids by Fermentation Methods are extremely complex, contain substantial amounts of albumen, residual
Alkane, the accessory substance etc. of fermentation medium and other bacterial metabolisms, therefore the long-chain biatomic acid and chemical method that fermentation method obtains
Obtain long-chain or short chain diacid is compared, the product acquisition of the binary acid of polymer grade is increasingly difficult, and flow is increasingly complex, therefore obtains
The nylon salt for obtaining polymer grade is also increasingly difficult.
The content of the invention
In order to overcome deficiency of the prior art, the invention provides a kind of preparation method of long-chain nylon salt.This method
The production of long-chain biatomic acid product and the production of nylon salt are coupled, eliminate operating procedure, the long-chain nylon of production
Salt can reach polymer grade requirement.
The preparation method of the long-chain nylon salt of the present invention, including：
I, long-chain biatomic acid termination zymotic fluid is pre-processed to remove solid content and liquid wax；
II, the obtained zymotic fluids of step I are acidified, obtain the mixed liquor of the solid containing long-chain biatomic acid；
III, by the mixed liquors of the obtained solids containing long-chain biatomic acid of step II, either the mixed liquor is filtered obtains
Filter cake, mixed with organic solvent, the alkali for accounting for long-chain biatomic acid weight 0.05% ~ 5.0% is added into above-mentioned system, after being well mixed
Carry out organic phase and aqueous phase separation；
After organic phase washed with water after IV, separation, adsorbent, filtering and removing solid content are added；
V, under conditions of stirring, binary amine aqueous solution is slowly added in the organic phase obtained to step IV, and slowly drop
Temperature is to 10 DEG C ~ 30 DEG C, and binary amine aqueous solution feeding quantity accounts for 40wt% ~ 75wt% of total binary amine aqueous solution feeding quantity, and charging terminates
Stop stirring, stand, preferably stand 30min ~ 60min, then separated organic phase and aqueous phase；
Remainder binary amine aqueous solution is added in aqueous phase obtained by VI, step V, system temperature is 50 DEG C ~ 80 DEG C, system
PH value control 6.0 ~ 7.5, then concentrated, crystallization and dry, obtain long-chain nylon product salt.
It is microorganism metabolite obtained from liquid wax fermentation that zymotic fluid is terminated in the inventive method, described in step I,
The long-chain biatomic acid general molecular formula wherein contained is CnH2n-2O4, wherein n is 10-18, and organic acid can be single long-chain binary
Acid or hybrid long chain dicarboxylic acid.After terminating zymotic fluid heat inactivation, the impurity such as filtering and removing thalline, mistake can be carried out
Filter can use conventional method and the equipment such as membrane filtration.
In the inventive method, the acidifying described in step II can use conventional method to carry out.The pH value of the acidifying is 2.0
~4.0.Acid used in the above-mentioned acidifying of the present invention can be the H of any concentration2SO4、HNO3, HCl or H3PO4.Temperature is controlled during acidifying
Spend for 80 DEG C ~ 100 DEG C.
Organic solvent used in step III is the ethers for being insoluble in water, preferably isopropyl ether, butyl ether, isobutyl ether, amyl ether, different
The one or more of amyl ether, hexyl ether etc..The addition of organic solvent is 1 with long-chain biatomic acid weight ratio:1~15:1, be preferably
2:1~7:1.
Alkali described in step III is sodium acid carbonate, in sodium carbonate, sodium hydroxide, saleratus, potassium carbonate, potassium hydroxide
One or more, preferably sodium hydroxide or potassium hydroxide.
After point going aqueous phase in the inventive method, in step IV, deionized water washing organic phase can be added once or once
More than, and isolate aqueous phase.
In the inventive method, the adsorbent in step IV is the one or more in activated carbon, atlapulgite etc., is preferably
Activated carbon, more preferably Powdered Activated Carbon, average pore diameter 10-6~10-4Mm, addition are long-chain biatomic acid weight
0.01wt% ~ 2.0wt%, adsorption time are 30min ~ 60min.
In the inventive method, the diamine added in step V is with H2N ( CH2）mNH2General molecular formula, wherein m
=5 ~ 16, including but not limited to pentanediamine, hexamethylene diamine, octamethylenediamine, nonamethylene diamine, decamethylene diamine, hendecane diamines, dodecamethylene diamine,
One or more in tridecane diamine, tetradecane diamines, pentadecane diamines and hexadecane diamines.
In the inventive method, binary amine aqueous solution used, the concentration of wherein diamine are in step V and step VI
20wt%~50wt%.In the present invention, total addition of diamine is 1.0 ~ 1.2 times of long-chain biatomic acid, preferably 1.0 ~ 1.1 times,
In mol.
In the inventive method, step V under agitation, part binary amine aqueous solution is slowly added into organic phase, and
Slow cooling is to 10 DEG C ~ 30 DEG C, the purpose is to make long-chain biatomic acid constantly react generation nylon salt, while makes part long-chain two
First acid crystallizes precipitations in a manner of the crystal grain of suitable size, is settled down in the aqueous phase that nylon salt has been dissolved in lower floor, stands, organic phase with
Aqueous phase is sufficiently separated.The organic solvent of recovery need not be refined and recycled simultaneously, effectively reduce being refined into for solvent
This, improves production efficiency.
In the inventive method, in step VI, system temperature is 50 DEG C ~ 80 DEG C, and is stirred, and it is 6.0 ~ 7.5 to control pH, preferably
For 6.8 ~ 7.2, it is set fully to react generation long-chain nylon salt.
In the inventive method, the aqueous solution progress that technology long-chain nylon salt general in industry may be selected in step VI is dense
Contracting, crystallize and dry, to obtain long-chain nylon product salt.
The preparation process that the inventive method purifies organic solvent long-chain biatomic acid and long-chain nylon salt is coupled, that is, utilizes
The pilot process product of ether solvent purification long-chain biatomic acid directly prepares long-chain nylon salt with diamine reactant aqueous solution, saves
The tediously long crystallization for preparing polymer grade long-chain biatomic acid product, filtering, drying and solvent recovery step, reduce equipment throwing
Money, has saved energy consumption, has reduced production cost.And resulting long-chain nylon salt disclosure satisfy that polymer grade requirement, with
After preparing long-chain biatomic acid, then react generation nylon salt method compare, yield can improve 2% or so, this to lifted industrial products
The market competitiveness be particularly important.The solvent phase that the refined preparation process with nylon salt of long-chain biatomic acid uses simultaneously
Together, and recovered solvent need not be refined and recycled, the equipment for eliminating solvent reclamation, shorten the operation cycle, be improved
Production efficiency.
The inventive method, while high-purity nylon product salt is obtained, also simple with technical process, energy consumption, material
Low advantage.
Embodiment
The preparation method of the long-chain nylon salt of the present invention is further illustrated below by embodiment.In the present invention, wt% is matter
Measure fraction.
In the inventive method, liquid wax, thalline, the culture medium not utilized, metabolite are contained in long-chain biatomic acid zymotic fluid
And microorganism secretion thing etc., especially wherein containing impurity such as a large amount of protein, pigments.Long-chain biatomic acid terminates zymotic fluid and entered
Row pretreatment can use the acquisition of this area usual way, for example by after termination zymotic fluid heating, stand, divide the liquid for going to upper strata
Wax, then cooling and filtration sterilization；Or enter micro-filtration or ultrafiltration apparatus after terminating zymotic fluid heating, remove thalline and liquid wax
Deng.
Embodiment 1
200mL is taken to be fermented to obtain C by Candida tropicalis12H22O4Zymotic fluid, concentration are 160g/L zymotic fluid.Heating
To 80 DEG C, through ceramic micro filter membrane filtration, the liquid wax for removing thalline and remnants obtains filtrate.Add H in filtrate2SO4Adjust pH value to
3.0,2h is stood, is obtained containing C12H22O4The solution of solid, and it is filtrated to get C12H22O4Filter cake.
Obtained C12H22O4Filter cake and isopropyl ether（Isopropyl ether and C12H22O4Weight ratio is 7：1）After mixing, add
1wt%NaOH aqueous solution 32g, and 85 DEG C are heated to, static 60min, divide sub-cloud aqueous phase；Again 30mL is added into solvent phase to go
Ion water washing organic phase, divides aqueous phase again；Then to 0.3g activated carbons insulation decolouring 30min is added in organic phase, then
It is filtered to remove the C that activated carbon is dissolved12H22O4Isopropyl ether phase.
Stream plus 52mL 20wt% the hexamethylene diamine aqueous solution into organic phase, and slow cooling, to 20 DEG C, charging stops after terminating
Only stir, stand 60min, separate the recycled solvent on upper strata.By lower floor's heated aqueous to 60 DEG C, and add under agitation
The 30mL 20wt% hexamethylene diamine aqueous solution, the pH for adjusting solution is 7.0, makes fully reaction generation long-chain nylon salt.Will dissolving
The aqueous solution of long-chain nylon salt is concentrated, crystallized and dried, to obtain long-chain nylon product salt.
Experimental result is shown in Table 1.
Embodiment 2
200mL is taken to be fermented to obtain C by Candida tropicalis12H22O4Zymotic fluid, concentration are 160g/L zymotic fluid.Heating
To 80 DEG C, through ceramic micro filter membrane filtration, the liquid wax for removing thalline and remnants obtains filtrate.Add H in filtrate2SO4Adjust pH value to
3.0,2h is stood, is obtained containing C12H22O4The solution of solid, and it is filtrated to get C12H22O4Filter cake.
Obtained C12H22O4Filter cake mixes and n-butyl ether（N-butyl ether and C12H22O4Weight ratio is 6：1）Mixing, to mixed liquor
10wt%KOH aqueous solution 20g are added, 135 DEG C is mixed and heated to, static 60min, divides sub-cloud aqueous phase；Again into solvent phase
50mL deionized waters washing organic phase is added, divides aqueous phase again；The insulation of 0.2g activated carbons is added into organic phase to decolourize
30min, activated carbon is then filtered to remove, the C dissolved12H22O4N-butyl ether phase.
Stream plus 30mL 30wt% the hexamethylene diamine aqueous solution into organic phase, and slow cooling, to 20 DEG C, charging stops after terminating
Only stir, stand 60min, separate the recycled solvent of upper strata phase.By lower floor's heated aqueous to 80 DEG C, and add under agitation
The 25mL 30wt% hexamethylene diamine aqueous solution, the pH for adjusting solution is 7.2, makes fully reaction generation long-chain nylon salt.Will dissolving
The aqueous solution of long-chain nylon salt is concentrated, crystallized and dried, to obtain long-chain nylon product salt.
Experimental result is shown in Table 1.
Embodiment 3
200mL is taken to be fermented to obtain C by Candida tropicalis13H24O4Zymotic fluid, concentration are 154g/L zymotic fluid.Heating
To 70 DEG C, through ceramic micro filter membrane filtration, the liquid wax for removing thalline and remnants obtains filtrate.Add H in filtrate2SO4Adjust pH value to
2.4, and 95 DEG C are heated to, obtain containing C13H24O4The mixed liquor of solid, and it is filtrated to get C13H24O4Filter cake.
Obtained C13H24O4Filter cake and n-butyl ether（N-butyl ether and C13H22O4Weight ratio is 2：1）Mixing, is added thereto
15wt%Na2CO3Aqueous solution 50g, 100 DEG C are mixed and heated to, static 60min, divides sub-cloud aqueous phase；Added again into solvent phase
60mL deionized waters wash organic phase, divide aqueous phase again；0.15g activated carbons insulation decolouring 30min is added to organic, then
Activated carbon is filtered to remove, the C dissolved13H24O4N-butyl ether phase.
Stream plus 32mL 40wt% the decamethylene diamine aqueous solution into organic phase, and slow cooling, to 30 DEG C, charging stops after terminating
Only stir, stand 45min, separate the recycled solvent of upper strata phase.By lower floor's heated aqueous to 70 DEG C, and add under agitation
The 24mL 40wt% decamethylene diamine aqueous solution, the pH for adjusting solution is 6.8, makes fully reaction generation long-chain nylon salt.Will dissolving
The aqueous solution of long-chain nylon salt is concentrated, crystallized and dried, to obtain long-chain nylon product salt.
Experimental result is shown in Table 1.
Embodiment 4
Take the C that 200mL concentration is 145g/l14H26O4Zymotic fluid, 70 DEG C are heated to, through ceramic micro filter membrane filtration, remove bacterium
Body and remnants liquid wax obtain filtrate.Add H in filtrate2SO4PH value is adjusted to 2.4, and is heated to 95 DEG C, obtains containing C14H26O4
The aqueous solution of solid.
Obtained C14H26O4The aqueous solution and isopropyl ether（Isopropyl ether and C14H22O4Weight ratio is 6：1）Mixing, add thereto
Enter 5wt%NaHCO3Aqueous solution 58g, 65 DEG C are mixed and heated to, static 60min, divides sub-cloud aqueous phase；Add again into solvent phase
Enter 30mL deionized waters washing organic phase, divide aqueous phase again；0.20g activated carbons insulation decolouring 30min is added into organic phase,
Activated carbon is then filtered to remove, the C dissolved12H22O4Isopropyl ether phase.
Stream plus 30mL 20wt% the pentanediamine aqueous solution into organic phase, and slow cooling, to 10 DEG C, charging stops after terminating
Only stir, stand 50min, separate the recycled solvent of upper strata phase.By lower floor's heated aqueous to 80 DEG C, and add under agitation
The 30mL 20wt% pentanediamine aqueous solution, the pH for adjusting solution is 7.0, makes fully reaction generation long-chain nylon salt.Will dissolving
The aqueous solution of long-chain nylon salt is concentrated, crystallized and dried, to obtain long-chain nylon product salt.
Experimental result is shown in Table 1.
Comparative example 1
200mL is taken to be fermented to obtain C by Candida tropicalis12H22O4Zymotic fluid, concentration are 160g/L zymotic fluid.Heating
To 80 DEG C, through ceramic micro filter membrane filtration, the liquid wax for removing thalline and remnants obtains filtrate.Add H in filtrate2SO4Adjust pH value to
3.0,2h is stood, is obtained containing C12H22O4The solution of solid, and it is filtrated to get C12H22O4Filter cake.
Obtained C12H22O4Filter cake and isopropyl ether（Isopropyl ether and C12H22O4Weight ratio is 7：1）After mixing, add
1wt%NaOH aqueous solution 32g, and 85 DEG C are heated to, static 60min, divide sub-cloud aqueous phase；Again 30mL is added into solvent phase to go
Ion water washing organic phase, divides aqueous phase again；Then to 0.3g activated carbons insulation decolouring 30min is added in organic phase, then
It is filtered to remove the C that activated carbon is dissolved12H22O4Isopropyl ether phase.
Stream plus 52mL 20wt% the hexamethylene diamine aqueous solution into organic phase, while insulation prevents binary acid crystal at 85 DEG C
Separate out, and be sufficiently stirred the reaction generation nylon salt of the hexamethylene diamine in the binary acid and the aqueous solution for making isopropyl ether, then stop stirring
60min is stood, isopropyl ether phase is layered with nylon saline solution.The aqueous solution progress that lower floor has been dissolved to long-chain nylon salt is dense
Contracting, crystallize and dry, to obtain long-chain nylon product salt.
Experimental result is shown in Table 1.
Comparative example 2
200mL is taken to be fermented to obtain C by Candida tropicalis12H22O4Zymotic fluid, concentration are 160g/L zymotic fluid.Heating
To 80 DEG C, through ceramic micro filter membrane filtration, the liquid wax for removing thalline and remnants obtains filtrate.Add H in filtrate2SO4Adjust pH value to
3.0,2h is stood, is obtained containing C12H22O4The solution of solid, and it is filtrated to get C12H22O4Filter cake.
Obtained C12H22O4Filter cake and isopropyl ether（Isopropyl ether and C12H22O4Weight ratio is 7：1）After mixing, add
1wt%NaOH aqueous solution 32g, and 85 DEG C are heated to, static 60min, divide sub-cloud aqueous phase；Again 30mL is added into solvent phase to go
Ion water washing organic phase, divides aqueous phase again；Then to 0.3g activated carbons insulation decolouring 30min is added in organic phase, then
It is filtered to remove the C that activated carbon is dissolved12H22O4Isopropyl ether phase.
Isopropyl ether after decolouring is mutually cooled to 10 DEG C, obtains containing crystallization C12H22O4Isopropyl ether mixed liquor.Will mixing
Liquid is centrifugally separating to obtain the wet crystal containing 10wt% isopropyl ethers, is placed in vacuum desiccator and is heated to 95 DEG C, and returns simultaneously
The isopropyl ether solvents of volatilization are received, after solvent evaporation is clean, obtain qualified C12H22O4Product.
Pure hexamethylene diamine is made into the about 20wt% aqueous solution with deionized water, added in reactor, under 70 DEG C of stirrings, is delayed
The slow C for adding equivalent12H22O4Product, control ph is 7.0, you can obtains long-chain nylon saline solution.By long-chain nylon salt
The aqueous solution concentrated, crystallized and dried, to obtain long-chain nylon product salt.
Experimental result is shown in Table 1.
Experimental result prepared by the nylon salt of table 1
From table 1, compared with comparative example method, the purity of nylon salt is high obtained by the inventive method, and total nitrogen content is low, Buddhist nun
Imperial salt high income.
Claims (12)
1. a kind of preparation method of long-chain nylon salt, including：
I, long-chain biatomic acid termination zymotic fluid is pre-processed to remove solid content and liquid wax；
II, the obtained zymotic fluids of step I are acidified, obtain the mixed liquor of the solid containing long-chain biatomic acid；
III, by the mixed liquor of the obtained solids containing long-chain biatomic acid of step II either the filtered obtained filter cake of the mixed liquor,
Mixed with organic solvent, the alkali for accounting for long-chain biatomic acid weight 0.05% ~ 5.0% is added into above-mentioned system, is carried out after well mixed
Organic phase and aqueous phase separation；
After organic phase washed with water after IV, separation, adsorbent, filtering and removing solid content are added；
V, under conditions of stirring, binary amine aqueous solution is slowly added in the organic phase obtained to step IV, and slow cooling is extremely
10 DEG C ~ 30 DEG C, binary amine aqueous solution feeding quantity accounts for 40wt% ~ 75wt% of total binary amine aqueous solution feeding quantity, and charging terminates to stop
Stirring, stand, then separated organic phase and aqueous phase；
Remainder binary amine aqueous solution is added in aqueous phase obtained by VI, step V, and system temperature is risen to 50 DEG C ~ 80 DEG C, body
The pH value control of system then concentrated, crystallization and is dried 6.0 ~ 7.5, obtains long-chain nylon product salt.
2. in accordance with the method for claim 1, it is characterised in that：Long-chain biatomic acid general molecular formula described in step I is CnH2n- 2O4, wherein n is 10-18, organic acid either single long-chain biatomic acid, or hybrid long chain dicarboxylic acid.
3. in accordance with the method for claim 1, it is characterised in that：Acidulated condition described in step II：PH value is 2.0 ~ 4.0,
Temperature is 80 DEG C ~ 100 DEG C, and acid used is H2SO4、HNO3, HCl and H3PO4In one or more.
4. in accordance with the method for claim 1, it is characterised in that：Organic solvent used in step III is ether solvent, is selected from
One or more in isopropyl ether, butyl ether, amyl ether, hexyl ether, addition and the long-chain biatomic acid weight ratio of organic solvent are 1:1~
15:1。
5. in accordance with the method for claim 1, it is characterised in that：The addition and long-chain of organic solvent used in step III
Binary acid weight ratio is 2:1~7:1.
6. in accordance with the method for claim 1, it is characterised in that：Alkali described in step III is sodium acid carbonate, sodium carbonate, hydrogen
One or more in sodium oxide molybdena, saleratus, potassium carbonate, potassium hydroxide.
7. in accordance with the method for claim 1, it is characterised in that：Adsorbent in step IV is Powdered Activated Carbon, average hole
A diameter of 10-6~10-4Mm, addition be long-chain biatomic acid weight 0.01wt% ~ 2.0wt%, adsorption time be 30min ~
60min。
8. in accordance with the method for claim 1, it is characterised in that：The diamine added in step V is with H2N ( CH2）mNH2General molecular formula, wherein m=5 ~ 16.
9. according to the method described in claim 1 or 8, it is characterised in that：The diamine added in step V include pentanediamine, oneself
Diamines, octamethylenediamine, nonamethylene diamine, decamethylene diamine, hendecane diamines, dodecamethylene diamine, tridecane diamine, tetradecane diamines, pentadecane
One or more in diamines and hexadecane diamines.
10. according to the method described in claim 1 or 8, it is characterised in that：Diamine used is water-soluble in step V and step VI
Liquid, its concentration are 20wt% ~ 50wt%.
11. in accordance with the method for claim 1, it is characterised in that：Total addition of diamine be long-chain biatomic acid 1.0 ~
1.2 times, in mol.
12. in accordance with the method for claim 1, it is characterised in that：Step VI by the heated aqueous that step V is obtained to 50 DEG C ~
80 DEG C, and it is 6.8 ~ 7.2 to control pH.
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