CN108017535A - A kind of method that long-chain biatomic acid is extracted from zymotic fluid - Google Patents
A kind of method that long-chain biatomic acid is extracted from zymotic fluid Download PDFInfo
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- CN108017535A CN108017535A CN201610933532.XA CN201610933532A CN108017535A CN 108017535 A CN108017535 A CN 108017535A CN 201610933532 A CN201610933532 A CN 201610933532A CN 108017535 A CN108017535 A CN 108017535A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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Abstract
The invention discloses a kind of method that long-chain biatomic acid is extracted from zymotic fluid.This method includes：The pretreated termination acidified crystallization of zymotic fluid, adds water to be mixed with beating, adds pyridine compounds and their, membrane filtration, sodium hydroxide solution is added into filtrate, and the crystallization being obtained by filtration is dissolved with water Hybrid Heating, through adsorbing, filtering, it is acidified with acid, crystallizes into filtrate, obtains long-chain biatomic acid product.The long-chain biatomic acid extracted using the method for the present invention has the advantages that purity is high, color and luster is white, protein content is low and product is loosely easily dry.
Description
Technical field
The present invention relates to a kind of C10~C18The method of binary acid extraction, particularly from C10~C18Carried in normal alkane fermentation liquor
The method for taking long-chain biatomic acid.
Background technology
Signified long-chain biatomic acid general molecular formula of the invention is CnH2n-2O4, wherein n is 10-18, is that microorganism utilizes alkane
Metabolite obtained from fermentation, is present in zymotic fluid by long-chain biatomic acid in the form of double salt.
Long-chain biatomic acid is the metabolite obtained from microbial fermentation n-alkane.Its zymotic fluid is one complicated
Heterogeneous system, wherein containing unreacted n-alkane, microbial cell and fragment, the culture medium not utilized and metabolite with
And secretion of microorganism etc., especially wherein contain the impurity such as a large amount of protein, pigment, influence the purity and appearance matter of product
Amount.
Long carbochain biatomic acid is a kind of fine chemical product for having important and extensive industrial use, is the advanced perfume (or spice) of synthesis
The important source material of material, high performance engineering plastics, high-grade hot melt adhesive etc..Production of Long-chain Dicarboxylic Acids by Fermentation Methods is strong to react specificity
With reaction condition it is gentle the advantages that, gradually instead of traditional chemical synthesis, receive domestic and international most attention, be new material
The development of industry opens wide space.
At present, the main process of extraction long-chain biatomic acid general in industry, including：By zymotic fluid heat inactivation, enter
Micro-filtration or ultrafiltration apparatus, removing mycoprotein etc., the filtrate clarified, adds sulfuric acid to be acidified to pH value 2.0~4.0, and is stirring
Lower heating to be mixed, obtains long-chain biatomic acid crystallization aqueous solution, the aqueous solution that cools down simultaneously filters, and the filter cake is washed with water to neutrality, and
With air blow drying, long-chain biatomic acid filter cake is obtained.
During long-chain biatomic acid crude acid is extracted, the albumen such as insoluble thalline can by micro-filtration or ultrafiltration in zymotic fluid
To remove, and soluble protein is entered in filtrate together with long-chain biatomic acid salt.It is changed into long-chain biatomic acid salt is acidified
In long-chain biatomic acid crystallization process, the soluble protein that isoelectric precipitation or denaturation separate out in acid condition is deposited the two of precipitation
First acid embedding, can not also remove even if by way of filtering, washing, and cause protein in the long-chain biatomic acid of extraction acquisition to contain
Amount is higher.By the way that the long-chain biatomic acid color and luster of the method acquisition is yellow, viscosity is big, easily lumps, protein content height, is not suitable under being used as
Swim the raw material of production.
CN102191187A discloses a kind of preparation method of long-chain biatomic acid, extraction long-chain biatomic acid used in it
Method：It is demulsified after fermentation, is separated off thalline and residual hydrocarbon, clear liquid activated carbon decolorizing with filter membrane, destainer is used
H2SO4Or HCl acidizing crystals, press filtration, washing, drying, drying obtain product long-chain biatomic acid.This method is using in industry
The method of the general extraction long-chain biatomic acid crude product of manufacturing enterprise, this method obtain product nitrogen content and are much larger than 30ppm.It is although clear
Liquid is decolourized with activated carbon, but still cannot remove most of soluble protein, and soluble protein separates out and quilt during acidizing crystal
It is embedded in long-chain biatomic acid, the presence of high molecular weight protein makes that the long-chain biatomic acid crystalli-zation cake viscosity of press filtration is big, crystalline particle
Gap is minimum or blocked, causes washing difficult, impurity can not wash removal wherein the pigment embedded, ash grade, and make product matter
Measure poor, limit application.
CN102476990A discloses a kind of method of extracting and refining long-chain biatomic acid crude product, comprises the following steps：1)
Filtrate after long-chain biatomic acid is fermented is acidified with acid to obtain mixed liquor with 40~100 DEG C of extractant Hybrid Heating, and it is 2 to adjust pH value
~6, extractant is selected from C4~C10One or more in monohydric alcohol；2) Liquid liquid Separation is carried out after mixed liquor being sufficiently mixed standing
Obtain extraction phase；3) it is dry after desolventizing by extraction phase crystallisation by cooling, the long-chain biatomic acid product after being purified.This method
Using the Methods For Purification long-chain biatomic acid of extraction, it there is extracting yield and product purity be low etc..Particularly this method exists
Using monohydric alcohol extraction long-chain biatomic acid under acid condition, it may occur that esterification, and the long-chain biatomic acid ester and two generated
First acid co-dissolve will necessarily be adhered to plane of crystal in binary acid crystallisation by cooling or be embedded in crystalline substance in monohydric alcohol extraction phase
Within body so that dibasic acid ester is necessarily included in final products, reduces product purity.
CN1611478A is disclosed one kind and is saltoutd using mono-salt from one or more C10-C18In the zymotic fluid of n-alkane
The method for extracting simultaneously refining long-chain biatomic acid, comprises the following steps：I, the heated demulsification of zymotic fluid, separation and recovery alkane are terminated
Afterwards, then it is acidified, crystallizes, long-chain biatomic acid filter cake is obtained by filtration；II, the binary acid wet cake obtained by step I, which alkalizes, is made pH
For 6.0~7.0 binary acid mono-salt solution, while salting-out agents are added, and heating makes its all dissolve, and is cooled to after warm
Simultaneously long-chain biatomic acid mono-salt crystal cake is obtained by filtration in room temperature；III, the long-chain biatomic acid mono-salt crystal cake obtained by step II
Add alkali soluble solution to generate the double salting liquids of long-chain biatomic acid completely, and filter out solid content；IV, make the acidification of filtrate obtained by step III
The double salt of long-chain biatomic acid are completely converted into long-chain biatomic acid, then crystallized, be filtered, washed and dried step and obtain long-chain binary
Acid product.This method is that salting-out agents are added into system, can so make protein solubility reduce and with long-chain biatomic acid salt from
Separated out in solution, and again without the effective ways of deproteination matter in subsequent step, so that protein can not effectively be taken off
Remove, so as to have impact on the purity of product, total nitrogen content is high.
The content of the invention
For the deficiency of long-chain biatomic acid extraction process disclosed in the prior art, the present invention provides one kind to utilize Aqueous phase
From C10~C18The method that long-chain biatomic acid is extracted in normal alkane fermentation liquor, compared with the prior art, is carried using the method for the present invention
The long-chain biatomic acid obtained has the advantages that color and luster is white, protein content is low and product is loosely easily dry.
The method provided by the invention that long-chain biatomic acid is extracted from zymotic fluid, including：
I, it is preprocessed to terminate zymotic fluid, obtains and contains long-chain biatomic acid salt filtrate；
II, by long-chain biatomic acid salt acidification of filtrate, binary acid is fully crystallized precipitation, long-chain biatomic acid filter cake be obtained by filtration, washes
Wash；
Long-chain biatomic acid filter cake and water that step II is obtained, be mixed with beating by III；
Pyridine compounds and their is added in IV, the mixed serum obtained to step III；
V, the mixture for obtaining step IV carries out membrane filtration, obtains filtrate；
VI, add sodium hydroxide solution into the filtrate for obtaining step V, to form long-chain biatomic acid sodium salt, then crystallization analysis
Go out, long-chain biatomic acid sodium salt crystal is obtained after filtered, washing；
VII, dissolve the obtained crystallizations of step VI and water Hybrid Heating, adds adsorbent and adsorbs and filter, the acid adding into filtrate
Acidifying, makes binary acid be fully crystallized precipitation, filtered, washing, drying, obtain long-chain biatomic acid.
It is microorganism metabolite obtained from liquid wax fermentation that zymotic fluid is terminated in the method for the present invention, described in step I,
The long-chain biatomic acid general molecular formula wherein contained is CnH2n-2O4, wherein n is 10-18, can be a kind of single long-chain biatomic acid,
It can also be hybrid long chain dicarboxylic acid.
In the method for the present invention, 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。
In the method for the present invention, when long-chain biatomic acid filter cake is mixed with beating with water in step III, water consumption is long-chain biatomic acid
50wt% ~ 500wt% of filter cake weight, is preferably 100wt% ~ 300wt%.
In the method for the present invention, the water described in step III is deionized water, and electrical conductivity is less than 0.1 μ s.
In the method for the present invention, the pyridine compounds and their that is added in step IV is pyridine, 2- picolines, 3- picolines,
One or more in 4- picolines, 2,3 dimethyl pyridine, 2,4- lutidines and 2,6- lutidines.
In the method for the present invention, the amount of the addition pyridine compounds and their described in step IV makes the pH value of slurries be 5.0 ~ 6.4, pyrrole
The reaction time of pyridine class compound and long-chain biatomic acid is 30 ~ 120min.
In the method for the present invention, the membrane filter system described in step V is micro-filtration or ultrafiltration, is preferably ultrafiltration, the hole of ultrafiltration membrane
Footpath is that molecular cut off is 1000 ~ 30000, is preferably 1000 ~ 5000.
In the method for the present invention, sodium hydroxide solution, the quality of sodium hydroxide solution are added in the filtrate obtained to step VI
Concentration is 10% ~ 40%, and the pH value of regulation system is 6.4 ~ 7.0, regenerates pyridine, while obtained long-chain biatomic acid mono-sodium salt knot
Crystalline substance, filtering obtain long-chain biatomic acid mono-salt filter cake, and pyridine compounds and their enters in filtrate.Long-chain two is washed with low temperature deionized water
First acid mono-salt filter cake, and the long-chain biatomic acid mono-salt filter cake after washing is dissolved in fresh deionized water, solution temperature 85
DEG C ~ 95 DEG C, while adsorbent is added, the filtrate containing long-chain biatomic acid sodium salt is obtained by filtration while hot.Used in the present invention is above-mentioned
Low temperature deionized water temperature is 5 DEG C ~ 15 DEG C.The above-mentioned adsorbent used of the present invention contains for activated carbon, diatomite, atlapulgite etc.
There are the one or more in the particulate matter in absorption duct.The dosage of the adsorbent is step（1）The 1% of termination zymotic fluid quality ~
5%。
In the method for the present invention, the acidifying described in step VII can use conventional method.The pH value of the acidifying for 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, preferably H2SO4。
The method of the present invention is water-soluble with pyridine compounds reaction generation by will be acidified the long-chain biatomic acid filter cake of filtering acquisition
The long-chain biatomic acid pyridiniujm of property, then separate out soluble protein under suitable slightly acidic condition, precipitation is made by ultrafiltration
Albumen is efficiently separated with water miscible long-chain biatomic acid pyridiniujm, is then alkalized by sodium hydroxide, mono-salt sodium salt knot
Brilliant, filtering and washing and etc. albumen is more effectively removed, while regenerate pyridine, the final acidified qualification that obtains
Long-chain biatomic acid product.
The present invention by long-chain biatomic acid is acidified, generation binary acid pyridiniujm, ultra-filtration filters, mono-salt crystallization filtering and acid
The separating steps such as change, make long-chain biatomic acid be separated with impurity more thorough, compared with traditional extraction technique, product color is color
Damp white, dried long-chain biatomic acid product is loose, product purity ＞ 99.5%, and total nitrogen content ＜ 30ppm, can meet downstream
The requirement of application.
Embodiment
The method that long-chain biatomic acid is extracted from zymotic fluid is further illustrated below by embodiment.In the present invention, wt% is
Mass fraction.
In the method for the present invention, liquid wax, thalline, the culture medium not utilized, metabolite and microorganism are contained in zymotic fluid
Secretion etc., especially wherein containing impurity such as a large amount of protein, pigments.It is usually to remove that step I, which terminates fermentation liquor pretreatment,
The impurity such as liquid wax and thalline, can use the method for micro-filtration and/or ultrafiltration be pre-processed, can also micro-filtration and/or ultrafiltration it
It is preceding first to carry out heat inactivation processing, for example following at least one scheme can be used：
（1）Zymotic fluid will be terminated and be heated to 75 DEG C ~ 90 DEG C, into micro-filtration or ultrafiltration apparatus, the impurity such as thalline and liquid wax is removed, obtain
To long-chain biatomic acid salt filtrate；
（2）Zymotic fluid will be terminated and heat 85 DEG C ~ 100 DEG C, it is 8~10 to adjust pH value, stands, then divides upper strata remaining liquid
Wax, the long-chain biatomic acid salting liquid of lower floor's mycetome are cooled to 30 DEG C ~ 90 DEG C, by micro-filtration and/or ultrafiltration apparatus, are filtered to remove
The impurity such as thalline obtain long-chain biatomic acid salt filtrate.
Comparative example 1
200mL is taken to be fermented to obtain C by Candida tropicalis12H22O4Zymotic fluid, concentration are the zymotic fluid of 160g/L, heat 95
DEG C, and it is 10 to adjust pH value, stands about 2h, then divides upper strata liquid wax.The long-chain biatomic acid salting liquid cooling of lower floor's mycetome
To 80 DEG C, filtrate is obtained by membrane filtration.Use H2SO4The pH value of filtrate is adjusted to 3.0, obtains C12H22O4Crystallize aqueous solution, mistake
Filter, is washed with water to neutrality, obtains wet cake, i.e. C12H22O4Long-chain biatomic acid.
Embodiment 1
The filter cake that comparative example 1 obtains and 90mL deionized waters are mixed with beating, add pyridine thereto, it is 5.4 to adjust pH value, is stirred
60min is reacted under the conditions of mixing.Then membrane filtration is carried out by the ultrafiltration apparatus that molecular cut off is 5000, obtains filtrate.To filter
It is 6.5 that sodium hydroxide is added in liquid and adjusts pH value, to form long-chain biatomic acid mono-sodium salt, and crystallized, filtering, with 10 DEG C of low temperature
Deionized water is washed, and obtains the crystallization of long-chain biatomic acid mono-sodium salt.This crystallization is mixed and heated to 95 with fresh deionized water
DEG C, while add 2g activated carbons and adsorbed, then filter, H is added into filtrate2SO4The pH value of filtrate is adjusted to 3.0, is obtained
C12H22O4Aqueous solution, filtering are crystallized, and is washed with water to neutrality, obtains wet cake, then C is obtained through dry12H22O4Product.
Obtained experimental data is shown in Table 1.
Embodiment 2
200mL is taken to be fermented to obtain C by Candida tropicalis13H24O4Zymotic fluid, concentration are the zymotic fluid of 154g/L, heat 85
DEG C, filtrate is obtained through membrane filtration, uses H2SO4The pH value of filtrate is adjusted to 3.0, obtains C13H24O4Aqueous solution is crystallized, filtering, uses water
Washing obtains wet cake to neutrality.
Filter cake and 60mL deionized waters are mixed with beating, add 3- picolines thereto, it is 5.6 to adjust pH value, stirring
Under the conditions of react 60min.Then membrane filtration is carried out by the ultrafiltration apparatus that molecular cut off is 30000, obtains filtrate.To filtrate
It is 7.0 that middle addition sodium hydroxide, which adjusts pH value, to form long-chain biatomic acid mono-sodium salt, and crystallized, filtering, is gone with 10 DEG C of low temperature
Ion water washing, obtains the crystallization of long-chain biatomic acid mono-sodium salt.This crystallization is mixed and heated to 90 DEG C with fresh deionized water,
Add 2g activated carbons at the same time to be adsorbed, then filter, H is added into filtrate2SO4The pH value of filtrate is adjusted to 3.0, is obtained
C13H24O4Aqueous solution filtering is crystallized, and is washed with water to neutrality, obtains wet cake, then C is obtained through dry13H24O4Product.
Experimental data is shown in Table 1.
Embodiment 3
200mL is taken to be fermented to obtain C by Candida tropicalis14H26O4Zymotic fluid, concentration are the zymotic fluid of 176g/L, are heated to
80 DEG C, through ceramic micro filter membrane filtration, the liquid wax for removing thalline and remnants obtains long-chain biatomic acid salt filtrate.Add H into filtrate2SO4
PH value is adjusted to 2.4, obtains C14H26O4Aqueous solution is crystallized, filtering, is washed with water to neutrality, obtains wet cake.
Filter cake and 90mL deionized waters are mixed with beating, add 2,4- lutidines thereto, it is 5.4 to adjust pH value,
60min is reacted under stirring condition.Then membrane filtration is carried out by the ultrafiltration apparatus that molecular cut off is 1000, obtains filtrate.To
It is 6.8 that sodium hydroxide is added in filtrate and adjusts pH value, low with 10 DEG C to form long-chain biatomic acid mono-sodium salt, and crystallized, filtering
Warm deionized water washing, obtains the crystallization of long-chain biatomic acid mono-sodium salt.This crystallization is mixed and heated to fresh deionized water
85 DEG C, while add 2g activated carbons and adsorbed, then filter, H is added into filtrate2SO4The pH value of filtrate is adjusted to 3.0, is obtained
To C14H26O4Aqueous solution, filtering are crystallized, and is washed with water to neutrality, obtains wet cake, then C is obtained through dry14H26O4Product.
Experimental data is shown in Table 1.
Embodiment 4
200mL is taken to be fermented to obtain the C of 155g/L by Candida tropicalis13H24O4And C14H26O4Mixed acid fermentation liquid adds
Heat is to 80 DEG C, and through ceramic micro filter membrane filtration, the liquid wax for removing thalline and remnants obtains acylate filtrate.Add H into filtrate2SO4
PH value is adjusted to 3.0, obtains mixing C13H24O4And C14H26O4Aqueous solution is crystallized, filtering, is washed with water to neutrality, obtains wet filter
Cake.
Filter cake and 90mL deionized waters are mixed with beating, add pyridine thereto, it is 6.0 to adjust pH value, under stirring condition
React 60min.Then membrane filtration is carried out by the ultrafiltration apparatus that molecular cut off is 10000, obtains filtrate.Added into filtrate
It is 7.0 that sodium hydroxide, which adjusts pH value, to form long-chain biatomic acid mono-sodium salt, and crystallized, filtering, with 10 DEG C of low temperature deionized waters
Washing, obtains the crystallization of long-chain biatomic acid mono-sodium salt.This crystallization is mixed and heated to 90 DEG C with fresh deionized water, is added at the same time
Enter 2g activated carbons to be adsorbed, then filter, H is added into filtrate2SO4The pH value of filtrate is adjusted to 3.0, obtains C13H24O4With
C14H26O4Mixed crystallization aqueous solution filters, and is washed with water to neutrality, obtains wet cake, then obtain C through dry13H24O4With
C14H26O4Product mix.
Experimental data is shown in Table 1.
Comparative example 2
The method of this comparative example extraction long-chain biatomic acid is as follows：
It is 155g/L C to take 200mL concentration13H24O4And C14H26O4Mixed dibasic acid zymotic fluid is heated to 80 DEG C, through ceramic micro filter
Membrane filtration, the liquid wax for removing thalline and remnants obtain acylate filtrate.Add H into filtrate2SO4PH value is adjusted to 3.0, is obtained
Mix C13H24O4And C14H26O4Aqueous solution is crystallized, filtering, is washed with water to neutrality, obtains wet cake.
Mixed with 300mL water with wet cake, then pH value is adjusted to 6.0 with the NaOH solution of 10mol/L, added at the same time
40gNaCl, is again heated to 90 DEG C, is then cooled to 80 DEG C of maintenance 30min, is slowly cooled to room temperature, mixing binary is obtained by filtration
Sour mono-sodium salt filter cake.The NaOH solution adjusting pH value that filter cake adds 10mol/L is 9, and the powder activity of 1wt% is added into solution
Charcoal, the adsorption treatment 30min at 60 DEG C.The double salting liquids of long-chain biatomic acid of clarification are obtained by filtration, 3mol/L is added into solution
H2SO4, adjust pH value to be heated to 80 DEG C, static to be cooled to room temperature, filtered, washing and drying steps obtain to 3.0
C13H24O4And C14H26O4Mix acid product.
Experimental data is shown in Table 1.
Comparative example 3
The method of this comparative example extraction long-chain biatomic acid is as follows：
Take the C that 200mL concentration is 160g/L12H22O4Dibasic acid fermentation liquor, is heated to 90 DEG C and carries out demulsification point removing remaining liquid
Wax, the zymotic fluid that thalline is contained in lower floor are filtered with the ultrafiltration membrane of 1000 molecular weight of retention, obtain ultrafiltration clear liquid, are adding 3g
Activated carbon carries out decolorization, the H of decoloration clear liquid 3mol/L2SO4PH value is adjusted to be subsequently cooled to room temperature to 3.0 acidizing crystals,
Filtered, washing, drying and drying, obtain C12H22O4Dicarboxylic acid product.
The property of 1 long-chain biatomic acid product of table
| Project | Total acid content wt% | Ash content wt% | Total nitrogen μ g/g |
| Embodiment 1 | 99.89 | 0.012 | 18 |
| Embodiment 2 | 99.90 | 0.019 | 16 |
| Embodiment 3 | 99.95 | 0.008 | 17 |
| Embodiment 4 | 99.97 | 0.012 | 15 |
| Comparative example 1 | 98.97 | 0.170 | 112 |
| Comparative example 2 | 99.40 | 0.092 | 35 |
| Comparative example 3 | 99.31 | 0.085 | 92 |
Claims (14)
1. a kind of method that long-chain biatomic acid is extracted from zymotic fluid, including：
I, it is preprocessed to terminate zymotic fluid, obtains and contains long-chain biatomic acid salt filtrate；
II, by long-chain biatomic acid salt acidification of filtrate, binary acid is fully crystallized precipitation, long-chain biatomic acid filter cake be obtained by filtration, washes
Wash；
Long-chain biatomic acid filter cake and water that step II is obtained, be mixed with beating by III；
Pyridine compounds and their is added in IV, the mixed serum obtained to step III；
V, the mixture for obtaining step IV carries out membrane filtration, obtains filtrate；
VI, add sodium hydroxide solution into the filtrate for obtaining step V, to form long-chain biatomic acid sodium salt, then crystallization analysis
Go out, long-chain biatomic acid sodium salt crystal is obtained after filtered, washing；
VII, dissolve the obtained crystallizations of step VI and water Hybrid Heating, adds adsorbent and adsorbs and filter, the acid adding into filtrate
Acidifying, makes binary acid be fully crystallized precipitation, filtered, washing, drying, obtain long-chain biatomic acid.
2. in accordance with the method for claim 1, it is characterised in that：Zymotic fluid is terminated described in step I and utilizes liquid wax for microorganism
Metabolite obtained from fermentation, wherein the long-chain biatomic acid general molecular formula contained is CnH2n-2O4, wherein n is 10-18.
3. in accordance with the method for claim 1, it is characterised in that：The pyridine compounds and their added in step IV is pyridine, 2-
Picoline, 3- picolines, 4- picolines, 2,3 dimethyl pyridine, 2,4- lutidines and 2,6- lutidines
In one or more.
4. according to any methods of claim 1-3, it is characterised in that：Addition pyridine compounds and their described in step IV
Amount makes the pH value of slurries be 5.0 ~ 6.4, and the reaction time of pyridine compounds and their and long-chain biatomic acid is 30 ~ 120min.
5. in accordance with the method for claim 1, it is characterised in that：The pH value of acidifying described in step II is 2.0 ~ 4.0, used
Acid be any concentration H2SO4、HNO3, HCl or H3PO4。
6. in accordance with the method for claim 1, it is characterised in that：Long-chain biatomic acid filter cake is mixed with beating with water in step III
When, water consumption is 50wt% ~ 500wt% of long-chain biatomic acid filter cake weight, is preferably 100wt% ~ 300wt%.
7. according to the method described in claim 1 or 6, it is characterised in that：Water described in step III is deionized water, electrical conductivity
Less than 0.1 μ s.
8. in accordance with the method for claim 1, it is characterised in that：Membrane filter system described in step V is micro-filtration or ultrafiltration, excellent
Elect ultrafiltration as, the aperture of ultrafiltration membrane is that molecular cut off is 1000 ~ 30000, is preferably 1000 ~ 5000.
9. in accordance with the method for claim 1, it is characterised in that：It is molten that sodium hydroxide is added in the filtrate obtained to step VI
Liquid, the mass concentration of sodium hydroxide solution is 10% ~ 40%, and it is 6.4 ~ 7.0 to adjust pH value.
10. in accordance with the method for claim 1, it is characterised in that：Washing described in step VI is washed with low temperature deionized water
Wash, low temperature deionized water temperature is 5 DEG C ~ 15 DEG C.
11. in accordance with the method for claim 1, it is characterised in that：In step VII, the crystallization that step VI is obtained and water are mixed
Close and dissolve by heating, 85 DEG C ~ 95 DEG C of solution temperature.
12. in accordance with the method for claim 1, it is characterised in that：In step VII, adsorbent used is activated carbon, diatom
One or more in soil, atlapulgite；The dosage of the adsorbent terminates the 1% ~ 5% of zymotic fluid quality for step I.
13. in accordance with the method for claim 1, it is characterised in that：In step VII, the pH value of the acidifying is 2.0 ~ 4.0,
Acid is the H of any concentration2SO4、HNO3, HCl or H3PO4。
14. in accordance with the method for claim 1, it is characterised in that：In step I, the pretreated method of zymotic fluid is terminated extremely
Less selected from one of following method：
（1）Zymotic fluid will be terminated and be heated to 75 DEG C ~ 90 DEG C, into micro-filtration or ultrafiltration apparatus, thalline and liquid wax impurity is removed, obtain
Long-chain biatomic acid salt filtrate；
（2）Zymotic fluid will be terminated and heat 85 DEG C ~ 100 DEG C, it is 8~10 to adjust pH value, stands, then divides upper strata remaining liquid
Wax, the long-chain biatomic acid salting liquid of lower floor's mycetome are cooled to 30 DEG C ~ 90 DEG C, by micro-filtration and/or ultrafiltration apparatus, are filtered to remove
Thalline impurity, obtains long-chain biatomic acid salt filtrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610933532.XA CN108017535B (en) | 2016-11-01 | 2016-11-01 | Method for extracting long-chain dicarboxylic acid from fermentation liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610933532.XA CN108017535B (en) | 2016-11-01 | 2016-11-01 | Method for extracting long-chain dicarboxylic acid from fermentation liquor |
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| Publication Number | Publication Date |
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| CN114478235A (en) * | 2020-10-28 | 2022-05-13 | 中国石油化工股份有限公司 | Method for purifying organic acid in fermentation liquor |
| CN114685260A (en) * | 2020-12-29 | 2022-07-01 | 中国石油化工股份有限公司 | Method for purifying long-chain dicarboxylic acid |
| CN114685267A (en) * | 2020-12-29 | 2022-07-01 | 中国石油化工股份有限公司 | Method for crystallizing long-chain dicarboxylic acid and method for purifying long-chain dicarboxylic acid |
| CN114685261A (en) * | 2020-12-29 | 2022-07-01 | 中国石油化工股份有限公司 | Refining method of long-chain dicarboxylic acid |
| US11999689B2 (en) | 2019-12-19 | 2024-06-04 | Cathay Biotech Inc. | Method and system for extracting long chain dicarboxylic acid |
| US12017182B2 (en) | 2019-12-24 | 2024-06-25 | Cathay Biotech Inc. | Method and system for refining long chain dicarboxylic acid |
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| CN114685267B (en) * | 2020-12-29 | 2024-09-03 | 中国石油化工股份有限公司 | Crystallization method of long-chain dicarboxylic acid and purification method of long-chain dicarboxylic acid |
| CN114685260B (en) * | 2020-12-29 | 2024-09-03 | 中国石油化工股份有限公司 | Process for purifying long-chain dicarboxylic acid |
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