CN100494136C - Ammonium sulfate salting-out process for extracting and separating 1,3-propylene glycol from microbial fermented liquid - Google Patents
Ammonium sulfate salting-out process for extracting and separating 1,3-propylene glycol from microbial fermented liquid Download PDFInfo
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- CN100494136C CN100494136C CNB2006101346958A CN200610134695A CN100494136C CN 100494136 C CN100494136 C CN 100494136C CN B2006101346958 A CNB2006101346958 A CN B2006101346958A CN 200610134695 A CN200610134695 A CN 200610134695A CN 100494136 C CN100494136 C CN 100494136C
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- ammediol
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- fermented liquid
- ammonium sulfate
- separating
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- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000007788 liquid Substances 0.000 title claims abstract description 18
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910052921 ammonium sulfate Inorganic materials 0.000 title claims abstract description 10
- 235000011130 ammonium sulphate Nutrition 0.000 title claims abstract description 10
- 230000000813 microbial effect Effects 0.000 title claims description 8
- 238000005185 salting out Methods 0.000 title claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title abstract 6
- 239000006228 supernatant Substances 0.000 claims abstract description 25
- 239000000047 product Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 31
- 238000004821 distillation Methods 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 11
- 238000000855 fermentation Methods 0.000 claims description 8
- 230000004151 fermentation Effects 0.000 claims description 8
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 claims description 6
- 238000000108 ultra-filtration Methods 0.000 claims description 5
- 230000006837 decompression Effects 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 9
- 238000001704 evaporation Methods 0.000 abstract description 5
- 230000003311 flocculating effect Effects 0.000 abstract description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 abstract description 3
- 230000001376 precipitating effect Effects 0.000 abstract 2
- 239000002244 precipitate Substances 0.000 abstract 1
- 238000004062 sedimentation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 4
- 238000012262 fermentative production Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 150000007523 nucleic acids Chemical class 0.000 description 3
- 102000039446 nucleic acids Human genes 0.000 description 3
- 108020004707 nucleic acids Proteins 0.000 description 3
- -1 polytrimethylene terephthalate Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011345 viscous material Substances 0.000 description 3
- 241000193830 Bacillus <bacterium> Species 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 238000000703 high-speed centrifugation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 241000588747 Klebsiella pneumoniae Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
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Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The present invention belongs to the field of bioengineering technology, and is especially technology and process of extracting and separating 1, 3-propylene glycol from fermented liquid. The process includes the following steps: the first ultrafiltering, centrifuging or flocculating to eliminate thallus from the fermented liquid, the subsequent evaporating and concentrating the supernatant, adding ammonium sulfate and precipitating or filtering to obtain supernatant, further concentrating the supernatant to eliminate water and precipitating, filtering or centrifuging to eliminate residual precipitate, and final distilling the supernatant and rectifying to obtain 1, 3-propylene glycol product. The process is simple, has low separating cost, short separating time and high product purity, and may be used widely in extracting 3-propylene glycol from fermented liquid.
Description
Technical field
The invention belongs to technical field of bioengineering, relate to the isolation technique of microbial fermentation solution, specially refer to and from microbial fermentation solution, separate 1, the method for ammediol.
Background technology
As everyone knows, 1, ammediol is a kind of important chemical material, with ethylene glycol, 1,2-propylene glycol and 1.4-butyleneglycol have same purposes, but it and terephthalic acid synthetic new polyester material polytrimethylene terephthalate (PTT) have the not available good characteristic of many polyester materials, good continuous printing and dyeing that present as need not to add any speciality chemical in the tint permanence of recovery of elasticity, uvioresistant, ozone and the oxynitride of nylon sample, low static, low water absorption, the panchromatic scope and biodegradable etc.These have all shown 1, the application prospect that ammediol is fine, but its expensive price has hindered its application.Since fermentative Production 1, ammediol become may since, researcher makes great efforts to explore a separation method of not only having saved trouble but also can reduce cost always.
Extraction separation 1 from microbial fermentation solution at present, ammediol, adopt carried disease germs fermented liquid through high speed centrifugation or through film (as tunica fibrosa) filtering separation cell more, extract as DE863632397 and US5008473, molecular sieve such as WO0125178 or vacuum distillation method purification 1, ammediol by extraction agent then.Problems such as in the above-mentioned technology, high speed centrifugation not only energy consumption is higher, and separating power is limited, for the production of large industrial chemicals, exists separating power less, and disengaging time is long.In fermented liquid, directly add flocculating aids/flocculation agent, help to precipitate part thalline, nucleic acid and albumen, but the salt in the fermented liquid can crystallization and separate out, and still can form viscous substance in vacuum distillation process, hinders 1, the evaporation of ammediol.People Biotechnology Progress such as Baltycka (2000,16:76-79) open report adopts reaction, extraction, its general step is, in fermented liquid, add aldehyde, make 1, ammediol and aldehyde condensation, slough in the organic phase behind the water, with o-Xylol or toluene or ethylbenzene extraction, obtain 1 by hydrolysis then, ammediol.As seen, the operation of reaction, extraction arts demand multistep causes separation efficiency lower thus, the operating procedure complexity, and problems such as the difficult control of operational condition are promoted industry and are acquired a certain degree of difficulty, and research in this respect at present still is in laboratory stage.People such as Malinowski are at Biotechnology Progress (1999,13 (2): 127-30) report adopts the liquid-liquid extraction method, but also have with a certain distance from industrialization at present, the problem of existence is that extraction efficiency is lower, and the extraction agent that specificity is strong is selected comparatively difficulty.
Summary of the invention
The objective of the invention is at present fermentative Production 1, some problems that exist in the technology of ammediol later separation purified product, as the cost height, separating power is little, and the underpressure distillation later stage salt crystallization and viscous substance occur and hinder problems such as cut evaporation, and propose a kind ofly from fermented liquid, to separate 1, the effective ways of ammediol, make Production by Microorganism Fermentation 1, ammediol technically, viable economically.
Technical solution of the present invention is:
At first the thalline in the fermented liquid is removed with ultrafiltration or method centrifugal or flocculation, the supernatant liquor distillation is concentrated to 30%～10% of original volume, add ammonium sulfate (saturation ratio is 30%-100%) by 1: 0.5～1: 0.1 volume ratio,, obtain supernatant liquor by sedimentation or filtering separation precipitation; The gained supernatant liquor is continued distillation, remove the water in the supernatant liquor, remove residual throw out by sedimentation or filtering separation precipitation or 1000-5000 rev/min of low-speed centrifugal, then with supernatant liquor by normal pressure or underpressure distillation then the method for rectifying obtain 1, the ammediol product.The present invention solves present fermentative Production 1, and being difficult to of existing in the ammediol separating technology separate, the high problem of cost, and advantage of the present invention is that technology is simple, separation costs is low, and disengaging time is short, the product purity height, can be widely used in extraction separation 1 from microbial fermentation solution, ammediol.
Effect of the present invention and benefit are:
Overcome extraction separation 1 from microbial fermentation solution at present, many drawbacks that ammediol technology exists are simplified technology, and cost reduces, economically feasible.Be in particular in: at first with the method for ultrafiltration the thalline in the fermented liquid 100% is removed, and nucleic acid a large amount of in the fermented liquid, albumen, polysaccharide can be removed, it is incomplete to have solved flocculating settling, a large amount of sedimentation dopes also must be centrifugal etc. problem.The water that distills is collected and is used for preparing substratum and alkali lye, conserve water resource not only, and with evaporation carry secretly 1, ammediol is reclaimed, and has reduced product losses; The effect that adds ammonium sulfate is the ionic strength that has increased solution, and the ammoniumsulphate soln of formation is strengthened salting-out effect, and further concentrated solution amplifying nucleic acid, albumen, polysaccharide and part organic salt and inorganic salt precipitation is separated out; The salt crystallization and the viscous substance that have also solved simultaneously the appearance of underpressure distillation later stage influence 1, problems such as ammediol evaporation.
Embodiment
Below be described in detail technical solution of the present invention and specific embodiment.
Step 1
At first the thalline in the fermented liquid is removed, will be crossed the distillation of film liquid then and be concentrated to 30%～10% of original volume with ultrafiltration or method centrifugal or flocculation.
Step 2
With the concentrated solution that step 1) obtains, the volume ratio adding ammonium sulfate (saturation ratio is 30%～100%) by 1:0.5～1:0.1 then by sedimentation or filtering separation throw out, gets supernatant liquor.
Step 3
With step 2) supernatant liquor continuation distillation, remove the water in the supernatant liquor, by the throw out of sedimentation, filtration, low-speed centrifugal (1000～5000 rev/mins) separating residual, get supernatant liquor then.
Step 4
The step 3) supernatant liquor is obtained 1 by normal pressure or underpressure distillation, the thick product of ammediol.
Step 5
With step 4) gained 1, the thick product of ammediol obtains 1 by the method for rectifying, the ammediol product.
Embodiment:
Used fermented liquid is to adopt Cray Bai Shi bacillus (Klebsiella pneumoniae) batch formula stream glycerol adding fermentative production 1 in the present embodiment, and ammediol is resulting, wherein 1, and the concentration of ammediol is 63g/L.
Cray Bai Shi bacillus (K.pneumoniae) is available from Chinese common micro-organisms DSMZ (CGMCC), culture presevation number: 1.1736.
Sepn process divided for five steps:
1) get the 1000mL fermented liquid, the ultra-filtration membrane of employing is the product of Japanese NIPRO company, model FB-150AGA, useful area 1.5m
2, molecular weight cut off 5,000 dalton, mould material is a secondary cellulose acetate, the thalline in the fermented liquid 100% can be removed, and carries out underpressure distillation at Rotary Evaporators then, vacuum tightness is 0.095MPa ,≤60 ℃ of temperature controls, and the volume of the concentrated solution that obtains is 300mL.
2) leave standstill cool to room temperature after, add 100mL 40% ammonium sulfate, stir the back suction filtration, obtain throw out and supernatant liquor 1.
3) supernatant liquor 1 is continued distillation, remove the water in the supernatant liquor, by the throw out of sedimentation or filtration or 1000～5000 rev/mins of low-speed centrifugal separating residuals, get supernatant liquor 2 then.
4) with supernatant liquor 2 by underpressure distillation, vacuum tightness is 0.095MPa, heats in oil bath, collect 130～150 ℃ be rich in 1, the cut of ammediol, 1, the thick product of ammediol.
5) with 1, it is 1 more than 95% that the thick product of ammediol obtains purity by rectifying, the ammediol product, and the rate of recovery is 85%.
Claims (1)
1. ammonium sulfate salting-out process extraction separation 1 from microbial fermentation solution, ammediol is characterized in that:
1) at first the thalline in the fermented liquid is removed with the method for ultrafiltration;
2) the supernatant liquor distillation is concentrated to 30%～10% of original volume, volume ratio adding saturation ratio by 1:0.5～1:0.1 is the ammonium sulfate of 30%-100%, be 1000-5000 rev/min low-speed centrifugal disgorging then by natural subsidence, filtration or rotating speed, get supernatant liquor;
3) with 2) the gained supernatant liquor continues distillation, removes the water in the supernatant liquor, is that 1000-5000 rev/min low-speed centrifugal is removed residual throw out by natural subsidence, filtration or rotating speed then, supernatant liquor;
4) with 3) the gained supernatant liquor by the decompression or air distillation obtain 1, the thick product of ammediol;
5) with 4) the thick product of gained obtains 1 by the method for rectifying, the ammediol product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101346958A CN100494136C (en) | 2006-12-08 | 2006-12-08 | Ammonium sulfate salting-out process for extracting and separating 1,3-propylene glycol from microbial fermented liquid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101346958A CN100494136C (en) | 2006-12-08 | 2006-12-08 | Ammonium sulfate salting-out process for extracting and separating 1,3-propylene glycol from microbial fermented liquid |
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| Publication Number | Publication Date |
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| CN1974513A CN1974513A (en) | 2007-06-06 |
| CN100494136C true CN100494136C (en) | 2009-06-03 |
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| CN101875598B (en) * | 2009-04-30 | 2013-11-06 | 中国石油天然气股份有限公司 | Separation method of 1,3-propylene glycol fermentation liquid |
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