CN1434122A - Two-stage double-zymolyte integrated fermentation productive method for 1,3-propylene alcohol - Google Patents
Two-stage double-zymolyte integrated fermentation productive method for 1,3-propylene alcohol Download PDFInfo
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- CN1434122A CN1434122A CN 03119280 CN03119280A CN1434122A CN 1434122 A CN1434122 A CN 1434122A CN 03119280 CN03119280 CN 03119280 CN 03119280 A CN03119280 A CN 03119280A CN 1434122 A CN1434122 A CN 1434122A
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000000855 fermentation Methods 0.000 title claims abstract description 22
- 230000004151 fermentation Effects 0.000 title claims abstract description 20
- -1 1,3-propylene alcohol Chemical compound 0.000 title abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 124
- 235000011187 glycerol Nutrition 0.000 claims abstract description 57
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 37
- 239000008103 glucose Substances 0.000 claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 32
- 230000008569 process Effects 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 238000009423 ventilation Methods 0.000 claims description 16
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 230000009466 transformation Effects 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 230000005587 bubbling Effects 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 235000009508 confectionery Nutrition 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000011218 seed culture Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000002609 medium Substances 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 208000015181 infectious disease Diseases 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 241000588747 Klebsiella pneumoniae Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 241000588923 Citrobacter Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000003570 biosynthesizing effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 241000588919 Citrobacter freundii Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 241000193403 Clostridium Species 0.000 description 1
- 241000193171 Clostridium butyricum Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 241000411968 Ilyobacter Species 0.000 description 1
- 241000588748 Klebsiella Species 0.000 description 1
- 241000186660 Lactobacillus Species 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 241001052560 Thallis Species 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- AIMMVWOEOZMVMS-UHFFFAOYSA-N cyclopropanecarboxamide Chemical compound NC(=O)C1CC1 AIMMVWOEOZMVMS-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000012262 fermentative production Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229940039696 lactobacillus Drugs 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000012807 shake-flask culturing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Abstract
The present invention relates to a two-stage double-zymolyte integrated fermentation productino method of 1,3-propylene alcohol, belonging to the field of biological synthesis production technology of 1,3-propylene glycol. It is characterized by that said invented two-stage seed culture uses glucose and glycerine as mixed double-substrate, and can integrate the two-stage seed culture under the aerobic condition and glycerine anaerobic conversion under the anaerobic condition in same fermentation tank to implement them, and uses the complete consumption of glucose as conversion condition from aerobic to anaerobic fermentation. Said invention can reduce process steps, and can raise utilization rate of equipment, and can shorten into production period.
Description
Technical field:
1, two sections integrated fermentation method for producing of Double bottom thing of ammediol relate to 1, and the production technical field of ammediol refers more particularly to 1, the biosynthesizing production method technical field of ammediol.
Background technology:
1, ammediol (1,3-propanediol, 1,3-PD) be a kind of important chemical material, except that being used as the solvent, mainly be used as the monomer of synthesizing polyester, urethane, with 1 as other dibasic alcohol, 3-PD is that the polytrimethylene terephthalate (PTT) that monomer is produced is a kind of new polyester material, have easy dyeing, good springiness, good flexibility, drape, low static, advantage such as biodegradable, be mainly used in producd fibers and textiles, as carpet, panty hose, Sportswear etc.Industrial main employing chemical synthesis and biological synthesis process carry out 1 at present, the production of ammediol, shortcoming such as chemical synthesis has that facility investment is big, technical difficulty is high, needs heavy metal catalyst, contaminate environment, raw material are non-renewable, therefore, each state all is devoted to develop biological process and produces 1, the technology of 3-PD.Biological synthesis process mainly is under the effect of biological catalyst, with transformation of glycerol is 1, ammediol, at present, can be used for 1, the microorganism of the biosynthesizing production method of ammediol mainly has: genus such as Klebsiella, Citrobacter, Clostridium, Ilyobacter, Lactobacillus, Enterobatcer, wherein studying maximum is Klebsiella pneumoniae (Ke Shi pneumobacillus), Citrobacter freundii (Fu Shi lemon bacterium) and Clostridiumbutyricum (butyric acid shuttle shape sporeformer).Wherein Ke Shi pneumobacillus and Fu Shi Citrobacter are in facultative anaerobe, and facultative anaerobe grows faster under aerobic condition.
At present, utilizing facultative anaerobe is that the processing step of 1,3 propylene glycol is mainly as biological catalyst with transformation of glycerol: (is example with fermented liquid 4L): 1, seed activation (24 hours); 2, carry out first order seed under aerobic condition and cultivate, carbon source is glycerine or glucose (volume 50ml, 12 hours); 3, carrying out secondary seed under aerobic condition cultivates, carbon source is glycerine or glucose (volume 500ml, 12 hours), and this stage mainly is that seed is carried out enlarged culturing, make bacterial classification reach certain scale, for next step transformation of glycerol is created better starting condition; 4, in the anaerobically fermenting stage (volume 4L, 60 hours), substrate is a glycerine, and this stage is to be 1 with transformation of glycerol under anaerobic, and ammediol is that carbon source is grown with glycerine also as the thalline of biological catalyst simultaneously.In above-mentioned steps, the cultivation of the secondary of seed is to carry out in two systems respectively with next step glycerine anaerobism conversion under the aerobic condition, make the fermentation period lengthening like this, reducing usage ratio of equipment reduces, increase operation steps simultaneously, and changing over to the process of another system, increased the chance of bacteria infection, for subsequent technique brings disadvantageous effect from a system.
Summary of the invention:
The objective of the invention is to, overcome the above-mentioned shortcoming of prior art, proposed a kind of 1, two sections integrated fermentation method for producing of Double bottom thing of ammediol, this method serves as to mix the Double bottom thing with glucose and glycerine, the secondary of seed under aerobic condition cultivated and the anaerobism conversion of glycerine is integrated in the device and carries out, reduced processing step, improved usage ratio of equipment, the time of the aerobic cultivation of thalline is shortened greatly, promptly shorten the cycle of fermentation, do not influenced 1 again, the concentration that ammediol is final; Owing to there is not the process of system's conversion, also reduced the chance of bacteria infection,
The present invention contains following steps successively:
The seed activation of facultative anaerobe;
At aerobic condition, be that carbon source is carried out the first order seed cultivation with glucose;
At aerobic condition, be that carbon source is carried out the secondary seed cultivation with glucose;
Under anaerobic, be biological catalyst with above-mentioned facultative anaerobe body, be 1 with transformation of glycerol, ammediol;
It is characterized in that, it serves as to mix the Double bottom thing that above-mentioned secondary seed is cultivated with glucose and glycerine, secondary seed under the above-mentioned aerobic condition cultivated and anaerobic condition under transformation of glycerol be integrated in the same fermentor tank and carry out, and whether run out of with glucose and to be aerobic condition to the anaerobism conversion, it contains following steps:
(1) seed activation of facultative anaerobe;
(2) be carbon source with glucose, under aerobic condition, carry out first order seed and cultivate;
(3) during the integrated fermention medium that will contain glucose and glycerine is packed fermentor tank into, will cultivate through above-mentioned first order seed
The seed of facultative anaerobe insert in the fermentor tank, form integrated fermented liquid; Under 35 ℃～38 ℃ temperature, feed
Air stirs, and beginning to carry out with glucose is the aerobic cultivation of thalline of main carbon source;
(4) when the glucose consumption in the above-mentioned integrated fermented liquid is intact, stop bubbling air, add glycerine and ammonium sulfate;
Under 35 ℃～38 ℃ temperature, feed nitrogen, stir, change over to and under the anaerobic condition glycerine is converted to 1,3
The stage of-propylene glycol; In this process, need to add glycerine to keep the concentration of glycerine, guarantee to have enough sweet
Oil is changed; This process is attended by by product ethanol, acetate and lactic acid and generates;
(5) when not regrowth of thalline, technological process finishes.
In (3) step of above-mentioned integrated fermenting process, the content ratio of glucose and glycerine is 1 in the described integrated fermention medium: (0.8～1.2).In (3) step of above-mentioned integrated fermenting process, the ventilation of air is than being 0.3vvm～1.0vvm.In (4) step of above-mentioned integrated fermenting process, the ventilation of nitrogen is than being 0.3vvm～1.0vvm.In (4) step of above-mentioned integrated fermenting process,, the concentration of glycerine is remained between 10g/L～20g/L by adding glycerine.In (4) step of above-mentioned integrated fermenting process, when by product alcoholic acid content meets or exceeds 2g/L, increase nitrogen ventilation ratio, increase and stir revolution.
Experimental results show that, utilize proposed by the invention 1, two sections integrated fermentation method for producing of Double bottom thing of ammediol, can reduce processing step, improve usage ratio of equipment, shorten process cycle and do not influence 1, the concentration that ammediol is final has also avoided system to change the chance of the bacteria infection that is caused.
Embodiment:
Select amphimicrobian Ke Shi pneumobacillus (Klebsiella pneumoniae) as producing bacterial classification.Experiment 1: the prescription of substratum: LB solid medium: every liter of volume substratum contains yeast powder 5.0g, peptone 10.0g, NaCl 10.0g, agar 15.0g, pH7.0.Seed culture medium: every liter of volume substratum contains glucose 20g, K
2HPO
4.3H
2O 4.45g, KH
2PO
4, 1.3g, (NH
4)
2SO
4
2.0g, MgSO
4.7H
2O 0.2g, CaCO
32.0g, yeast powder 1.0g, trace element solution I 2.0ml,
Fe
2+Solution 1.0ml, pH7.0.Integrated fermention medium: every liter of volume substratum contains glucose 2.5g, glycerine 2.0g (glucose and glycerine ratio are 1: 0.8),
K
2HPO
4.3H
2O?4.45g，KH
2PO
4，1.3g，(NH
4)
2SO
4?2.0g，MgSO
4.7H
2O?0.2g，
CaCl
2.2H
2O 0.02g/L, yeast powder 1.0g, trace element solution I 2.0ml, Fe
2+Solution
1.0ml，pH7.0。
Wherein, the composition of above-mentioned micro-I (mg/L): MgSO
4.4H
2O 100, ZnCl
270, Na
2MoO
42H
2O 35, H
3BO
360, CoCl
2.6H
2O 200, CuSO
4.5H
2O 29.28, NiCl
26H
2O 25,37%HC 10.9ml experimental procedure: 1) seed activation: insert LB solid inclined-plane by culture presevation inclined-plane picking one ring Klebsiella pneumoniae lawn and activate, cultivate after 12 hours for 37 ℃, picking one ring lawn inserts solid LB flat board again, cultivates for 37 ℃ and obtains single bacterium colony after 12 hours.2) the seed one-level under the aerobic condition is cultivated: single bacterium colony of picking from the LB flat board of step 1), insert the 300ml shake-flask culture, and liquid amount 50ml, 37 ℃, stir revolution 150rpm, cultivate 12h.3) two sections aerobic cultivation stages of the integrated ferment-seeded of Double bottom thing: the integrated fermention medium that 4L is sterilized is in advance packed in the fermentor tank, with the 2nd) go on foot in the seed liquor access fermentor tank that obtains, under 37 ℃, stir, the stirring revolution is 400rpm, bubbling air, ventilation add 4N NaOH and regulate the potential of hydrogen of mixed fermentation liquid for neutral than being 0.3vvm.In this process, by detect the content of glucose with biosensor, explanation glucose runs out of when the content of glucose is 0, and this moment, the OD value of thalline was 1.5, reached the requirement of glycerine anaerobism conversion, at this moment changed next stage over to the thalline biomass.The used time in this stage is 2.5 hours.4) two periods integrated anaerobic fermentation transformation stages of Double bottom thing: this stage stops bubbling air, adds glycerine to 20g/L, add simultaneously ammonium sulfate to 4g/L to replenish nitrogenous source.Feed nitrogen then, ventilation, is stirred under 37 ℃ than for 0.3vvm, and stirrings revolution is 400rpm, and is neutrality with the potential of hydrogen that adding 4N NaOH regulates mixed fermentation liquid.In this course, by detect the concentration of glycerine with high performance liquid chromatograph (HPLC), its concentration is remained between 10g/L～20g/L, when the concentration of glycerine is lower than 10g/L, add glycerine, make its concentration reach 20g/L, to guarantee that it is 1 that enough transformation of glycerol are arranged, ammediol.Change behind the anaerobic condition about 4 hours over to, begin to have 1, ammediol generates, and also is attended by by-product acetic acid, ethanol and lactic acid simultaneously and generates.Whole process is along with the continuous adding of glycerine, and the concentration of thalline and 1,3 propylene glycol is also in continuous increase.5) when the biomass (OD) of thalline when reaching 7.4, no longer include thalline and generate, also no longer including transformation of glycerol is 1, ammediol, and technological process finishes, and the used time is 55.5 hours, and record 1 this moment, and the concentration of ammediol is 54.23g/L.
Below 5 groups the experiment under the prerequisite that does not change other step and processing condition, changed the content ratio of glucose and glycerine in the integrated fermention medium respectively, changed the ventilation ratio of air and nitrogen, after experiment finishes, obtain the data shown in the table 1, the finished product concentration refers in the table 11, the concentration of ammediol.
| Group | The aerobic cultivation of seed | The glycerine anaerobism transforms | ||||||||
| Glucose and glycerine ratio | The air ventilation is than (vvm) | Stir commentaries on classics degree (rpm) | Cell concentration (OD) | Incubation time (h) | The nitrogen ventilation is than (vvm) | Stir commentaries on classics degree (rpm) | Cell concentration (OD) | Transformation time (h) | The finished product concentration (g/L) | |
| ??1 | 1∶0.8 | ????0.5 | ??400 | ??1.5 | ??2.5 | ???0.5 | ??400 | ???7.4 | ??55.5 | ???54.23 |
| ??2 | 1∶1 | ????0.5 | ??400 | ??1.6 | ??2.8 | ???0.5 | ??400 | ???9.3 | ??56 | ???61.2 |
| ??3 | 1∶1.2 | ????0.5 | ??400 | ??1.8 | ????3 | ???0.5 | ??400 | ???8.6 | ??57 | ???60.8 |
| ??4 | 1∶1 | ????0.3 | ??400 | ??1.5 | ??3.5 | ???0.3 | ??400 | ???8.4 | ??57 | ???57.2 |
| ??5 | 1∶1 | ????0.8 | ??400 | ??1.7 | ??2.7 | ???0.8 | ??400 | ???7.8 | ??55.2 | ???63.8 |
| ??6 | 1∶1 | ????1.0 | ??400 | ??1.75 | ??2.6 | ???1.0 | ??400 | ???8.8 | ??56 | ???64.1 |
Table 1
From 6 groups shown in the table 1 experiments as can be known, when the aerobic cultivation stage of the seed of integrated fermenting process finished, the time that is consumed only was 2～3.5 hours, shortened greatly with traditional method (cultivate the bacterial classification of identical biomass, required time the 12h) time of comparing.
From testing 1,2,3 as can be known, in integrated fermention medium, the content ratio of glucose and glycerine is 1: when (0.8～1.2) [in integrated fermention medium, every liter of substratum contains (glucose 2.5g respectively, glycerine 2.0g), (glucose 2.5g, glycerine 2.5g), (glucose 2.5g, glycerine 3g)], with glucose thalline that carbon source generated when reaching the required biomass of glycerine conversion, glucose just runs out of, can not be retained in the glycerine anaerobism transformation stage, to the conversion generation restraining effect of glycerine.
In glycerine anaerobism conversion process, can be attended by by product ethanol, acetate and lactic acid and generate, alcoholic acid exists and can produce toxic side effect to fermented liquid, and to thalline and 1, the generation of ammediol is unfavorable.Therefore, under the situation identical with other condition of the 2nd experiment, in the glycerine anaerobism conversion process of integrated fermenting process, when concentration of ethanol reaches 2g/L, 0.8vvm is compared in the ventilation that increases nitrogen, increase stirring velocity to 500rpm, when technological process finished, the biomass that records thalline was 9.4,1, the concentration of ammediol is 68.7g/L, the ventilation ratio of suitable increase nitrogen is described, accelerates stirring velocity, ethanol is fully volatilized, help thalli growth and 1, the conversion of ammediol.The increase of nitrogen ventilation ratio should be no more than 1.0vvm; The increase of stirring velocity also should be no more than 500rpm (in normal ranges).
In the integrated fermentative Production 1 of two sections Double bottom things of the present invention, in the process of ammediol, the temperature of integrated fermentation stage and stirring revolution all are normal ranges, and temperature is selected can be in 35 ℃～38 ℃ of normal ranges, and stirring velocity can be chosen in normal ranges 200～500rpm.Be used to regulate potential of hydrogen and can select other alkaline solution, as potassium hydroxide, ammoniacal liquor etc.In addition, the ventilation of aerobic stage air than and the ventilation ratio of anaerobic stages nitrogen can be unequal, need only the two all in 0.3～1.0vvm scope.
Can prove by above-mentioned experiment, proposed by the invention 1, two sections integrated fermentation method for producing of Double bottom thing of ammediol, reduced processing step, improve usage ratio of equipment, the time of the aerobic cultivation of thalline is shortened greatly, promptly shortened the cycle of fermentation, do not influence 1 again, the concentration that ammediol is final; Owing to do not have the process of system's conversion, also reduced the chance of bacteria infection.
Claims (6)
1,1, two sections integrated fermentation method for producing of Double bottom thing of ammediol, contain following steps successively:
The seed activation of facultative anaerobe;
At aerobic condition, be that carbon source is carried out the first order seed cultivation with glucose;
At aerobic condition, be that carbon source is carried out the secondary seed cultivation with glucose;
Under anaerobic, be biological catalyst with above-mentioned facultative anaerobe body, be 1 with transformation of glycerol, ammediol;
It is characterized in that, it serves as to mix the Double bottom thing that above-mentioned secondary seed is cultivated with glucose and glycerine, secondary seed under the above-mentioned aerobic condition cultivated and anaerobic condition under transformation of glycerol be integrated in the same fermentor tank and carry out, and whether run out of with glucose and to be aerobic condition to the anaerobism conversion, it contains following steps:
(1) seed activation of facultative anaerobe;
(2) be carbon source with glucose, under aerobic condition, carry out first order seed and cultivate;
(3) during the integrated fermention medium that will contain glucose and glycerine is packed fermentor tank into, will cultivate through above-mentioned first order seed
The seed of facultative anaerobe insert in the fermentor tank, form integrated fermented liquid; Under 35 ℃～38 ℃ temperature, feed
Air stirs, and beginning to carry out with glucose is the aerobic cultivation of thalline of main carbon source;
(4) when the glucose consumption in the above-mentioned integrated fermented liquid is intact, stop bubbling air, add glycerine and ammonium sulfate;
Under ℃ temperature of 35C～38, feed nitrogen, stir, change over to and under the anaerobic condition glycerine is converted to 1,3
The stage of-propylene glycol; In this process, need to add glycerine to keep the concentration of glycerine, guarantee to have enough sweet
Oil is changed; This process is attended by by product ethanol, acetate and lactic acid and generates;
(5) when not regrowth of thalline, technological process finishes.
2, as claimed in claim 11, two sections integrated fermentation method for producing of Double bottom thing of ammediol is characterized in that, in (3) step of above-mentioned integrated fermenting process, the content ratio of glucose and glycerine is 1 in the described integrated fermention medium: (0.8～1.2).
3, as claimed in claim 11, two sections integrated fermentation method for producing of Double bottom thing of ammediol is characterized in that, in (3) step of above-mentioned integrated fermenting process, the ventilation of air is than being 0.3vvm～1.0vvm.
4, as claimed in claim 11, two sections integrated fermentation method for producing of Double bottom thing of ammediol is characterized in that, in (4) step of above-mentioned integrated fermenting process, the ventilation of nitrogen is than being 0.3vvm～1.0vvm.
5, as claimed in claim 11, two sections integrated fermentation method for producing of Double bottom thing of ammediol is characterized in that, in (4) step of above-mentioned integrated fermenting process, by adding glycerine, the concentration of glycerine are remained between 10g/L～20g/L.
6, as claimed in claim 11, two sections integrated fermentation method for producing of Double bottom thing of ammediol is characterized in that, in (4) step of above-mentioned integrated fermenting process, when by product alcoholic acid content meets or exceeds 2g/L, increase nitrogen ventilation ratio, increase and stir revolution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03119280 CN1206362C (en) | 2003-03-07 | 2003-03-07 | Two-stage double-zymolyte integrated fermentation productive method for 1,3-propylene alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03119280 CN1206362C (en) | 2003-03-07 | 2003-03-07 | Two-stage double-zymolyte integrated fermentation productive method for 1,3-propylene alcohol |
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| CN1206362C CN1206362C (en) | 2005-06-15 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006128381A1 (en) * | 2005-06-03 | 2006-12-07 | Tsinghua University | Method for preparing 1,3-propanediol by using glycerine as the by-product of the biological diesel oil |
| CN100463968C (en) * | 2006-01-27 | 2009-02-25 | 华侨大学 | Process for preparing 1,3-propylene glycol and dihydroxy acetone by bio-catalytic conversion of glycerol |
| US8324434B2 (en) | 2008-03-02 | 2012-12-04 | Dow Global Technologies, Llc | Hydrogenation process |
-
2003
- 2003-03-07 CN CN 03119280 patent/CN1206362C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006128381A1 (en) * | 2005-06-03 | 2006-12-07 | Tsinghua University | Method for preparing 1,3-propanediol by using glycerine as the by-product of the biological diesel oil |
| CN1327001C (en) * | 2005-06-03 | 2007-07-18 | 清华大学 | Method for producing 1,3-propylene glycol through using glycerin of by-product from biologic diesel oil |
| CN100463968C (en) * | 2006-01-27 | 2009-02-25 | 华侨大学 | Process for preparing 1,3-propylene glycol and dihydroxy acetone by bio-catalytic conversion of glycerol |
| US8324434B2 (en) | 2008-03-02 | 2012-12-04 | Dow Global Technologies, Llc | Hydrogenation process |
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| Publication number | Publication date |
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| CN1206362C (en) | 2005-06-15 |
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