CN114806961A - Fermentation medium and method for producing bio-based 1, 3-propylene glycol - Google Patents
Fermentation medium and method for producing bio-based 1, 3-propylene glycol Download PDFInfo
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- propanediol
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- 238000000855 fermentation Methods 0.000 title claims abstract description 126
- 230000004151 fermentation Effects 0.000 title claims abstract description 126
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000011573 trace mineral Substances 0.000 claims abstract description 44
- 235000013619 trace mineral Nutrition 0.000 claims abstract description 44
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 32
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 30
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 28
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims abstract description 19
- 229940035437 1,3-propanediol Drugs 0.000 claims abstract description 19
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims abstract description 19
- 239000004202 carbamide Substances 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 14
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 14
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 14
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229960002089 ferrous chloride Drugs 0.000 claims abstract description 14
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000011565 manganese chloride Substances 0.000 claims abstract description 14
- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 14
- 229940099607 manganese chloride Drugs 0.000 claims abstract description 14
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 14
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 14
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011592 zinc chloride Substances 0.000 claims abstract description 14
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 11
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 8
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims abstract description 8
- 235000019838 diammonium phosphate Nutrition 0.000 claims abstract description 8
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 8
- 241000588748 Klebsiella Species 0.000 claims abstract description 7
- 238000000909 electrodialysis Methods 0.000 claims description 18
- 238000010612 desalination reaction Methods 0.000 claims description 16
- 238000005374 membrane filtration Methods 0.000 claims description 6
- 238000000108 ultra-filtration Methods 0.000 claims description 6
- 239000005696 Diammonium phosphate Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 3
- 238000012262 fermentative production Methods 0.000 claims description 2
- 238000011081 inoculation Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000009655 industrial fermentation Methods 0.000 claims 1
- 239000002609 medium Substances 0.000 abstract description 23
- 235000013877 carbamide Nutrition 0.000 abstract description 16
- 239000001963 growth medium Substances 0.000 abstract description 15
- 150000003839 salts Chemical class 0.000 abstract description 15
- 239000007788 liquid Substances 0.000 abstract description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 abstract description 7
- 239000000843 powder Substances 0.000 abstract description 6
- 240000004808 Saccharomyces cerevisiae Species 0.000 abstract description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 abstract description 3
- 235000019341 magnesium sulphate Nutrition 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 238000004659 sterilization and disinfection Methods 0.000 description 14
- 230000001954 sterilising effect Effects 0.000 description 12
- 238000005265 energy consumption Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 6
- 235000011130 ammonium sulphate Nutrition 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 5
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 3
- 235000019289 ammonium phosphates Nutrition 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229940041514 candida albicans extract Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 150000002894 organic compounds Chemical group 0.000 description 2
- 125000001477 organic nitrogen group Chemical group 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- -1 polytrimethylene terephthalate Polymers 0.000 description 2
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000012138 yeast extract Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 239000000592 Artificial Cell Substances 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- AWADHHRPTLLUKK-UHFFFAOYSA-N diazanium sulfuric acid sulfate Chemical compound [NH4+].[NH4+].OS(O)(=O)=O.[O-]S([O-])(=O)=O AWADHHRPTLLUKK-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/20—Bacteria; Culture media therefor
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/38—Chemical stimulation of growth or activity by addition of chemical compounds which are not essential growth factors; Stimulation of growth by removal of a chemical compound
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/18—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic polyhydric
Abstract
The invention discloses a fermentation medium and a method for producing bio-based 1, 3-propylene glycol, wherein the fermentation medium comprises glycerol, yeast powder, urea, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, magnesium sulfate, a trace element solution and water; the trace element solution comprises ferrous chloride, cobalt chloride, zinc chloride, manganese chloride, copper chloride and sodium molybdate, the trace elements are dissolved by water or hydrochloric acid, and the content of the trace elements in the trace element solution is controlled to be 1-10 g/L; the method comprises the steps of adopting Klebsiella as a fermentation strain, inoculating the Klebsiella in the fermentation culture medium for fermentation to obtain a fermentation liquid containing 1, 3-propanediol, purifying the fermentation liquid to obtain the purified 1, 3-propanediol, wherein the fermentation culture medium can obviously reduce the salt concentration in the fermentation liquid in the process of producing PDO by fermentation, and can also obtain relatively higher target product concentration, and the production cost is relatively reduced.
Description
Technical Field
The invention relates to the field of new materials (raw materials) of bio-based fibers, in particular to a fermentation medium and a method for producing bio-based 1, 3-propylene glycol.
Background
1, 3-Propanediol (PDO) and 2, 3-Butanediol (BDO) are important chemical raw materials, and the PDO is a key raw material for synthesizing the memory fiber polytrimethylene terephthalate (PTT).
At present, in the process of producing PDO by a microbial fermentation method, organic nitrogen is yeast extract powder and inorganic nitrogen is ammonium sulfate in used nitrogen sources, wherein the organic nitrogen yeast extract powder has slow effect, the inorganic nitrogen ammonium sulfate has fast effect, and phosphorus is also an important element of synthetic cells, so dipotassium hydrogen phosphate and potassium dihydrogen phosphate are conventional components in a fermentation medium. However, in the practical process, when PDO is produced by a microbial fermentation method, the obtained 1, 3-propylene glycol (PDO) fermentation liquor has high salt content, which causes great trouble for the later separation of 1, 3-propylene glycol, so that the quality of the purified product of 1, 3-propylene glycol (PDO) is influenced by the salt content, and the salt content is easy to exist in the wastewater.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an improved fermentation medium, which can obviously reduce the salt concentration in the fermentation liquor in the process of producing 1, 3-Propanediol (PDO) by fermentation, and can also obtain relatively higher 1, 3-Propanediol (PDO) product concentration and relatively reduce the production cost.
The invention also provides an application of the fermentation medium in production of the bio-based 1, 3-propylene glycol.
In order to achieve the purpose, the invention adopts a technical scheme that:
a fermentation medium for producing 1, 3-propanediol by biological fermentation comprises the following components in addition amounts:
the trace element solution comprises trace elements and water or hydrochloric acid for dissolving the trace elements, the trace elements comprise ferrous chloride, cobalt chloride, zinc chloride, manganese chloride, copper chloride and sodium molybdate, the charging mass ratio of the ferrous chloride, the cobalt chloride, the zinc chloride, the manganese chloride, the copper chloride and the sodium molybdate is (0.5-2.0): (0.2-0.8): and the content of the trace elements in the trace element solution is controlled to be 1-10 g/L.
Further, the fermentation medium comprises the following components in addition amount:
the trace element solution consists of the following components: ferrous chloride, cobalt chloride, zinc chloride, manganese chloride, copper chloride, sodium molybdate and water or hydrochloric acid, wherein the charging mass ratio of the ferrous chloride, the cobalt chloride, the zinc chloride, the manganese chloride, the copper chloride and the sodium molybdate is (0.5-2.0): (0.2-0.8): and the content of trace elements in the trace element solution is controlled to be 1-6 g/L.
According to some preferred aspects of the present invention, the feeding mass ratio of the urea, the diammonium hydrogen phosphate and the ammonium dihydrogen phosphate is 1: 0.2-0.35: 0.08-0.25, and the addition mass of the diammonium hydrogen phosphate is larger than that of the ammonium dihydrogen phosphate.
According to some preferred aspects of the invention, the charging mass ratio of the ferrous chloride, the cobalt chloride, the zinc chloride, the manganese chloride, the copper chloride and the sodium molybdate is (0.5-1.5): (0.2-0.5): (0.5-0.8): (0.2-0.4): (0.3-0.5): (0.4-0.6).
According to some preferred aspects of the invention, the pH of the fermentation medium is 6.5-7.5.
The invention provides another technical scheme that: a method for the biological fermentative production of 1, 3-propanediol comprising: the method comprises the steps of adopting Klebsiella as a fermentation strain, inoculating the Klebsiella into the fermentation culture medium for fermentation to obtain fermentation liquor containing 1, 3-propanediol, and then purifying the fermentation liquor to obtain the purified 1, 3-propanediol.
According to some preferred and specific aspects of the invention, the purification comprises ultrafiltration, electrodialysis desalination, performed in sequence.
According to the invention, the fermentation medium is sterilized by membrane filtration before inoculation.
According to some preferred aspects of the invention, the process of fermentation is carried out on an industrial fermentor, the process of fermentation being controlled in that: the fermentation temperature is 34-38 deg.C, the air amount is 0.1-0.5vvm, the pH value is 6.5-7.5, and the fermentation is carried out under the stirring condition of 40-80 rpm.
According to some preferred aspects of the invention, the concentration of glycerol is maintained at 5-30g/L by adding fresh glycerol during the fermentation process.
In the invention, the magnesium sulfate and other trace elements are used, and the raw materials can contain crystal water or be anhydrous.
In the invention, the preparation of the fermentation medium is convenient, and the magnesium sulfate represents magnesium sulfate heptahydrate, but does not represent that only magnesium sulfate heptahydrate can be used in the invention, and anhydrous magnesium sulfate can also be used, and only the conversion of the addition amount is needed; other components possibly containing crystal water in the trace elements can be dried before being added, so that the accurate measurement and compounding of each component are facilitated.
In the present invention, urea (urea), also called urea and carbamide, is used, and the chemical formula is CH 4 N 2 O or CO (NH) 2 ) 2 It is an organic compound composed of carbon, nitrogen, oxygen and hydrogen, and is a white crystal. One of the simplest organic compounds is the major nitrogen-containing end product of the metabolic breakdown of proteins in mammals and certain fish.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the method is based on the problems that the prior 1, 3-propylene glycol fermentation liquor contains too much salt, has high difficulty in later separation, is incomplete in separation, has high separation cost, is difficult in sewage treatment and the like. After continuous practical summary, it is considered by analysis that PDO is generated due to the metabolism of the bacteria, organic acids such as succinic acid, acetic acid, lactic acid, etc. are generated, and in addition, after ammonium ions in the ammonium sulfate used as the nitrogen source are consumed, sulfate ions remain in the fermentation broth, the pH value of the fermentation broth is also reduced, in order to maintain the pH value of the fermentation broth to be neutral, an alkaline substance such as sodium hydroxide (which can be added in the form of an aqueous solution) is generally automatically fed into the fermentation broth, sodium ions and anions are combined to form a salt, wherein the sulfate radicals and the sodium ions are combined to form sodium sulfate which cannot be degraded, potassium ions in the existing phosphorus source such as potassium dihydrogen phosphate and dipotassium hydrogen phosphate remain in the fermentation broth to increase the salt content of the fermentation broth, the salt in the fermentation broth is separated and purified by an electrodialysis desalination process in a post-extraction process, and the salt-containing wastewater finally enters a wastewater treatment system, non-degradable sodium sulfate can increase the difficulty and cost of wastewater treatment.
Based on the analysis and summary, the invention innovatively provides a novel nitrogen and phosphorus source formula-a method for replacing conventional ammonium sulfate by the combination of urea and ammonium phosphate, on one hand, the concentration of salt in sewage can be reduced, the influence of the salt on the anaerobic and aerobic treatment processes of the sewage is reduced, the concentration of inorganic salt in the wastewater with qualified discharge indexes such as COD (chemical oxygen demand) and the like is reduced, the environmental influence is reduced, and the anhydrous treatment difficulty is reduced; on the other hand, the salt content of the fermentation liquor is reduced, the load of an electrodialysis desalination process is lightened, the power consumption is reduced, and after the original formula is replaced by the new formula, the concentration of sulfate ions in the fermentation liquor can be reduced, so that the total salt content of the fermentation liquor is reduced, the conductivity of the fermentation liquor is reduced by 18%, the electrodialysis desalination energy consumption is reduced by nearly 18%, the annual electricity cost is saved by about 80 ten thousand yuan, in addition, the treatment capacity of the electrodialysis equipment is improved, and the economic benefit is improved; furthermore, under the same nitrogen content, the urea dosage is 45.45% of the ammonium sulfate (the urea dosage is 45.45% of the ammonium sulfate, theoretically, the cost can be saved by 150 yuan per ton of PDO produced, and the production cost can be saved by 300 ten thousand yuan per year in the whole plant), and the urea can be used as a nitrogen source and a carbon source, so that the cost of raw materials in the PDO fermentation process can be saved.
Meanwhile, the fermentation medium can adopt a filtration sterilization mode, on one hand, the problem that urea is decomposed due to high temperature adopted in the existing common high-temperature sterilization process is solved, on the other hand, the steam consumption in the sterilization process is greatly reduced, the production cost of PDO is reduced, the original high-temperature sterilization is replaced by sterilization in a membrane filtration mode, the steam consumption is greatly reduced, and the annual culture medium sterilization energy consumption is over 330 ten thousand yuan.
In addition, the nitrogen and phosphorus source formula of the invention, namely the combination of urea and ammonium phosphate and the combined fermentation of specific trace elements, also realizes a relatively excellent fermentation level, so that the PDO content in the fermentation liquid can reach more than 95 g/L.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise.
FIG. 1 is a schematic process flow diagram employed in an embodiment of the present invention;
wherein, 1, a membrane filter; 2. filtering out the bacteria culture medium; 3. a fermentation tank; 4. fermentation liquor; 5. an ultrafiltration device; 6. ultrafiltering the filtrate; 7. an electrodialysis unit; 8. desalting solution.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
In the following, all starting materials are either commercially available or prepared according to methods conventional in the art, unless otherwise indicated. In the following, each of the trace elements in the trace element solution is an anhydrous component. The data were determined by methods common in the art for each experiment.
Example 1
The embodiment provides a fermentation medium and a method for producing 1, 3-propylene glycol by adopting the fermentation medium through biological fermentation, wherein the fermentation medium comprises the following components in addition amount: 10g/L of glycerol; 1g/L of yeast powder; 1.2g/L of urea; diammonium phosphate is 0.3 g/L; 0.2g/L of ammonium dihydrogen phosphate; magnesium sulfate heptahydrate 0.15 g/L; 1mL/L of trace element solution; the balance of water;
the trace element solution comprises: the trace elements are dissolved by hydrochloric acid (mass fraction is 5%), the mass ratio of the ferrous chloride, the cobalt chloride, the zinc chloride, the manganese chloride, the copper chloride and the sodium molybdate is 1: 0.4: 0.6: 0.3: 0.4: 0.5, and the content of the trace elements in the trace element solution is controlled to be 5 g/L.
Performing biological fermentation on the fermentation culture medium to produce 1, 3-propylene glycol, wherein the method adopts the process flow shown in figure 1, firstly, a membrane filter 1 (50 nm ceramic membrane is adopted as the membrane) is adopted to perform membrane filtration on the fermentation culture medium to obtain the filtration sterilizationThe culture medium 2 is then placed in a fermentation tank 3, the Klebsiella as a fermentation strain is inoculated in the filtered bacteria culture medium 2 for fermentation, and the fermentation process is controlled as follows: fermenting at 36 deg.C with introduced air of 0.2vvm and pH of 6.75 under stirring at 60rpm, adding new glycerol to make glycerol concentration about 10g/L, fermenting for 48 hr to obtain fermentation broth 4, ultrafiltering with ultrafilter 5 to obtain ultrafiltrate 6, electrodialysis desalting with electrodialysis device 7 in 12-stage series connection, and continuously operating, wherein the membrane area of each stage is 125m 2 The operation voltage is 1V/pair of membranes, the initial concentrated water of electrodialysis is pure water, the electrode chamber liquid is 0.05mol/L sodium sulfate solution, the conductivity is controlled to be less than or equal to 2000 mus/cm at the end point of electrodialysis desalination, desalted liquid 8 is obtained, and then the purified 1, 3-propylene glycol is obtained through other rectification and adsorption treatments.
The experimental data of the fermentation liquid obtained by feeding the fermentation liquid into the tank for 48 hours are shown in Table 1.
TABLE 1
The culture medium adopts membrane filtration sterilization, the main energy consumption is power consumption, and the power consumption of the culture medium per unit volume is as follows: 5 kw.h/m 3 According to the price of electricity of 0.77 yuan/(kw.h), the disinfection cost of the culture medium per unit volume is calculated to be 3.85 yuan/m 3 . In addition, as can be seen from the data in Table 1, the PDO fermentation level adopting the new formula can reach 96.27g/L, the conductivity of the fermentation liquor is reduced by about 23 percent compared with that of the fermentation liquor of the following comparative example, the fermentation liquor is subjected to electrodialysis desalination after ultrafiltration, and the desalination energy consumption is 11.6 kw.h/m 3 Compared with the comparative example fermentation liquor electrodialysis desalination energy consumption is reduced by 18.6%.
Comparative example
Basically, the method is the same as the method of the embodiment 1, and the method only differs from the method in that: replacing urea in a fermentation medium with 2.6g/L ammonium sulfate, and replacing ammonium phosphate with 0.71g/L dipotassium hydrogen phosphate and 0.35g/L potassium dihydrogen phosphate so as to ensure equal addition amounts of nitrogen and phosphorus; meanwhile, the membrane filtration sterilization mode is changed into high-temperature sterilization treatment (effective sterilization at 125 ℃ for 20 minutes).
Wherein, in the fermentation liquor obtained by fermentation for 48 hours, the sodium sulfate is 3.4g/L, and the conductivity is 17250 mus/cm.
The culture medium adopts a high-temperature sterilization mode of keeping the temperature at 125 ℃ for 20 minutes for sterilization, the main energy consumption is steam, and the steam consumption of the culture medium per unit volume is as follows: 0.1 ton/m 3 The disinfection cost of the culture medium per unit volume is calculated to be 20 yuan/m according to the steam price of 200 yuan/ton 3 . The fermentation liquor is subjected to electrodialysis desalination after ultrafiltration, and the desalination energy consumption is 14.25 kw.h/m 3 。
Example 2
The embodiment provides a fermentation medium and a method for producing 1, 3-propylene glycol by adopting the fermentation medium through biological fermentation, wherein the fermentation medium comprises the following components in addition amount: 15g/L of glycerol; 1.2g/L of yeast powder; 1.5g/L of urea; diammonium phosphate 0.3 g/L; 0.2g/L of ammonium dihydrogen phosphate; magnesium sulfate heptahydrate 0.15 g/L; 1mL/L of trace element solution; the balance of water;
the trace element solution comprises: the trace elements are dissolved by hydrochloric acid (mass fraction is 5%), the mass ratio of the ferrous chloride to the cobalt chloride to the zinc chloride to the manganese chloride to the copper chloride to the sodium molybdate is 1.5: 0.2: 0.5: 0.2: 0.3: 0.4, and the content of the trace elements in the trace element solution is controlled to be 4 g/L.
The process for producing 1, 3-propanediol by biological fermentation is the same as in example 1.
The experimental data of the fermentation liquid obtained by feeding the fermentation liquid into the tank for 48 hours are shown in Table 2.
TABLE 2
As can be seen from the data in Table 2, the PDO fermentation level can reach 97.95g/L by adopting the new formula. Compared with the prior fermentation liquor, the conductivity of the fermentation liquor is reduced by about 27 percent, and the fermentation liquor is subjected to electrodialysis desalination and dehydration after ultrafiltrationThe energy consumption of the salt is 11.3 kw.h/m 3 Compared with the comparative example fermentation liquor electrodialysis desalination energy consumption is reduced by 20.7%.
Example 3
The embodiment provides a fermentation medium and a method for producing 1, 3-propylene glycol by adopting the fermentation medium through biological fermentation, wherein the fermentation medium comprises the following components in addition amount: 10g/L of glycerol; 1g/L of yeast powder; 1.2g/L of urea; diammonium phosphate is 0.3 g/L; 0.2g/L of ammonium dihydrogen phosphate; magnesium sulfate heptahydrate 0.15 g/L; 1mL/L of trace element solution; the balance of water;
the trace element solution comprises: the trace elements are dissolved by hydrochloric acid (mass fraction is 5%), the mass ratio of the ferrous chloride to the cobalt chloride to the zinc chloride to the manganese chloride to the copper chloride to the sodium molybdate is 1.5: 0.5: 0.8: 0.4: 0.5: 0.6, and the content of the trace elements in the trace element solution is controlled to be 6 g/L.
The process for producing 1, 3-propanediol by fermentation by a biological method is the same as in example 1.
The experimental data of the fermentation liquid obtained by feeding the fermentation liquid into the tank for 48 hours are shown in Table 3.
TABLE 3
As can be seen from the data in Table 3, the PDO fermentation level adopting the new formula can reach 98.02g/L, the conductivity of the fermentation liquor is reduced by about 22.3% compared with that of the comparative fermentation liquor, the fermentation liquor is subjected to electrodialysis desalination after ultrafiltration, and the desalination energy consumption is 12.0 kw.h/m 3 Compared with the comparative example fermentation liquor electrodialysis desalination energy consumption is reduced by 15.8%.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A fermentation medium is characterized in that the fermentation medium is used for producing 1, 3-propanediol by biological fermentation, and the fermentation medium comprises the following components in addition amounts:
the trace element solution comprises trace elements and water or hydrochloric acid for dissolving the trace elements, the trace elements comprise ferrous chloride, cobalt chloride, zinc chloride, manganese chloride, copper chloride and sodium molybdate, the feeding mass ratio of the ferrous chloride, the cobalt chloride, the zinc chloride, the manganese chloride, the copper chloride and the sodium molybdate is (0.5-2.0): (0.2-0.8): 0.2-0.8), and the content of the trace elements in the trace element solution is controlled to be 1-10 g/L.
2. The fermentation medium of claim 1, comprising the following components in the following amounts:
the trace element solution consists of the following components: the trace element solution comprises ferrous chloride, cobalt chloride, zinc chloride, manganese chloride, copper chloride, sodium molybdate and water or hydrochloric acid, wherein the charging mass ratio of the ferrous chloride to the cobalt chloride to the zinc chloride to the manganese chloride to the copper chloride to the sodium molybdate is (0.5-2.0) to (0.2-0.8), and the content of trace elements in the trace element solution is controlled to be 1-6 g/L.
3. The fermentation medium according to claim 1 or 2, wherein the mass ratio of the urea to the diammonium phosphate to the ammonium dihydrogen phosphate is 1: 0.2-0.35: 0.08-0.25, and the mass of the diammonium phosphate added is greater than that of the ammonium dihydrogen phosphate.
4. The fermentation medium according to claim 1 or 2, wherein the charging mass ratio of the ferrous chloride, the cobalt chloride, the zinc chloride, the manganese chloride, the copper chloride and the sodium molybdate is (0.5-1.5) to (0.2-0.5) to (0.5-0.8) to (0.2-0.4) to (0.3-0.5) to (0.4-0.6).
5. The fermentation medium of claim 1, wherein the fermentation medium has a pH of 6.5 to 7.5.
6. A method for producing 1, 3-propanediol by biological fermentation, the method comprising: the method comprises the steps of adopting Klebsiella as a fermentation strain, inoculating the Klebsiella into the fermentation medium of any one of claims 1-5, fermenting to obtain a fermentation liquor containing 1, 3-propanediol, and purifying the fermentation liquor to obtain the purified 1, 3-propanediol.
7. The method for the fermentative production of 1, 3-propanediol according to claim 6, wherein the purification comprises ultrafiltration and electrodialysis desalination in sequence.
8. The method for producing 1, 3-propanediol by biological fermentation according to claim 6, wherein the fermentation medium is sterilized by membrane filtration before inoculation.
9. The method for producing 1, 3-propanediol by biological fermentation according to claim 1, wherein the fermentation process is performed in an industrial fermentation tank, and the fermentation process is controlled as follows: the fermentation temperature is 34-38 deg.C, the air amount is 0.1-0.5vvm, the pH value is 6.5-7.5, and the fermentation is carried out under the stirring condition of 40-80 rpm.
10. The method for producing 1, 3-propanediol by biological fermentation according to claim 1, wherein the concentration of glycerol is always 5-30g/L by adding new glycerol during the fermentation process.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1357628A (en) * | 2001-12-05 | 2002-07-10 | 大连理工大学 | Two-step microbial fermentation process of producing propylene glycol |
| CN101376899A (en) * | 2007-08-30 | 2009-03-04 | 黑龙江辰能生物工程有限公司 | Method for producing 1,3-propanediol by fermentation method with urea as nitrogen source |
| CN110541004A (en) * | 2019-09-30 | 2019-12-06 | 江南大学 | Method for producing 1, 3-propylene glycol |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1357628A (en) * | 2001-12-05 | 2002-07-10 | 大连理工大学 | Two-step microbial fermentation process of producing propylene glycol |
| CN101376899A (en) * | 2007-08-30 | 2009-03-04 | 黑龙江辰能生物工程有限公司 | Method for producing 1,3-propanediol by fermentation method with urea as nitrogen source |
| CN110541004A (en) * | 2019-09-30 | 2019-12-06 | 江南大学 | Method for producing 1, 3-propylene glycol |
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