CN106497992A - Method for preparing gluconic acid or gluconate by using supergravity technology - Google Patents
Method for preparing gluconic acid or gluconate by using supergravity technology Download PDFInfo
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- CN106497992A CN106497992A CN201611048589.8A CN201611048589A CN106497992A CN 106497992 A CN106497992 A CN 106497992A CN 201611048589 A CN201611048589 A CN 201611048589A CN 106497992 A CN106497992 A CN 106497992A
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- gluconic acid
- gluconate
- glucose
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- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 title claims abstract description 58
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000000174 gluconic acid Substances 0.000 title claims abstract description 40
- 235000012208 gluconic acid Nutrition 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000005516 engineering process Methods 0.000 title claims abstract description 25
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 title claims abstract description 17
- 229940050410 gluconate Drugs 0.000 title claims abstract description 17
- 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 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000001301 oxygen Substances 0.000 claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 45
- 239000008103 glucose Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 108010015776 Glucose oxidase Proteins 0.000 claims abstract description 26
- 239000004366 Glucose oxidase Substances 0.000 claims abstract description 26
- 229940116332 glucose oxidase Drugs 0.000 claims abstract description 26
- 235000019420 glucose oxidase Nutrition 0.000 claims abstract description 26
- 229940088598 enzyme Drugs 0.000 claims abstract description 25
- 102000004190 Enzymes Human genes 0.000 claims abstract description 24
- 108090000790 Enzymes Proteins 0.000 claims abstract description 23
- 102000016938 Catalase Human genes 0.000 claims abstract description 13
- 108010053835 Catalase Proteins 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 15
- 239000000376 reactant Substances 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 17
- 230000003647 oxidation Effects 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 14
- 238000012546 transfer Methods 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 17
- 150000003839 salts Chemical class 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000000855 fermentation Methods 0.000 description 11
- 230000004151 fermentation Effects 0.000 description 11
- 230000008859 change Effects 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000002255 enzymatic effect Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 241000219095 Vitis Species 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 239000004227 calcium gluconate Substances 0.000 description 4
- 229960004494 calcium gluconate Drugs 0.000 description 4
- 235000013927 calcium gluconate Nutrition 0.000 description 4
- NEEHYRZPVYRGPP-UHFFFAOYSA-L calcium;2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(O)C([O-])=O.OCC(O)C(O)C(O)C(O)C([O-])=O NEEHYRZPVYRGPP-UHFFFAOYSA-L 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 235000009392 Vitis Nutrition 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- NDVRKEKNSBMTAX-BTVCFUMJSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;phosphoric acid Chemical compound OP(O)(O)=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O NDVRKEKNSBMTAX-BTVCFUMJSA-N 0.000 description 2
- NAOLWIGVYRIGTP-UHFFFAOYSA-N 1,3,5-trihydroxyanthracene-9,10-dione Chemical compound C1=CC(O)=C2C(=O)C3=CC(O)=CC(O)=C3C(=O)C2=C1 NAOLWIGVYRIGTP-UHFFFAOYSA-N 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 235000009754 Vitis X bourquina Nutrition 0.000 description 2
- 235000012333 Vitis X labruscana Nutrition 0.000 description 2
- 235000014787 Vitis vinifera Nutrition 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229960005069 calcium Drugs 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 239000000176 sodium gluconate Substances 0.000 description 2
- 235000012207 sodium gluconate Nutrition 0.000 description 2
- 229940005574 sodium gluconate Drugs 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 208000000058 Anaplasia Diseases 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000007184 Hibiscus schizopetalus Nutrition 0.000 description 1
- 244000197258 Hibiscus schizopetalus Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 108010093096 Immobilized Enzymes Proteins 0.000 description 1
- 108010091086 Recombinases Proteins 0.000 description 1
- 102000018120 Recombinases Human genes 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 description 1
- 239000000159 acid neutralizing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- -1 cation salt Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 125000003051 glycosyloxy group Chemical group 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011670 zinc gluconate Substances 0.000 description 1
- 235000011478 zinc gluconate Nutrition 0.000 description 1
- 229960000306 zinc gluconate Drugs 0.000 description 1
Classifications
-
- 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
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
- C12P7/58—Aldonic, ketoaldonic or saccharic acids
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Biotechnology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a method for preparing gluconic acid or gluconate by a supergravity technology. In the process of enzyme catalytic oxidation, the reaction temperature is 30-60 ℃, the concentration of glucose is 100-1000g/L, and the dosage of glucose oxidase and catalase is 0.1-5% of the mass of glucose. Compared with the traditional method for preparing gluconic acid by oxidizing the glucolase in the ventilating and stirring kettle, the method has the advantages of high mass transfer efficiency of oxygen, enzyme dosage reduction, greatly shortened reaction time, cost reduction and easy industrialization.
Description
Technical field
The invention belongs to the field of chemical synthesis, and in particular to one kind is catalyzed Portugal by high-gravity technology by glucoseoxidase
The method that grape sugar prepares gluconic acid or gluconate.
Background technology
Gluconic acid and its salt are the important Organic chemical products of a class.Gluconic acid can be prevented in dairy processing industry
Mammary calculus is precipitated；Make acidic flavoring agent in food formula；For configuring auxiliary agent, the leather vitriol of abluent, fabric processing and intermetallic composite coating
Tanning agent, Deruster for metal, the water reducer of concrete, biodegradable chelating agen, the antisettling agent of secondary oil recovery in building industry
Deng.Gluconic acid is obtained metal cation salt with reactive metal oxides such as sodium, calcium, zinc, ferrous irons, and they are in chemical industry, food, doctor
The industries such as medicine, light industry have a wide range of applications.It is many that sodium gluconate is used for water treatment, plating etc. as excellent chelating agen
Individual department；Calcium gluconate, zinc, ferrous iron, magnesium etc. are used for food service industry, supplement needed by human body element.
At present, the manufacturer of gluconic acid and its salt is concentrated mainly on the states such as China, Japan, France, the U.S. in the world
Family, wherein China are global maximum gluconic acid and its salt manufacturing country and exported country.The recent statistics data display of 2013,
The sodium gluconate production capacity of China is 147.46 ten thousand tons, actual production proportion up to global production capacity more than 70%.Portugal of China
There are Shandong Kaison Biochemical Co., Ltd., Yanzhou bio tech ltd of Parkson, mountain in the manufacturing enterprise of grape saccharic acid and its salt
Eastern Xiwang Group Co., Ltd etc., and mainly there is the contributing 150,000 tons of production capacity of sieve lid of France in external manufacturer, Japanese
Hibiscus rosa-sinensis' about 130,000 tons of production capacity of chemistry, about 80,000 tons of production capacity of Jungbunzlauer of Switzerland.Industrialized glucose
The method of acid and its salt synthesis mainly has catalytic oxidation, electrolytic oxidation, fermentation method and enzyme process.With catalytic oxidation and electrolysis
Oxidizing process is compared, fermentation method is so that its reaction condition is gentle, the succinct environmental protection of process route, the low advantage of product cost, have become
Gluconic acid and its dominant technology of salt production.But still suffer from production process fermentation time length, product purity not enough, zymocyte
Body needs the problems such as further processing.Enzyme process is then the specificity using glucoseoxidase, by Fructus Vitis viniferae under molecular oxygen effect
Glycoxidative become gluconic acid lactone, while produce hydrogen peroxide.Gluconic acid lactone automatic hydrolysis generation gluconic acid, and mistake
Hydrogen oxide is then decomposed into oxygen and water under catalatic effect.Enzyme process compared with fermentation method with the production cycle shorter,
Safe operation is simple, the advantages such as low and product purity is high invested by plant and equipment, is increasingly paid close attention to by researcher.
At present, domestic Production by Enzymes gluconic acid and its salt also relevant report.Enzyme preparation manufacturer Jie Neng sections biological engineering
Zhou Hongwei of company limited et al. once in 2007 and delivered respectively within 2009 Production by Enzymes calcium gluconate new technology [food
Product and fermentation industry, 2007,33 (7):99-101] and a step enzyme method be directly produced paper [food and the fermentation of zinc gluconate
Industry, 2007,35 (10):77-80], simple Jie has been done to the technological process and process conditions of Production by Enzymes gluconate
Continuing and study. Wang Di of Xiwang Group Co., Ltd etc. produces the base of calcium gluconate method in existing free state combined-enzyme method
Improved on plinth, glucoseoxidase and catalase are added sodium alginate and silica gel mixed solution, then instills chlorine
Change fixed-type in calcium solution；By glucoseoxidase and being fixed of catalase, realize that enzyme liquid is separated, improve Portugal
Glucoseoxidase and catalatic recycling rate of waterused, reduce the use cost of enzyme, have saved production cost, by this law
Calcium gluconate product purity height [CN201310457583.6] of production.Tan Tianwei of Beijing University of Chemical Technology etc. develops one kind
Novel carriers, can effectively facilitate glucoseoxidase/catalase and microsphere supported covalent attachment, substantially increase fixation
Change efficiency, and significantly extend the service life of mixed immobilized glucose oxidase/catalase, can Reusability,
Low production cost [CN201210488451.5].In addition, the Yang Meng of Inner Mongol Yu Wang biotechnologies development corporation, Ltd.
The Zhang Bingtuan [CN201410439491.X] of [CN201410189476.4], Dancheng Caixin Sugar Co., Ltd., the south of the River are big
Yu Xiaobin [CN201410707720.1] etc. also all applied using resolvase or immobilized enzyme prepare gluconic acid and its
The patent of salt.
When enzyme process oxidizing glucose prepares gluconic acid and its salt, the participation of oxygen is essential condition.However,
The oxygen that enzyme can be utilized can only be dissolved in the dissolved oxygen in water, and the level of dissolved oxygen directly affects the efficiency of reaction.Many institutes
Known, under room temperature, 1atm, dissolubility of the oxygen in water is very low, only 8.11mg/L (0.25mmol/L).The bottom of relative to
The amount of thing glucose（100-1000g/L, 0.5-5mol/L）, the amount of dissolved oxygen in water just started just to be consumed end in reaction.Will
Think the efficiency for persistently keeping enzymatic oxidation, then need the volume transmission quality coefficient for increasing oxygen.In retort, the mass transfer of oxygen is improved
Speed is mainly stirred and ventilation by increasing.But ventilation is excessive not only to cause energy waste, foam to increase generation and escape liquid,
Reduce activity coefficient, and sugar liquid moisture can also evaporate too fast, be that sugared concentration increases, unfavorable to reacting.And long-time is increased and is stirred
Mix the deactivation rate increase that will also result in enzyme.Therefore, select suitable reactor to improve the volume transmission quality coefficient of oxygen, allow and reacted
In journey, dissolved oxygen remains at higher level, and for enzymatic oxidation efficiency is improved, reducing energy consumption has important value.
Content of the invention
Prepare for enzymatic oxidation glucose that the oxygen transfer rate existed during gluconic acid and its salt is low to be lacked
Fall into, it is an object of the invention to provide a kind of strengthen oxygen transfer efficiency by supergravity reactor, so as to improve enzyme law catalysis oxygen
Change the method that glucose prepares gluconic acid and its salt efficiency.
The present invention provide one kind by high-gravity technology by glucoseoxidase catalysis glucose prepare gluconic acid or
The method of gluconate, it is characterised in that it comprises the following steps：
1）Glucose and water heated and stirred are dissolved to reaction temperature, are sprayed on the revolving bed of supergravity reactor, is passed through air,
Its dissolved oxygen is made to reach saturation；
2）The glucoseoxidase of catalytic amount, catalase are added in reactant liquor, circular response is simultaneously introduced alkali or acid
Nertralizer adjusts reactant liquor pH；
3）Treat that glucose consumption terminates, stopped reaction when reactant liquor pH remains unchanged, postmenstruation neutralization, concentration, crystallization, dry at
Gluconic acid or gluconate is obtained after reason.
Supergravity reactor of the present invention can be horizontal supergravity reactor, or the reaction of vertical hypergravity
Device, or internal-circulation type supergravity reactor.
Step 1）The concentration of middle D/W is 100-1000g/L.
Step 1）Middle reaction temperature is 30-60 DEG C；Flow rate of liquid is 1mL/s-10mL/s；Air and D/W
Gas liquid ratio is 1:5-20；Revolving bed rotating speed is 750-3000r/min.Preferred liquid flow velocity 2-5mL/s, gas liquid ratio is 1:5-1:
10, reaction temperature is 40-50 DEG C, and revolving bed rotating speed is 1000-1500 r/min.
Step 2）The 0.1-5% of middle glucoseoxidase, catalatic consumption for glucose quality（I.e.：The Portugal of 100g
Grape sugar, glucoseoxidase are 0.1-5g with catalatic consumption）；Glucoseoxidase and catalatic enzyme activity ratio
For 1:1-1:10.It is preferred that the 0.5-2% of glucoseoxidase, catalatic consumption for glucose quality, glucoseoxidase
It is 1 with catalatic enzyme activity ratio:2-1:5, during enzymatic oxidation reaction temperature at 30-60 DEG C, preferably 40-50
℃.
Step 2）Employed in alkali or acid neutralizing agent be sodium hydroxide, potassium hydroxide, calcium hydroxide, zinc oxide, oxidation
Magnesium, ferrous oxide, Calcium Carbonate etc.；Reactant liquor pH is controlled between 6-8.
Step 3）When middle concentration of glucose is reduced to 0.1-0.5g/L, reaction terminates.
The present invention strengthened using high-gravity technology glucoseoxidase catalytic oxidation of glucose prepare gluconic acid and its
Oxygen mass transfer efficiency during salt.High-gravity technology is the unique flow behavior using multiphase flow system under the conditions of hypergravity,
Strengthen relative velocity between phase and phase and contact with each other, so as to realize efficient mass transfer, diabatic process and chemical reaction process.
Under powerful centrifugal action produced by supergravity reactor, huge shear stress overcomes surface tension, can make liquid
Body stretches out huge phase border contact interface, so as to greatly strengthen mass transport process.Portugal is prepared in enzyme law catalysis oxidizing glucose
During grape saccharic acid and its salt, air through gas inlet tube by being introduced tangentially into rotor exocoel, by turning in the presence of gas pressure
Filler is entered at sub- outer rim.The mixed solution that glucose and enzyme are formed introduces rotor internal cavity by liquid inlet tube, through shower nozzle sprinkle
On rotor inner edge.The liquid for entering rotor is acted on by filler in rotor, and circumferential speed increases, and produced centrifugal force will
Which pushes rotor periphery to.In the process, the filled dispersion of liquid, crushing-type are into surface area that is great, constantly updating, tortuous
Runner exacerbate the renewal of liquid surface.So, fabulous oxygen mass transfer condition is defined in internal rotor, breach enzyme and urge
The restriction of oxygen transfer inefficiency during oxidation, the volume transmission quality coefficient of oxygen are 5-10 times of reactor.So as to add
Fast response speed, improves reaction efficiency.Reaction terminate after, liquid thrown by rotor leave through liquid outlet tube after shell collects super
Heavy-duty machine.Gas leaves rotor from rotor center, is drawn by gas outlet tube, completes oxygen mass transfer and enzyme-catalyzed change oxidation reaction mistake
Journey.
Beneficial effect：
What the present invention was provided prepares gluconic acid or gluconic acid by high-gravity technology by glucoseoxidase catalysis glucose
The method of salt is compared with gluconic acid and its salt method is prepared with advantages below in traditional reactor：
1st, the present invention overcomes the restriction of oxygen transfer inefficiency in enzymatic oxidation course of reaction using high-gravity technology, oxygen
Volume transmission quality coefficient is 20-100 times of traditional reactor.So as to accelerate reaction rate, reaction efficiency is improved.
2nd, high-gravity technology used in the present invention has general applicability, for the enzymatic oxidation of other oxygen consumptions is reacted
There is reference function.
Description of the drawings
Oxyty change in Fig. 1 supergravity reactors；
Oxyty change in Fig. 2 there-necked flasks；
Oxyty change in Fig. 3 fermentation tanks；
The horizontal supergravity reactor designs of Fig. 4 are illustrated.
Specific embodiment
According to following embodiments, the present invention may be better understood.However, the content described by embodiment is merely to illustrate
The present invention, and should not also without limitation on the present invention described in detail in claims.
Supergravity reactor employed in following examples is in the Ministry of Education of Beijing University of Chemical Technology high gravity technology
The reactor provided by the heart, wherein horizontal supergravity reactor structure are shown in signal Fig. 1.
Embodiment 1
Water is sprayed on supergravity reactor rotor from charging aperture, flow speed control is in 3mL/s, rotor speed 1000rpm；From air inlet
Mouth is passed through high pure nitrogen；Dissolved oxygen in water content is determined in liquid outlet opening, after dissolved oxygen is 0, high pure nitrogen air is switched to,
Air velocity is 20mL/s, and gas liquid ratio is 1:6.7, dissolved oxygen in water content is determined in liquid outlet opening, its result is shown in Fig. 1.By scheming
Middle data can be calculated and be learnt, in supergravity reactor, after 10s, dissolved oxygen in water concentration reaches maximum, now, the volume of oxygen
Mass tranfer coefficient reaches 4200h-1.
Reference examples 1
In there-necked flask, add water, magnetic agitation to connect high pure nitrogen from one of bottleneck, another bottleneck emptying, the 3rd bottle
Mouth insertion dissolved oxygen electrode, keeps whole system closed.High pure nitrogen is passed through, the residual oxygen being dissolved in the water is driven out of.Treat dissolved oxygen
After 0, high pure nitrogen is switched to air, air velocity is 20 mL/s, determines there-necked flask dissolved oxygen in water content anaplasia at any time
Change curve, its result is shown in Fig. 2.Can be calculated by data in figure and be learnt, in there-necked flask, dissolved oxygen in water concentration reaches after 150min
Maximum is arrived, now, the volume transmission quality coefficient of oxygen reaches 1.43h-1.
Reference examples 2
Water is added in fermentation tank, stirring is opened, is passed through high pure nitrogen, drives the residual oxygen being dissolved in the water out of.Treat that dissolved oxygen is 0
Afterwards, high pure nitrogen is switched to air, air velocity is 20 mL/s, determines dissolved oxygen content in fermentation tank and change over curve,
Its result is shown in Fig. 3.Can be calculated by data in figure and be learnt, in fermentation tank, dissolved oxygen in water concentration reaches maximum after 5.7min,
Now, the volume transmission quality coefficient of oxygen reaches 201.5h-1.
Knowable to result of the embodiment 1 with reference examples 1 and 2, the oxygen volume transmission quality coefficient of supergravity reactor is far above logical
There-necked flask or fermentation tank that often oxidation of glucose is used（About 20-2900 times）.High oxygen volume transmission quality coefficient
So that the mass transfer rate of oxygen is increased substantially, promote the limit of oxygen in glucose oxidation reaction process so as to solve glucoseoxidase
System.
Embodiment 2
Glucose-phosphate buffer by the 5L 100g/L for preparing（pH=7.5）Horizontal hypergravity is sprayed into from liquid inlet opening
In reactor, wherein glucose solution flow velocity 5mL/s；Rotor speed 1500rpm, reactor jacket temperature are 40 DEG C；From liquid
Discharging opening is released glucose solution Posterior circle and is sprayed in reactor.Air, gas flow rate 50mL/s, gas liquid ratio are passed through from air inlet
For 1:10；To be recycled stable after, by the glucoseoxidase for having configured and catalase（Respectively 1000IU and 2000IU）
Add in reactant liquor, start clock reaction, timing sampling determines glucose using HPLC and gluconic acid content results are shown in Table 1.
Treat that glucose content is less than below 0.1g/L stopped reaction.
Table 1
| Time（min） | 0 | 15 | 30 | 45 | 60 | 120 |
| Glucose content（g/L） | 100 | 63.4 | 25.7 | 9.3 | 2.1 | 0.05 |
| Gluconic acid content（g/L） | 0 | 38.9 | 80.1 | 98.7 | 106.1 | 107.8 |
Reference examples 3
Glucose-phosphate buffer by the 500mL 100g/L for preparing（pH=7.5）It is put in there-necked flask, speed of agitator
400rpm, bath temperature are controlled at 40 DEG C, are continuously passed through air, gas flow rate 20mL/s；By Fructus Vitis viniferae glycosyloxy after temperature reaches
Change enzyme and catalase（Respectively 1000IU and 2000IU）Add in reactant liquor, start clock reaction, timing sampling is adopted
HPLC determines glucose and gluconic acid content results are shown in Table 2.Treat that glucose content is less than below 0.1g/L stopped reaction.
Table 2
| Time（h） | 0 | 0.5 | 1 | 2 | 4 | 8 |
| Glucose content（g/L） | 100 | 85.3 | 65.7 | 35.5 | 10.7 | 0.1 |
| Gluconic acid content（g/L） | 0 | 16.0 | 35.4 | 71.3 | 95.2 | 106.7 |
From embodiment 2 compared with reference examples 3, in supergravity reactor, due to increasing oxygen mass transfer speed, enzymatic oxidation
Process is accelerated, and reaches time of the glucose content less than 0.1g/L much smaller than in there-necked flask；Further, since during course of reaction
Between short, equal enzyme dosage（Glucoseoxidase and catalase are respectively 1000IU and 2000IU）The lower Fructus Vitis viniferae that can be catalyzed
Sugar amount is also lifted（500g in embodiment 2>50g in reference examples 3）.
Embodiment 3
The glucose for preparing the 200g/L of 10L is sprayed in horizontal supergravity reactor from liquid inlet opening, wherein glucose
Solution flow rate 2mL/s；Rotor speed 1100rpm, reactor jacket temperature are 40 DEG C；Glucose solution is released from liquid outlet opening
Posterior circle is sprayed in reactor.Air is passed through from air inlet, gas flow rate 30mL/s, gas liquid ratio are 1:15；To be recycled stable after,
By the glucoseoxidase for having configured and catalase（Respectively 2500IU and 4000IU）Add in reactant liquor, start timing
Reaction, in course of reaction, Deca 1mol/L sodium hydroxide solution control reactant liquor pH is maintained between 6.5-7.5, timing sampling,
Glucose content is determined using glucose sensor analyzer and is less than below 0.1g/L stopped reaction, the response time is 100min,
HPLC is adopted to determine gluconic acid yield for 95%.
Embodiment 4
The glucose of the 5L 100g/L for preparing is sprayed in horizontal supergravity reactor from liquid inlet opening, wherein glucose
Solution flow rate 2mL/s；Rotor speed 1100rpm, reactor jacket temperature are 40 DEG C；Glucose solution is released from liquid outlet opening
Flow into afterwards and be placed with the there-necked flask of calcium carbonate solid, supernatant is circulated in penetrating reactor again.Air is passed through from air inlet,
Gas flow rate 20mL/s, gas liquid ratio are 1:10；To be recycled stable after, by the glucoseoxidase for having configured and catalase
（Respectively 2500IU and 4000IU）Add in reactant liquor, start clock reaction, reactant liquor is controlled by Calcium Carbonate in course of reaction
PH maintains 6.5 or so, and timing sampling determines glucose content using glucose sensor analyzer and stops less than below 0.1g/L
Only react, the response time is 45min.HPLC is adopted to determine gluconic acid yield for 93%.
Embodiment 5
The glucose for preparing the 500g/L of 2 L is added in internal-circulation type supergravity reactor, and adds zinc oxide solid to use
In control reactant liquor pH, rotor speed 800rpm is adjusted, reactor jacket temperature is 35 DEG C；Air, gas are passed through from air inlet
Flow velocity 20mL/s；By the glucoseoxidase for having configured and catalase（Respectively 5000IU and 20000IU）Add reaction
In liquid, start clock reaction timing sampling, glucose content is determined using glucose sensor analyzer and is less than below 0.1g/L
Stopped reaction, response time are 60min.HPLC is adopted to determine gluconic acid yield for 97%.
Claims (9)
1. a kind of method that high-gravity technology prepares gluconic acid or gluconate, it is characterised in that it comprises the following steps：
1）D/W is sprayed on the revolving bed of supergravity reactor, air is passed through so as to which dissolved oxygen reaches saturation；
2）The glucoseoxidase of catalytic amount, catalase are added in reactant liquor, circular response is simultaneously introduced nertralizer
Adjust reactant liquor pH；
3）Treat that glucose consumption terminates, stopped reaction when reactant liquor pH remains unchanged, postmenstruation neutralization, concentration, crystallization, dry at
Gluconic acid or gluconate is obtained after reason.
2. the method that a kind of high-gravity technology according to claim 1 prepares gluconic acid or gluconate, its feature
It is, the supergravity reactor is that horizontal supergravity reactor, vertical supergravity reactor or internal-circulation type hypergravity are anti-
Answer device.
3. the method that a kind of high-gravity technology according to claim 1 prepares gluconic acid or gluconate, its feature
It is, step 1）Described in D/W concentration be 100-1000g/L.
4. the method that a kind of high-gravity technology according to claim 1 prepares gluconic acid or gluconate, its feature
It is, step 1）Middle reaction temperature is 30-60 DEG C；Flow rate of liquid is 1mL/s-10mL/s.
5. the method that a kind of high-gravity technology according to claim 1 prepares gluconic acid or gluconate, its feature
It is, step 1）Middle air is 1 with the gas liquid ratio of D/W:5-20；Revolving bed rotating speed is 750-3000r/min.
6. the method that a kind of high-gravity technology according to claim 1 prepares gluconic acid or gluconate, its feature
It is, step 2）The 0.1-5% of middle glucoseoxidase, catalatic consumption for glucose quality.
7. the method that a kind of high-gravity technology according to claim 1 prepares gluconic acid or gluconate, its feature
It is, step 2）Middle glucoseoxidase is 1 with catalatic enzyme activity ratio:1-1:10.
8. the method that a kind of high-gravity technology according to claim 1 prepares gluconic acid or gluconate, its feature
It is, step 2）Described in nertralizer be sodium hydroxide, potassium hydroxide, calcium hydroxide, zinc oxide, magnesium oxide, ferrous oxide or
At least one in Calcium Carbonate；Reactant liquor pH is controlled between 6-8.
9. the method that a kind of high-gravity technology according to claim 1 prepares gluconic acid or gluconate, its feature
It is, step 3）When middle concentration of glucose is reduced to 0.1-0.5g/L, reaction terminates.
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| CN102080106A (en) * | 2010-12-09 | 2011-06-01 | 山东西王生化科技有限公司 | Double enzyme method for preparing zinc gluconate |
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