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New technology of vitamin C production

Vitamin C, also known as ascorbic acid, is a widely used health care product, medicine, food additive and cosmetic nutrition agent. It is the catalyst of REDOX reaction of living cells, participates in various metabolism in the body, has the physiological function of promoting the synthesis of various hormones in the body, and is an indispensable vitamin to maintain human health. Over the years, the domestic and foreign vitamin C market demand continues to grow, the rapid development of China's vitamin C industry, China has become the world's largest vitamin C production and sales, in the global market plays a pivotal role. Now, there are more than ten enterprises producing vitamin C, the annual production capacity has exceeded 200,000 tons, the annual output reached about 170,000 tons, accounting for about 85% of the world, the annual export volume reached about 150,000 tons, the export amount reached nearly 900 million DOLLARS, accounting for about 80% of the global trade.


As early as the 1970s, the two-step fermentation method was first developed by Chinese researchers in the world. Over the years, Chinese researchers have been continuing to research and develop various aspects of vitamin C production process and have made a lot of achievements. Recently, Chinese scientists and technicians have made some innovations and improvements in the whole process of vitamin C production, and have obtained a number of patents. According to relevant data, there are several Chinese patents involved:


Wang Hongmin and others from Shandong Luwei Pharmaceutical Co., Ltd. invented a production process of vitamin C and applied for a Chinese patent: "an environmentally friendly production process of vitamin C with high industrialization". The patent was published on January 18, 2019. The patent number is CN109232488Ao. The environmentally friendly production process of vitamin C belongs to the technical field of heterocyclic compounds. It is characterized in that the process includes the coupling technology composed of activated carbon adsorption, chelating resin adsorption, negative resin adsorption, bipolar membrane electrodialysis. The main product of the coupling technology is crude VC, the by-product is sodium hydroxide solution, and the crude VC is used for the production of VC finished products in the fine process. The invention adopts the coupling technology of "activated carbon adsorption + chelating resin adsorption + negative resin adsorption + bipolar membrane electrodialysis" : the technology has good purification effect of feed liquid, high efficiency of electrodialysis to produce ascorbic acid, and long service cycle of bipolar membrane components; The biggest difference with existing technology is not the use of sulfuric acid, hydrochloric acid; There is no solid by-product sodium sulfate, nor high salt acid wastewater containing sodium gasification, environmental treatment costs and wastewater emissions are greatly reduced; The by-product of this process, sodium hydroxide solution, is used to adsorb fermentation tail gas VOC and carbon dioxide. The adsorbent is returned to purified sodium carbonate, and sodium carbate is returned to fermentation production.


New technology of vitamin C production


Xu Ke et al. from Nanjing University invented a vitamin C wastewater treatment process after in-depth research, and applied for a Patent in China: "an integrated reactor and method for in-depth treatment of vitamin C wastewater". The patent was published on May 22, 2018. The patent number is: The invention discloses an integrated reactor and A method for the in-depth treatment of vitrinite C wastewater, which belongs to the technical field of wastewater treatment, and mainly includes an integrated reactor, wastewater raw liquid tank, chloride ion detection device and extraction agent storage box. The integrated reactor is divided into biological reaction unit and salinity regulation unit. Biological response of single Yuan from the bottom of slime respectively within the area, anaerobic biological area, transition area anaerobic-aerobic biological area, anaerobic biological area anaerobic-aerobic biological area through a permeable membrane and osmosis membrane respectively two separated, using the chloride ions in the membrane extraction wastewater, prevent because of high chlorine ion concentration influences the activity of microscopic objects, reduce the efficiency of wastewater treatment. The organic phase of extractant can be post-treated to obtain chlorinated by-product and recycled. In short, the invention has excellent treatment effect of high salinity wastewater, stable effluent water, green environmental protection and high economic benefit.

Shi Guiyang et al. from Jiangnan University invented a production process for vitamin C precursor and applied for a Chinese patent: "A fermentation method for the production of vitamin C precursor 2-ketol gulongic acid". The patent number is CN109234350A and was published during January 18, 2019. The invention discloses a fermentation method for the production of 2-keto-l gulonic acid, a precursor of vitrinin C, In this method, 2 Ketogulonigenium vulgare was prepared by fermentation of Bacillus licheniformis and Ketogulonigenium vulgare, which had overgrown SLDH. The invention realized the "one pot method" conversion from D sorbitol to 2 ketone L gulonic acid, simplified the production process, shortened the fermentation period, and effectively reduced the production cost.


Wang Yaoming from Hefei Kejia Polymer Materials Technology Co., Ltd. invented a synthesis process of vitamin C and applied for a Patent in China: "a preparation of vitamin C by bipolar membrane electrodialysis". The patent was published in 2018-12-28, patent Number: The invention discloses a method for preparing vitamin C by bipolar membrane electrodialysis, which is installed by bipolar membrane electrodialysis. Firstly, the acid chamber in the bipolar membrane electrodialysis membrane reactor is supplied with sodium vitriol C solution, and the alkaline chamber in the bipolar membrane electrodialysis membrane reactor is supplied with deionized water. The anode and cathode chambers of bipolar membrane electrodialysis membrane reactor were respectively channeled with strong electrolyte solution. Then apply direct current at both ends of bipolar membrane electroosmotic membrane reactor to achieve the conversion of vitamin C sodium, vitamin C. In the electrodialysis process of the invention, the conversion rate of vitamin C sodium can be as high as ~ 99%, and the content of sodium ion can be reduced to less than 300mg/L. The preparation method is simple and does not consume any chemical reagents, avoiding the consumption of sulfuric acid and the production of sodium sulfate by product in the traditional process.


Xu Ke et al. from Nanjing University invented a vitamin C wastewater treatment process and applied for a Chinese patent: "a vitamin C wastewater pretreatment method by electrolysis and oxidation". The patent was published from May to 15, 2018. The patent number is CN108033625A. The invention and opened a vitamin C wastewater electrolysis oxidation pretreatment method, belonging to the wastewater treatment technology, the invention through three parts gradually wastewater degradation of vitamin C, the first step, by transforming the low foam activator with bubbling atomizing machine drum bubble wastewater in contact with vitamin C, enlarge the contact area, to the surface of the vitamin C wastewater activation; In the second step, a pulsed neutron activator is used to neutron-shock the wastewater to provide energy for the organic matter in the wastewater and make its internal electronic transition into an excited state. In the third step, the electrolytic oxidation reactor is used to carry out the final electrolytic oxidation of the wastewater activated by the first two steps. The efficiency of the final electrolytic oxidation decomposition can be greatly improved by step activation. In conclusion, the pretreatment effect of the invention is good, which creates good conditions for the subsequent biofortification process.


Xu Xiang et al. invented a synthesis process of vitamin C after in-depth research, and applied for a Patent in China: "a device and process for continuous production of vitamin C solution with sodium cologate as raw material". The patent number is CN108864005A. The invention belongs to the technical field of VC solution preparation, in particular relates to a device for continuous production of vitamin C solution with sodium cologate as raw material and butyl. Art. The production device consists of a decalnatation section, esterification section, conversion section and conversion cooling section connected successively. The section includes methanol feeding pipe, automatic weighing feeder, beating tank, first sulfuric acid tank and tubular cooling reactor; The conversion section includes NaHCO3 tank and tubular synthesis reactor. The sodium removal section is connected with the tubular esterification reactor in the esterification section through the first metering pump. The esterification section is connected with the tubular synthesis reactor in the conversion section through the second metering pump, and the conversion section is connected with the second fully closed explosion-proof solid-liquid separator in the conversion cooling section through the fourth centrifugal pump. The invention adopts dilute sulfuric acid acidification sodium gulonate 匸 process to avoid the production of a large number of acid and alkaline salt water. At the same time, the production process device adopts continuous, pipelining and intellectualized production technology, so that the overall labor intensity decreases significantly.


New technology of vitamin C production


Sun Jiu and others from Xi 'an Greide Chemical New Materials Co., LTD invented a vitamin C production process and applied for a Chinese patent: "A method to recover vitamin C". The invention discloses a method of recovering vitamin C, which is characterized in the following steps: Step 1: Obtain VC recrystallization mother liquor from VC recrystallization process in a proportion of 10%-35%, take another coarse VC solution, and inhale VC recrystallization mother liquor and coarse VC solution into the system to establish a vacuum concentrated crystallization system; Step 2: When the crystal length in the crystallizer reaches 60 meses, the crystals are separated and the VC reconsolidation mother liquor is returned to the system. Meanwhile, the VC recrystallization mother liquor is continuously inhaled, and the coarse VC solution is continuously inhaled for continuous concentrated crystallization and waste liquor is discharged. In step 3, VC recrystallization mother liquor began to be discharged after continuous separation of 1000 kg of crude VC crystals. After the system was stabilized, the crude VC crystals obtained could produce qualified finished VC after recrystallization. The invention improves the process yield and reduces the discharge of three wastes.


Xu Ke et al. from Nanjing University invented a vitamin C wastewater treatment process, and applied for a Chinese patent: "a vitamin C wastewater industrial advanced treatment method". The patent was published in 2018-II-02, patent number: CN108726801a. The invention discloses "an industrialized advanced treatment method for vitamin C wastewater", which belongs to the field of environmental engineering technology and mainly includes the following steps: (1) pre-treatment of wastewater: The wastewater is pumped into the filtration device through the submersible pump. After filtration, the suspended substances in the water are removed, and the pH is adjusted to 36, the ozone machine is used to pass ozone into the filtered wastewater. The ozone flow rate is 1.22.0m3 /h, the time is 1020min, and the ozone sustainment release carrier is added into the filtered wastewater 35 times in an equal amount. The total adding dose of ozone sustained-release carrier is 46g/L, and ozone is used for pre-oxidation treatment of filtered wastewater; (2) Electrolytic oxidation pretreatment: The saturated ozone waste water pump containing the ozone slow-release carrier is sent to the electrolytic oxidation reactor. The electrolytic oxidation reactor is 5070 graphite rods connected in series as the anode and the stainless steel shell of the reactor as the cathode. The operation mode of low voltage and high current is adopted. The current is 450500A, the voltage is 2025V, and the water inflow is 2.03.0m3 /h continuously and stays electrolysis for 2030min to improve the biodegradability of wastewater. (3) UBFMBBR bioenhancement treatment: In the first step, the UBFMBBR integrated reactor was started for 10 days. The influent was a mixture of rich organic carbon and NaCl, TOC of controlled influent was 100120mg/L, chloride ion concentration was 5000mg/L, and a layer of black and brown biofilm was obviously attached on the surface of biological rope in UBF area. It indicated that the reactor was successfully started and the acclimation and culture stage was entered. In the second step, the domestication and cultivation stage lasts for 35 days. The wastewater after the pretreatment by electrolysis and oxidation in step (3) is prepared in a certain proportion to the said organic carbon-rich wastewater. The TOC of controlled inlet water is 100120mg/L, and the wastewater in the proportion of inlet water increases gradually according to 20%, 40%, 60%, 80% and 100% of TOC. Each gradient runs to the TOC stability of outlet water, when the reactor inlet water is completely electrolytic pretreatment leaching water, the domestication stage ends and enters the load lifting stage. In the third step, the time of load lifting stage is 18 days. According to the proportion of 20%, 50% and 100% of TOC concentration of wastewater, organic carbon rich is added to the water until the TOC load of UBFMBBR integrated reactor rises to 0.104kg/(m3 • d) and enters the stage of full load stable operation. Hydraulic retention time is 1418h; (4) Data statistics: Regular sampling and testing were conducted for the electrolytic oxygenation pretreatment in step (2) and the biological enhancement treatment in step (3) UBFMBBR, to investigate the effects of carbon reduction, decolorization and nitrogen removal, and to determine the optimal process parameters by statistics and mapping.

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