CN105237591A - Process for preparing glucosamine from chitin through external circulation microwave-assisted acidolysis - Google Patents
Process for preparing glucosamine from chitin through external circulation microwave-assisted acidolysis Download PDFInfo
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- CN105237591A CN105237591A CN201510769010.6A CN201510769010A CN105237591A CN 105237591 A CN105237591 A CN 105237591A CN 201510769010 A CN201510769010 A CN 201510769010A CN 105237591 A CN105237591 A CN 105237591A
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Abstract
The invention provides a process for preparing glucosamine from chitin through external circulation microwave-assisted acidolysis, and relates to the technical field of preparing glucosamine from chitin. A reaction tank is connected with a microwave heater in a circulating mode, abandoned biomass rich in chitin and inorganic acid are added into the reaction tank for acidolysis, hydrolysate generated through acidolysis is filtered through a microfiltration combined ultrafiltration method so that impurities and macromolecule substances can be filtered out, and then concentration and crystallization are conducted to obtain glucosamine. By means of the process, the acid concentration in the catalysis process can be reduced, energy conservation and emission reduction are facilitated, the problems in the prior art can be effectively solved, continuous and large-scale processing can be conducted, and large-scale industrialized production can be easily achieved.
Description
Technical field
The present invention relates to the production technical field preparing glucosamine with chitin.
Technical background
Chitin, also known as chitin, is the homopolymer of N-acetyl-glucosamine, all extensively exists in animal and microorganism, especially abundant with content in the exoskeleton of aquatic Crustacean.China's chitin biomass resource reserves are large, wide material sources, be be only second to cellulosic second largest polymer substance, but major part can not get Appropriate application, causes great waste to resource at present, exploitation chitin derivative is the important channel of by-product resource, high-valued processing.
Adopt chitin to be hydrolyzed the synthesis that the glucosamine prepared can promote human body mucopolysaccharide, the metabolism in joint can be improved, be the important nutrient forming chondrocyte, can be used as the natural tissues composition of healthy articular cartilage.Along with the growth at human body age, in body, the shortage of glucosamine is more and more serious, and joint cartilage can constantly be degenerated and wearing and tearing, and glucosamine can help repair and safeguard cartilage, and can stimulate the growth of chondrocyte.But traditional technology adopts chitin to prepare glucosamine needs and completes under concentrated acid and high temperature, and environmental pollution is serious, and equipment requirements is high, the concentrated acid that reaction needed consumption is a large amount of.
Microwave, as a kind of hertzian wave, has reflection, refraction, transmission and ghost and carries out the characteristics such as transmission ofenergy.Different substances, reflection can be presented to microwave radiation, absorb and penetrate three kinds of different propertiess, metal species conductive surface energy microwave reflection, glass, plastics, ceramic lamp isolator can pass through and not absorb microwave, polarizable medium such as water, polar organic matter etc. then can absorb microwave, introduce the judder of molecule, and be transformed into heat energy, own temperature is raised.Be widely applied based on these characteristic microwave technology.Adopt microwave heating to be a kind of important application, have quick, efficient, even, sensitive, clean, pollution-free, labour intensity is low, the advantage such as energy-conservation, easy and simple to handle, and can promote speed and the process of reaction.
Although up to the present, the study mechanism of microwave accelerated reaction is understood not yet completely, and there is multiple different dispute, but the viewpoint of main flow is thought, microwave exposure is not only that rate of heating is fast, and to polar material, there is Heating selectivity, molecular vibration is accelerated, even can reduce the activation energy of reaction.Because the irradiation energy of microwave in 300MHz-3000MHz range of frequency is low, the change of molecular vibration energy level can not be caused, therefore generally, can not reaction mechanism be changed, but can accelerated reaction process.Canadian scientist RichardGedye in 1980 utilizes microwave to carry out organic synthesis and succeeds, speed of reaction is improved 1000 times of (Gedye etc., TetrahedronLett., 1986,26, p.279), afterwards, countries in the world scientist has further developed microwave catalysis, and makes microwave chemical become a new research field.The people such as the Liu Longfei of China adopt microwave radiation to combine with hydrochloric acid catalysis and to be hydrolyzed to Mierocrystalline cellulose, by the improvement of reaction parameter and processing condition, in reaction 50min hydrolyzed solution, concentration of reduced sugar reaches 36.7g/L, compare conventional heating in water bath gained concentration of reduced sugar to improve 14.4g/L(Liu Long and fly, Chemical Engineering Technology and exploitation, 2009,38, p.13), increase rate is very remarkable.The people such as Zhou Jicheng adopt microwave catalysis to react oxidative degradation technical finesse waste water, and 4-nitrophenols and phenol degrading rate all can reach more than 99%, and general photocatalysis technology degradation rate is only 85%-95%(CN201210570240.6).Up to now, microwave has been applied to building-up reactions, hydrolysis reaction and condensation reaction, and from applicable cases, compared with traditional technology, this reaction possesses that reaction is fast, productive rate is high, quality product high-technology advantage.
But the practical application of microwave catalysis is less, especially lack mass-producing application, mainly study mostly based on experimental size or lab scale level, major cause is that the device development of micro ware auxiliary catalysis is delayed.Large-scale at present microwave equipment is mainly used in the processes such as microwave heating, Micvowave Sterilization, microwave treatment waste, for be solid-state or semi-solid state material, and shaping device is lacked to the auxiliary catalysis of fluid foods.
In addition, at present about the hydrolysis reaction of microwave catalysis mainly concentrates on the hydrolysis of the biomass such as Mierocrystalline cellulose, starch and the degradation treatment of organic waste water, and it is less to prepare the research of glucosamine by microwave catalysis chitin hydrolysis reaction.Mainly contain Lin Jinmei etc. and report " research of Rapid Preparation of Glucosamine Hydrochloride under Microwave Radiation " (Lin Jinmei etc., Zhangzhou Normal College's journal (natural science edition), 4th phase in 2006), what it adopted is chitosan is raw material, chitosan is the product after chitin removes acetyl, and this is different from the chitin raw material that this technique uses.Zhu Yu rosy clouds Master's thesis " preparation of oligochitosan, compartment analysis and bacteriostatic activity research " reports and adopts microwave to carry out viscosity reduction, then the preparation of oligochitosan is carried out, its auxiliary catalysis system is heterogeneous, and the product of preparation is oligochitosan, and this is also one of the achievement in early stage of this research team.In addition, Guan Li etc. are in " Preparation of carboxymethyl chitosan under microwave irradiation ", propose the research (Guan Li etc. adopting microwave to carry out cm-chitosan, ACAD J GCP, 21 volume 4 phases in 2003), also different from the present invention, but all embody microwave catalysis and have a good application prospect.
Current technique adopts the hydrochloric acid (mass concentration >20%) of high density to be hydrolyzed, and hydrolysis yield is only 80%, and average per kilogram product consumes concentrated hydrochloric acid at more than 6kg, and follow-up water treatment pressure is larger.
Summary of the invention
In order to overcome the long reaction time existed in prior art, concentrated acid consumption is large, and the problems such as temperature of reaction is high, and energy consumption is large, the present invention proposes the processing method that a kind of new microwave catalysis prepares glucosamine.
Retort circulates with microwave heater and is connected by the present invention, chitinous abandoned biomass and mineral acid will be rich in add in retort and carry out acidolysis, then the hydrolyzed solution getting acidolysis generation combines hyperfiltration process by micro-filtration, after leaching impurity and macromolecular substance, through concentrated, crystallization, obtain glucosamine.
Microwave catalysis is applied to the production process of glucosamine by the present invention, and its raw material adopts and is rich in the shell of chitinous Crustacean, the biomass such as crust, fungi bacterium slag, fermentation mycelium waste residue of insect.The present invention adopts acid degradation assisted with microwave, can reduce the acid concentration of catalytic process, be conducive to energy-saving and emission-reduction.Adopt method of the present invention, effectively can solve problems of the prior art, and can scale process continuously, be easy to large-scale industrial production.
Outstanding advantages of the present invention and effect:
1, the technology of the present invention is introduced microwave radiation and is worked in coordination with acid hydrolysis catalysis chitin and prepare glucosamine, reaction times is short, catalytic efficiency is high, acid consumption is few, compared with conventional high-temperature strong acid preparation technology, there is the advantage that the requirement of equipment acid-resistant and anti-high-temperature is low, process is easy to control, process costs is low, be also conducive to energy-saving and emission-reduction.
2, the technology of the present invention is before microwave radiation concerted reaction, and chitin is first carried out pre-acidolysis, allows chitin fully dissolve, then carries out in conjunction with microwave treatment accelerated reaction, substantially increases chitin hydrolysis efficiency, also accelerates the reaction times.
3, the technology of the present invention is chitinous resource utilization, high-valued application provides new reliable approach, by promoting making full use of of the natural resource of this abundance of chitin, has the important meaning of Sustainable development.
In addition, mineral acid of the present invention be in sulfuric acid, phosphoric acid or hydrochloric acid at least any one.
The concentration of described mineral acid is 10% ~ 15%.The concentration of this mineral acid is compared traditional technology and is significantly reduced, and traditional technology acid concentration is generally 15% ~ 20%.
The temperature of reaction condition of described acidolysis is 80 ~ 100 DEG C.Traditional technology temperature needs High Temperature High Pressure usually.
In order to ensure normally carrying out of producing, reach efficient, energy-conservation effect, at circulation time, the flow velocity of feed liquid is 0.2 ~ 1.0m/s, and circular flow is 5 ~ 30m
3/ h.
Accompanying drawing explanation
Fig. 1 is a kind of structural representation of the present invention.
Embodiment
The glucosamine produced by technical solution of the present invention, there is the features such as high, the sour consumption of output is few, cost is low, and make chitin be able to efficiency utilization, improve comprehensive utilization of resources to be worth, and overcome that the acid amount that exists in prior art is large, long reaction time, the problems such as temperature of reaction is high, and degree of hydrolysis is low.Describe performance of the present invention in detail below by way of specific embodiment, object is to help reader better to understand spirit of the present invention, but not as the restriction to the scope of the present invention.
One, the preparation of system:
As shown in Figure 1, form primarily of stainless steel reaction tank 1, cooling system 2, microwave heater 3 and reflux condensation mode 4 device.
Stainless steel reaction tank 1 is provided with charging opening 11, drain hole 12 and refluxing opening 13, and the outer end of refluxing opening 13 connects reflux condensation mode apparatus 4.Retort 1 also arranges chuck 14, and chuck 14 and cooling system are formed to circulate by external circulating device 5 and be connected.Arrange whipping appts 15 in retort 1, being circulated with microwave heater 6 by recycle pump 6 in retort 15 is connected.Microwave heater 3 is also connected with microwave generator 7.
Wherein, stainless steel reaction tank 1(material is 316L), volume is 3.0M
3, adopt chuck heating or cooling, vortex stirrer, power of agitator 4.0KW, mixing speed 60-120rpm is adjustable; Configuration shell and tube cooler, material is stainless steel, cooling area 15 square meter.
Microwave heater, interior pipe adopts synthetic glass, and shell is stainless steel.Interior pipe nominal diameter 80, adopts column series arrangement, single tube height 1.5m.Microwave heating arranges upper, middle and lower three sections.
Microwave generator associated technical parameters: power supply is 3 phase 380V ± 10%, 50Hz; Adopt high power single-tube magnetron, microwave frequency 915MHz, microwave power 1KW ~ 10KW continuously adjustabe, magnetron cooling adopts water-cooled.Microwave from leakage performs national standard, and main equipment is entrusted has the company of qualification to manufacture and design.
Two, production technique:
Embodiment 1:
Micro ware auxiliary catalysis degrade chitin is utilized to prepare ammonia sugar glucose, get the chitin raw material prepared by fermentation mycelium waste residue, according to the quality of raw material, the mass concentration adding 3 times of volumes is the sulfuric acid of 10%, soak and clear up in advance for 1 hour, add deionized water again, make acid concentration in feed liquid 5%, stir and its composition is mixed.Start feed liquid outer circulation, control feed velocity 0.2m/s, circular flow 5m
3/ h, opens microwave generating apparatus, and microwave power configuration 1000W, controls feed temperature at 80 DEG C, 1.0 hours catalytic hydrolysis time; After hydrolysis terminates, close microwave generator and heating unit, close feed liquid external circulating system; Open vacuum recovery system, by vacuum concentration, reclaim the hydrochloric acid in hydrolyzed solution, the dilute acid soln of recovery can reuse.Feed liquid after concentrated after filtration, crystallization, obtain glucosamine product.
Embodiment 2:
Micro ware auxiliary catalysis degrade chitin is utilized to prepare ammonia sugar glucose, get the chitin raw material prepared by fermentation mycelium waste residue, according to the quality of raw material, the mass concentration adding 3 times of volumes is the hydrochloric acid of 15%, soak and clear up in advance for 1 hour, add deionized water again, make acid concentration in feed liquid 5%, stir and its composition is mixed.Start feed liquid outer circulation, control feed velocity 0.5m/s, circular flow 3m
3/ h, opens microwave generating apparatus, and microwave power configuration 1000W, controls feed temperature at 80 DEG C, 1.0 hours catalytic hydrolysis time; After hydrolysis terminates, close microwave generator and heating unit, close feed liquid external circulating system; Open vacuum recovery system, by vacuum concentration, reclaim the hydrochloric acid in hydrolyzed solution, the dilute acid soln of recovery can reuse.Feed liquid after concentrated after filtration, crystallization, obtain glucosamine product.
Embodiment 3:
Micro ware auxiliary catalysis degrade chitin is utilized to prepare ammonia sugar glucose, get the chitin raw material prepared by fermentation mycelium waste residue, according to the quality of raw material, the mass concentration adding 3 times of volumes is the hydrochloric acid of 15%, soak and clear up in advance for 2 hours, add deionized water again, make acid concentration in feed liquid 10%, stir and its composition is mixed.Start feed liquid outer circulation, control feed velocity 0.25m/s, circular flow 10m
3/ h, opens microwave generating apparatus, and microwave power configuration 5000W, controls feed temperature at 100 DEG C, 2.0 hours catalytic hydrolysis time; After hydrolysis terminates, close microwave generator and heating unit, close feed liquid external circulating system; Open vacuum recovery system, by vacuum concentration, reclaim the hydrochloric acid in hydrolyzed solution, the dilute acid soln of recovery can reuse.Feed liquid after concentrated after filtration, crystallization, obtain glucosamine product.
Embodiment 4:
Micro ware auxiliary catalysis degrade chitin is utilized to prepare ammonia sugar glucose, get the chitin raw material prepared by shrimp and crab shells, precomminution is to below 2cm, according to the quality of raw material, the mass concentration adding 3 times of volumes is the hydrochloric acid of 10%, soaks and clears up in advance for 1 hour, then add deionized water, acid concentration in feed liquid is made 5%, to stir and its composition is mixed.Start feed liquid outer circulation, control feed velocity 1m/s, circular flow 10m
3/ h, opens microwave generating apparatus, and microwave power configuration 5000W, controls feed temperature at 90 DEG C, 2.0 hours catalytic hydrolysis time; After hydrolysis terminates, close microwave generator and heating unit, close feed liquid external circulating system; Open vacuum recovery system, by vacuum concentration, reclaim the hydrochloric acid in hydrolyzed solution, the dilute acid soln of recovery can reuse.Feed liquid after concentrated after filtration, crystallization, obtain glucosamine product.
Embodiment 5:
Micro ware auxiliary catalysis degrade chitin is utilized to prepare ammonia sugar glucose, get the chitin raw material prepared by shrimp and crab shells, precomminution is to below 2cm, according to the quality of raw material, the mass concentration adding 3 times of volumes is the phosphoric acid of 15%, soaks and clears up in advance for 2 hours, then add deionized water, acid concentration in feed liquid is made 10%, to stir and its composition is mixed.Start feed liquid outer circulation, control feed velocity 1m/s, circular flow 30m
3/ h, opens microwave generating apparatus, and microwave power configuration 8000W, controls feed temperature at 95 DEG C, 2.0 hours catalytic hydrolysis time; After hydrolysis terminates, close microwave generator and heating unit, close feed liquid external circulating system; Open vacuum recovery system, by vacuum concentration, reclaim the hydrochloric acid in hydrolyzed solution, the dilute acid soln of recovery can reuse.Feed liquid after concentrated after filtration, crystallization, obtain glucosamine product.
Claims (5)
1. outer circulation microwave-assisted acidolysis chitin prepares the technique of glucosamine, it is characterized in that: retort being circulated with microwave heater is connected, chitinous abandoned biomass and mineral acid will be rich in add in retort and carry out acidolysis, then the hydrolyzed solution getting acidolysis generation combines hyperfiltration process by micro-filtration, after leaching impurity and macromolecular substance, through concentrated, crystallization, obtain glucosamine.
2. technique according to claim 1, is characterized in that: described mineral acid is sulfuric acid, phosphoric acid or hydrochloric acid.
3. technique according to claim 1 or 2, is characterized in that: the concentration of described mineral acid is 10% ~ 15%.
4. technique according to claim 1, is characterized in that: the temperature of reaction condition of described acidolysis is 80 ~ 100 DEG C.
5. technique according to claim 1, it is characterized in that: at circulation time, the flow velocity of feed liquid is 0.2 ~ 1.0m/s, and circular flow is 5 ~ 30m
3/ h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112090373A (en) * | 2020-09-21 | 2020-12-18 | 山东润德生物科技有限公司 | Glucosamine hydrochloride production hydrolysis unit |
| CN113967370A (en) * | 2020-07-23 | 2022-01-25 | 万华化学集团股份有限公司 | System device and method for removing volatile organic compounds in aqueous emulsion |
| CN114777453A (en) * | 2022-04-07 | 2022-07-22 | 扬州日兴生物科技股份有限公司 | High-efficient vacuum drying device is used in chitosan preparation |
| CN115448963A (en) * | 2022-10-21 | 2022-12-09 | 扬州日兴生物科技股份有限公司 | Preparation method of N-acetyl-D-glucosamine |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113967370A (en) * | 2020-07-23 | 2022-01-25 | 万华化学集团股份有限公司 | System device and method for removing volatile organic compounds in aqueous emulsion |
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| CN114777453A (en) * | 2022-04-07 | 2022-07-22 | 扬州日兴生物科技股份有限公司 | High-efficient vacuum drying device is used in chitosan preparation |
| CN114777453B (en) * | 2022-04-07 | 2022-11-15 | 扬州日兴生物科技股份有限公司 | Chitosan preparation is with high-efficient vacuum drying device |
| CN115448963A (en) * | 2022-10-21 | 2022-12-09 | 扬州日兴生物科技股份有限公司 | Preparation method of N-acetyl-D-glucosamine |
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Application publication date: 20160113 |