CN201578881U - Subcritical Fluid Extraction Device for Active Components of Natural Products - Google Patents
Subcritical Fluid Extraction Device for Active Components of Natural Products Download PDFInfo
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Abstract
本实用新型天然产物有效成分的亚临界流体萃取装置,由控制系统部分和浸出系统部分构成,其中浸出系统部分由萃取罐、蒸发罐、缓冲罐、冷凝器、溶剂罐、超声发生装置、真空泵、阻火器、压缩机、热水泵、热水箱构成;萃取罐一端通过调节阀和管道与溶剂罐相连接;真空泵一端通过管道和调节阀分别与萃取罐、蒸发罐、缓冲罐连接,另一端通过管道与阻火器连接;压缩机的一端通过管道和调节阀与缓冲罐连接,缓冲罐再通过管道和调节阀与萃取罐、蒸发罐相连接,萃取罐顶部设有超声发生装置,超声发生器置于所述萃取罐的外面。本实用新型根据萃取对象不同,将亚临界流体萃取技术与超声提取技术相结合,能提高萃取率、缩短提取时间。
The utility model subcritical fluid extraction device for active ingredients of natural products is composed of a control system part and a leaching system part, wherein the leaching system part is composed of an extraction tank, an evaporation tank, a buffer tank, a condenser, a solvent tank, an ultrasonic generator, a vacuum pump, Flame arrester, compressor, hot water pump and hot water tank; one end of the extraction tank is connected to the solvent tank through a regulating valve and a pipeline; one end of the vacuum pump is connected to the extraction tank, evaporation tank and buffer tank through a pipeline and a regulating valve, and the other end is connected to the The pipeline is connected to the flame arrester; one end of the compressor is connected to the buffer tank through a pipeline and a regulating valve, and the buffer tank is connected to the extraction tank and the evaporation tank through a pipeline and a regulating valve. An ultrasonic generator is installed on the top of the extraction tank. on the outside of the extraction tank. According to different extraction objects, the utility model combines the subcritical fluid extraction technology with the ultrasonic extraction technology, which can improve the extraction rate and shorten the extraction time.
Description
技术领域technical field
本实用新型涉及一种天然产物功效成分的提取装置,尤其涉及在超声辅助下,利用亚临界低级烷烃、四氟乙烷或六氟化硫等流体萃取天然产物脂溶性功效成分的装置。The utility model relates to an extraction device for functional components of natural products, in particular to a device for extracting fat-soluble functional components of natural products by using fluids such as subcritical lower alkanes, tetrafluoroethane or sulfur hexafluoride under the assistance of ultrasound.
背景技术Background technique
我国地域辽阔,复杂的地理环境与多变的气候条件造就了我国物种的多样性,尤其是具有医疗保健作用的特种油脂、香精香料、色素等天然资源相当丰富,如银杏、丁香、生姜、大蒜、洋葱、枸杞籽、沙棘、红辣椒、花椒、桂花、玫瑰花和茉莉花等。Our country has a vast territory, complex geographical environment and changeable climatic conditions have created the diversity of species in our country, especially the natural resources such as special oils, flavors and fragrances, pigments, etc. , onion, wolfberry seed, seabuckthorn, red pepper, pepper, osmanthus, rose and jasmine, etc.
天然产物中高附加值的生理活性物质因其热敏性,用常规热回流提取法和有机溶剂萃取法不仅得率低,而且功能成分受到破坏。超临界CO2萃取虽是较为理想的方法,具有萃取能力强、提取率高、产品品质好等优势,但必须在25MPa以上的超高压状态下才能进行。极高的压力限制了设备有效容积的放大,同时,较高的设备制造和运行成本制约了该技术在天然产物有效成分生产中的应用。因此,寻找一种高效提取天然产物中热敏性、易氧化活性成分,且便于工业化推广的新技术和装备,已成为近年来天然产物提取领域的研究热点。Due to their thermal sensitivity, the high value-added physiologically active substances in natural products not only have low yields but also destroy functional components by conventional heat reflux extraction methods and organic solvent extraction methods. Although supercritical CO2 extraction is an ideal method, which has the advantages of strong extraction capacity, high extraction rate, and good product quality, it must be carried out under ultra-high pressure conditions above 25MPa. The extremely high pressure limits the expansion of the effective volume of the equipment. At the same time, the high equipment manufacturing and operating costs restrict the application of this technology in the production of natural product active ingredients. Therefore, finding a new technology and equipment that can efficiently extract heat-sensitive and easily oxidized active ingredients in natural products, and is easy to industrialize, has become a research hotspot in the field of natural product extraction in recent years.
亚临界流体是指高于沸点,低于临界温度和临界压力,以流体形式存在的物质。亚临界流体萃取是以亚临界状态的流体或亚临界流体的混合溶液为溶媒,与溶质在系统内相继经过浸提、蒸发脱溶、压缩、冷凝回收等过程,从天然产物中提取目标组分的一种新技术。例如,当液化石油气(LPG)、丙烷、丁烷、高纯度异丁烷(R600a)、二甲醚(DME)、1,1,1,2-四氟乙烷(R134a)和六氟化硫等以亚临界流体状态存在时,分子的扩散性能增强,传质速度加快,对天然产物中弱极性以及非极性物质的渗透性和溶解能力显著提高。因而,上述亚临界流体特别适于天然产物中挥发油、油脂或脂溶性成分的萃取。亚临界环境下萃取,不破坏热敏性成分、目的物完全,被视为绿色环保、前景广阔的一项变革性技术。Subcritical fluid refers to a substance that exists in the form of a fluid above the boiling point and below the critical temperature and critical pressure. Subcritical fluid extraction uses subcritical state fluid or a mixed solution of subcritical fluid as a solvent, and successively undergoes leaching, evaporation precipitation, compression, condensation recovery and other processes with solutes in the system to extract target components from natural products a new technology. For example, when liquefied petroleum gas (LPG), propane, butane, high-purity isobutane (R600a), dimethyl ether (DME), 1,1,1,2-tetrafluoroethane (R134a) and hexafluoride When sulfur exists in a subcritical fluid state, the diffusion performance of molecules is enhanced, the mass transfer speed is accelerated, and the permeability and solubility of weakly polar and non-polar substances in natural products are significantly improved. Therefore, the above-mentioned subcritical fluid is particularly suitable for the extraction of volatile oil, fat or fat-soluble components in natural products. Extraction in a subcritical environment does not destroy heat-sensitive components and the target object is complete. It is regarded as a transformative technology with green environmental protection and broad prospects.
在国内现有的亚临界相关提取装置中,申请号为ZL200620135969.0的中国专利,公开日2006年10月11日,发明创造的名称是“适用于多种溶剂进行极性非极性中间体萃取的装置”,该申请公开了通过改变萃取溶剂组成以及系统内阀门、管道、设备的动作程序,满足不同溶剂对萃取温度、压力、时间和流向的要求,完成对动植物原料中有效成分的萃取。该装置兼顾了非极性、极性有效成分的提取工艺要求,其不足是工艺路线复杂,因而设备制造成本高;采用手动控制,操作繁琐。申请号为200610070495.0的中国专利,公开日2006年12月5日,发明创造的名称是“一种低压超临界萃取工艺及其装置”,该申请公开了以四氟乙烷作为超临界流体,选择性萃取非极性、弱极性及极性较强的物质。该发明采用超临界状态下的四氟乙烷,系统压力最高达8MPa,因而设备制造难度较大、成本较高。申请号为200710032663.1的中国专利,公开日2007年12月18日,发明创造的名称是“天然产物有效成分的超声强化亚临界水萃取方法及装置”,该申请公开了采用亚临界水为萃取介质,通过改变萃取参量对被提取物进行选择性提取。该发明的不足在于以亚临界水为萃取介质,萃取压力高达20MPa,因而设备制造难度较大、成本较高。上述国内所公开的亚临界流体萃取的相关装置,由于采用的萃取溶剂性质差别大,工艺不同,因此装置的结构各不相同。但普遍存在结构复杂、制造成本高;工作压力高、设备放大制造困难;且均采用人工控制,操作繁琐;同时加压溶剂萃取的萃取釜一般采用多个螺栓紧固、密封,装填料和出料非常不方便,而上述发明均未涉及装料口的具体结构。Among the existing subcritical related extraction devices in China, the Chinese patent application number ZL200620135969.0 was published on October 11, 2006. The name of the invention is "suitable for polar and non-polar intermediates in various solvents Extraction device", the application discloses that by changing the composition of the extraction solvent and the action procedures of the valves, pipelines, and equipment in the system, the requirements of different solvents for extraction temperature, pressure, time, and flow direction are met, and the extraction of active ingredients in animal and plant materials is completed. extraction. The device takes into account the extraction process requirements of non-polar and polar active ingredients. Its disadvantage is that the process route is complicated, so the equipment manufacturing cost is high; manual control is adopted, and the operation is cumbersome. The Chinese patent with the application number 200610070495.0 was published on December 5, 2006. The name of the invention is "a low-pressure supercritical extraction process and its device". The application discloses the use of tetrafluoroethane as a supercritical fluid. Non-polar, weakly polar and highly polar substances can be extracted by nature. The invention uses tetrafluoroethane in a supercritical state, and the system pressure can reach up to 8MPa, so the manufacturing of the equipment is difficult and costly. Chinese patent application number 200710032663.1, published on December 18, 2007, the name of the invention is "Ultrasonic Enhanced Subcritical Water Extraction Method and Device for Active Components of Natural Products", the application discloses the use of subcritical water as the extraction medium , to selectively extract the extract by changing the extraction parameters. The disadvantage of this invention is that subcritical water is used as the extraction medium, and the extraction pressure is as high as 20MPa, so the equipment manufacturing is relatively difficult and expensive. The above-mentioned devices related to subcritical fluid extraction disclosed in China have different structures due to the large difference in the properties of the extraction solvents used and the different processes. However, there are generally complex structures, high manufacturing costs, high working pressure, and difficulty in enlarging equipment; and they are all manually controlled, and the operation is cumbersome; at the same time, the extraction kettle for pressurized solvent extraction generally uses multiple bolts to fasten, seal, fill and discharge. The material is very inconvenient, and the above-mentioned inventions all do not relate to the specific structure of the charging port.
在国内现有的相关亚临界流体提取方法中,专利号为ZL 01108701.3的中国专利,公开日2001年8月2日,发明创造的名称是“亚临界液化石油气萃取除虫菊酯的方法”,该申请公开了采用亚临界液化石油气为溶剂,在温度为20-90℃,压力为0.3~3.5MPa工艺条件下,萃取20-300分钟,又在温度为20~90℃,压力为0.1~2MPa下,使液化石油气气化,从而分离出除虫菊酯。专利号为200610104744.3的中国专利,公开日2008年4月16日,发明创造的名称是“亚临界流体萃取溶剂及萃取方法”,该申请公开了一种亚临界流体萃取溶剂,包含从含化合物或组合物作为组成部分的原料中萃取一种化合物或组合物的萃取溶剂,其主要特点是以液态六氟化硫为萃取溶剂,该申请还公开了所述的亚临界流体萃取溶剂的萃取方法。上述国内所公开的亚临界提取方面的相关方法,由于选择的萃取剂不同,采用的方法也各不相同。但所公开的方法均局限于液化石油气、丙烷、丁烷、高纯度异丁烷、二甲醚、1,1,1,2-四氟乙烷和六氟化硫等某一种特定亚临界流体;同时当以上述亚临界流体为萃取介质时,对中等极性和极性化合物萃取效率偏低。上述方法均未涉及两种及两种以上亚临界流体混合物作为萃取介质、或加入夹带剂选择性萃取目标组分的方法。Among the existing related subcritical fluid extraction methods in China, the Chinese patent No. ZL 01108701.3 was published on August 2, 2001. The name of the invention is "Method for Extracting Pyrethrins from Subcritical Liquefied Petroleum Gas". The application discloses using subcritical liquefied petroleum gas as a solvent, extracting for 20-300 minutes at a temperature of 20-90°C and a pressure of 0.3-3.5MPa, and then extracting at a temperature of 20-90°C and a pressure of 0.1-2MPa Next, the liquefied petroleum gas is vaporized to separate the pyrethrins. The patent number is 200610104744.3 Chinese patent, the publication date is April 16, 2008, the name of the invention is "subcritical fluid extraction solvent and extraction method", the application discloses a subcritical fluid extraction solvent, which contains compounds or The composition is used as an extraction solvent for extracting a compound or composition from the raw materials of the constituent parts, and its main feature is to use liquid sulfur hexafluoride as the extraction solvent. The application also discloses the extraction method of the subcritical fluid extraction solvent. The above-mentioned methods related to the subcritical extraction disclosed in China adopt different methods due to the different extraction agents selected. But the disclosed methods are all limited to a specific sub-method such as liquefied petroleum gas, propane, butane, high-purity isobutane, dimethyl ether, 1,1,1,2-tetrafluoroethane and sulfur hexafluoride. Critical fluid; at the same time, when the above-mentioned subcritical fluid is used as the extraction medium, the extraction efficiency of medium polarity and polar compounds is low. None of the above methods involves a mixture of two or more subcritical fluids as an extraction medium, or a method for selectively extracting a target component by adding an entrainer.
为克服现有亚临界流体萃取装置自动化程度低、萃取釜装卸料繁琐、设备工作压力高;同时克服亚临界流体萃取方法仅局限于某一特定亚临界流体、对中等极性和极性化合物萃取效率低等缺陷,本发明充分利用液化石油气、高纯度异丁烷、二甲醚和六氟化硫等亚临界流体在相同温度下亚临界压力接近的特点,设计了一套结构简单、萃取釜开启方便、自动化程度高、且同时适于上述多种亚临界流体萃取的装置,并对利用该装置提取天然产物脂溶性或中等极性功效成分的方法进行了详细阐述。In order to overcome the low degree of automation of the existing subcritical fluid extraction device, the cumbersome loading and unloading of the extraction kettle, and the high working pressure of the equipment; at the same time, the subcritical fluid extraction method is limited to a specific subcritical fluid, and the extraction of medium polar and polar compounds Low efficiency and other defects, the present invention makes full use of the characteristics of subcritical fluids such as liquefied petroleum gas, high-purity isobutane, dimethyl ether and sulfur hexafluoride at the same temperature close to the subcritical pressure, and designs a set of simple structure, extraction It is a device that is easy to open, has a high degree of automation, and is suitable for the above-mentioned various subcritical fluid extractions, and describes in detail the method of using the device to extract fat-soluble or medium-polar functional components of natural products.
发明内容Contents of the invention
本实用新型的目的在于克服现有技术存在的上述缺陷,提供一种超声辅助亚临界流体萃取天然产物脂溶性功效成分的装置,该装置能同时适用于低级烷烃、二甲醚、四氟乙烷、六氟化硫等多种溶媒。The purpose of this utility model is to overcome the above-mentioned defects existing in the prior art, and to provide a device for ultrasonically assisted subcritical fluid extraction of fat-soluble functional components of natural products. , sulfur hexafluoride and other solvents.
本实用新型提供的超声辅助亚临界流体萃取装置通过如下方案实现:The ultrasonic-assisted subcritical fluid extraction device provided by the utility model is realized through the following scheme:
该装置主要由以下二大部分构成:The device is mainly composed of the following two parts:
浸出系统部分:该部分主要由萃取罐1、蒸发罐2、缓冲罐3、冷凝器4、溶剂罐5、超声发生装置11、真空泵9、阻火器10、压缩机8、热水泵7、热水箱6等构成。萃取罐1一端通过调节阀17、25和管道与溶剂罐5相连接,利用压差将溶剂罐5中的液态溶酶输入萃取罐1;另一端通过调节阀19和管道与蒸发罐2相连接,将提取产物和溶酶的混合物排入蒸发罐2中。真空泵9一端通过管道和调节阀13、14、20、21分别与萃取罐1、蒸发罐2、缓冲罐3连接,用于除去罐中不可压缩气体——空气等;另一端通过管道与阻火器10连接,将空气和极少量气化的萃取介质排出系统,并起到防火作用。压缩机8的一端通过管道和调节阀22与缓冲罐3连接,缓冲罐3再通过管道和调节阀14、21与萃取罐1、蒸发罐2相连接,将液态溶酶进行减压气化;另一端通过管道和调节阀15与冷凝器4连接,将经压缩的气态溶酶冷却液化。冷凝器4的另一端通过管道和调节阀18与溶剂罐5连接,将液化的溶酶注入溶剂罐5中;球阀33、34分别为循环冷却水的进出口。热水泵7一端通过管道和调节阀28分别与热水箱6连接;另一端通过管道和调节阀26、29与萃取罐1、蒸发罐2底部的加热夹套连接,为萃取罐1、蒸发罐2中液态的溶酶气化提供热量以及用来保证萃取罐处于恒温状态。Leaching system part: this part is mainly composed of
所述天然产物有效成分的亚临界流体萃取装置的萃取罐1顶部设有超声发生装置11,超声发生装置11与萃取罐1顶部相连,超声发生器11置于所述萃取罐1的外面,超声发生器11的换能头置于萃取罐1的上部。该部分将超声引入到亚临界流体萃取过程中,利用超声波在液体介质传播时所特有的空化效应,加上超声波传播产生的机械振动、微射流等多极效应,使功效物质更容易被提取出来。The top of the
所述萃取罐1为耐高温、高压的不锈钢材质的圆柱状装置,萃取罐盖采用萃取罐快开门装置12,方便浸出物料的装卸,以聚四氟乙烯材料作为密封环,保证系统的气密性。萃取罐底部有一不锈钢滤网,以防粉末原料堵塞管道出口,下端有一出口通过管道与蒸发罐相连;所述蒸发罐2、缓冲罐3、溶剂罐5为不锈钢材质的圆柱状或矩形状容器;所述热水箱6为不锈钢材质或塑料材质的圆柱形或矩形装置;所述冷凝器4为一管式冷却器,通过不断通入冷却水进行冷却,冷却器下侧设有一冷却水进口,上侧有一冷却水出口。The
所述压缩机8为隔膜压缩机,可调节和显示压力大小,压力范围为0~20MPa。萃取罐1根据实际需要可设计成各种体积,其它部分按萃取工艺要求配置成相应大小。The
控制系统部分:包括浸出温度调节控制、浸出时间控制、浸出次数控制、料溶比控制、脱溶温度调节控制、脱溶压力反馈控制、整个装置的电器控制、以及超温超压和泄漏报警等。该部分采用PLC设计,通过控制面板35上的参数设定,自动完成整个萃取过程。Control system part: including leaching temperature adjustment control, leaching time control, leaching frequency control, material-dissolution ratio control, precipitation temperature adjustment control, precipitation pressure feedback control, electrical control of the entire device, and over-temperature, over-pressure and leakage alarms, etc. . This part adopts PLC design, through the parameter setting on the
为便于工作温度和压力的自动控制,该装置在萃取罐1、蒸发罐2、缓冲罐3、冷凝器4和溶剂罐5设有压力测定器,在萃取罐1、蒸发罐2、缓冲罐3设有电接点式的温度测定器,压力测定器和温度测定器均有一端设于罐内部。首先由人工在控制面板35上设定浸出温度、浸出时间、浸出次数、料溶比和脱溶温度等萃取参数,通过系统的压力测定器和温度测定器反馈给PLC信号,再由PLC发出指令,控制各个阀门的开启,直至完成整个萃取过程。In order to facilitate the automatic control of working temperature and pressure, the device is equipped with pressure measuring devices in the
本装置的工作过程如下:The working process of this device is as follows:
(1)首先将物料装入料筒,再放入萃取罐内,用真空泵将容器中的空气抽尽;(1) First put the material into the barrel, then put it into the extraction tank, and use a vacuum pump to exhaust the air in the container;
(2)利用压差将溶剂罐内亚临界流体打入萃取罐内,采用循环热水对萃取罐进行加热,同时打开超声发生装置辅助萃取;(2) Use the pressure difference to pump the subcritical fluid in the solvent tank into the extraction tank, use circulating hot water to heat the extraction tank, and turn on the ultrasonic generating device to assist in the extraction;
(3)物料经一定时间萃取后,将液态的混合油(含有脂溶性成分的亚临界流体),从萃取罐底部放出,进入蒸发罐中进行减压蒸发,将混合油中的亚临界流体充分气化,蒸发过程中通过夹层的热水加热,以补充亚临界流体从液态到气态转化过程所需的热量,气化后的气体经压缩机压缩后在冷凝器中变为液体,回流到溶剂罐后循环使用;(3) After the material is extracted for a certain period of time, the liquid mixed oil (subcritical fluid containing fat-soluble components) is discharged from the bottom of the extraction tank, and enters the evaporation tank for decompression evaporation, and the subcritical fluid in the mixed oil is fully Gasification, during the evaporation process, the hot water in the interlayer is heated to supplement the heat required for the transformation of the subcritical fluid from liquid to gaseous state. The gasified gas is compressed by the compressor and becomes liquid in the condenser, and returns to the solvent Recycle after tank;
(4)萃取结束后,用压缩机将萃取罐内物料中的残留亚临界流体进行减压蒸发,待萃取罐压力到0Mpa后,再用真空泵进行负压蒸发,直至将压力降为-0.09MPa以下,打开萃取罐口,将残渣取出;(4) After the extraction is completed, use a compressor to evaporate the residual subcritical fluid in the material in the extraction tank under reduced pressure. After the pressure in the extraction tank reaches 0Mpa, use a vacuum pump to perform negative pressure evaporation until the pressure drops to -0.09MPa Next, open the mouth of the extraction tank and take out the residue;
(5)混和油经压缩机减压蒸发到0Mpa后,同样转换为用真空泵进行负压蒸发,至蒸发罐压力为-0.09MPa以下,将所提取的脂溶性物质从蒸发罐低部放出;(5) After the mixed oil is decompressed and evaporated to 0Mpa by the compressor, it is also converted to negative pressure evaporation with a vacuum pump until the pressure of the evaporation tank is below -0.09MPa, and the extracted fat-soluble substances are released from the lower part of the evaporation tank;
(6)以上过程除装卸物料由人工完成外,其它步骤均采用PLC程序设定、自动完成整个萃取过程。(6) Except for the loading and unloading of materials, the above process is done manually, and the other steps are set by PLC program to automatically complete the whole extraction process.
本实用新型提供的超声辅助亚临界流体萃取装置的萃取方法通过如下方案实现:将脂溶性物料放入萃取罐内,然后注入亚临界流体,在一定压力条件下,脂溶性物料在亚临界流体中,经过一定时间的超声辅助萃取,再辅以容器夹层的热水加热,使固态物料中的脂溶性成份逐渐向液态的亚临界流体中扩散,并最终达到一个平衡。然后将含有脂溶性成分的亚临界流体(混合油)从萃取罐底部排到气液分离容器(蒸发罐)中,通过压缩机进行减压蒸发,将亚临界流体从混合油液体中不断转化为气态,并在压缩机的作用下,再由气态压缩为液态,回流到溶剂罐循环使用。根据物料中脂溶性成分含量的多少,通过多次萃取,最终将物料的脂溶性成分充分提取。The extraction method of the ultrasonic-assisted subcritical fluid extraction device provided by the utility model is realized through the following scheme: put the fat-soluble material into the extraction tank, then inject the subcritical fluid, and under certain pressure conditions, the fat-soluble material is in the subcritical fluid After a certain period of ultrasonic-assisted extraction, supplemented by hot water heating in the interlayer of the container, the fat-soluble components in the solid material gradually diffuse into the liquid subcritical fluid, and finally reach an equilibrium. Then the subcritical fluid (mixed oil) containing fat-soluble components is discharged from the bottom of the extraction tank into the gas-liquid separation vessel (evaporation tank), and evaporated under reduced pressure by a compressor to continuously convert the subcritical fluid from the mixed oil liquid into Gaseous state, and under the action of the compressor, it is compressed from gaseous state to liquid state, and returned to the solvent tank for recycling. According to the amount of fat-soluble components in the material, through multiple extractions, the fat-soluble components of the material are finally fully extracted.
本实用新型提供的超声辅助亚临界流体萃取装置的萃取方法,包括有如下步骤:The extraction method of the ultrasonic-assisted subcritical fluid extraction device provided by the utility model includes the following steps:
(1)首先将原料进行预处理,制成30~120目的颗粒,包括去杂、粉碎、制粒等。然后将预处理的物料装入料筒,再放入萃取罐内,用真空泵将容器中的空气抽尽,真空度为-0.1MPa以下。(1) First, the raw materials are pretreated to make 30-120 mesh granules, including impurity removal, crushing, granulation, etc. Then put the pretreated material into the barrel, put it into the extraction tank, and use a vacuum pump to exhaust the air in the container, and the vacuum degree is below -0.1MPa.
(2)利用压力差将溶剂罐内亚临界流体注入萃取罐内,料溶比为1∶1~5,其中所述的亚临界流体可以是甲烷、乙烷、丙烷、异丙烷、丁烷、高纯度异丁烷、液化石油气、二甲醚、四氟乙烷、六氟化硫等的一种或者其中两种及两种以上的混合物。(2) Utilizing the pressure difference to inject the subcritical fluid in the solvent tank into the extraction tank, the material-solution ratio is 1: 1~5, wherein the subcritical fluid can be methane, ethane, propane, isopropane, butane, One of high-purity isobutane, liquefied petroleum gas, dimethyl ether, tetrafluoroethane, sulfur hexafluoride, etc., or a mixture of two or more of them.
(3)对于原料中的中等极性功能团的萃取,可在步骤(2)中加入以质量计1~10%萃取夹带剂,其中所述的萃取夹带剂可以是乙醇或丙酮,从而将混合溶剂调整为弱极性溶媒,以便实现中等极性成分的萃取和分离。(3) For the extraction of the medium polarity functional group in the raw material, can add 1~10% extraction entrainer by mass in step (2), wherein said extraction entrainer can be ethanol or acetone, thereby will mix The solvent is adjusted to a weakly polar solvent in order to realize the extraction and separation of medium polar components.
(4)采用循环热水对萃取罐进行加热,温度控制在20~80℃之间,压力控制在0.2~2.0MPa。采用超声辅助萃取,超声功率为50-2500W,超声频率20-50KHz。(4) Using circulating hot water to heat the extraction tank, the temperature is controlled between 20-80° C., and the pressure is controlled at 0.2-2.0 MPa. Ultrasound-assisted extraction is used, the ultrasonic power is 50-2500W, and the ultrasonic frequency is 20-50KHz.
(5)经过5~180min的超声辅助萃取后,将液态的混合油(含有脂溶性成分的亚临界流体)从萃取罐低部放出,进入蒸发罐进行减压蒸发,将混合油中的溶酶充分气化,蒸发过程中通过夹层的热水加热,补充溶酶从液态到气态转化过程中所需的热量,气化后的气体经压缩机压缩后在冷凝器中变为液体,回流到溶剂罐后循环使用。(5) After 5-180 minutes of ultrasonic-assisted extraction, the liquid mixed oil (subcritical fluid containing fat-soluble components) is released from the lower part of the extraction tank, and enters the evaporation tank for vacuum evaporation, and the lysozyme in the mixed oil is Fully gasified, heating through the hot water in the interlayer during the evaporation process, supplementing the heat required for the conversion of lysozyme from liquid to gaseous state, the gasified gas is compressed by the compressor and becomes liquid in the condenser, and returns to the solvent Recycle after canning.
(6)根据原料中脂溶性成分含量,萃取次数选择1~5次,每遍重复上述2、3和4的过程即可。也可通过增加1~3个缓存罐方式,实现2~4次的逆流萃取。(6) According to the content of fat-soluble components in the raw materials, the number of extractions is selected from 1 to 5 times, and the above-mentioned processes of 2, 3 and 4 can be repeated each time. It is also possible to achieve 2 to 4 countercurrent extractions by adding 1 to 3 buffer tanks.
(7)萃取结束后,用压缩机将萃取罐内物料中的残留溶酶进行减压蒸发,蒸发过程中通过夹层的热水加热,补充溶酶从液态到气态转化过程中所需的热量,待萃取罐压力降到0Mpa后,再用真空泵进行负压蒸发,直至将压力降为-0.09MPa以下,打开萃取罐口,将残渣取出。(7) After the extraction is finished, use a compressor to evaporate the residual lysozyme in the material in the extraction tank under reduced pressure. During the evaporation process, the hot water in the interlayer is heated to supplement the heat required for the lysozyme to convert from liquid to gaseous state. After the pressure of the extraction tank drops to 0Mpa, use a vacuum pump to evaporate under negative pressure until the pressure drops below -0.09MPa, open the mouth of the extraction tank, and take out the residue.
(8)混和油经压缩机减压蒸发到0Mpa后,同样转换为用真空泵进行负压蒸发,至蒸发罐压力为-0.09Mpa以下,将所提取的脂溶性物质从蒸发罐低部排出即可。(8) After the mixed oil is decompressed and evaporated to 0Mpa by the compressor, it is also converted to vacuum pump for negative pressure evaporation until the pressure of the evaporation tank is below -0.09Mpa, and the extracted fat-soluble substances can be discharged from the lower part of the evaporation tank. .
(9)以上参数在控制面板上进行设置后,装置可按照工艺要求自动完成萃取过程;上述各步骤也可通过手工操作完成萃取过程。(9) After the above parameters are set on the control panel, the device can automatically complete the extraction process according to the process requirements; the above steps can also be completed by manual operation.
本实用新型的优点:Advantage of the utility model:
(1)本实用新型装置能满足多种亚临界流体萃取工艺要求,并可根据需要制作不同规模的实验装置或中试装置;采用PLC控制,自动化程度高;罐体采用快开门结构设计,操作、维护非常简便。(1) The device of the utility model can meet the requirements of various subcritical fluid extraction processes, and can make experimental devices or pilot devices of different scales according to the needs; PLC control is adopted, and the degree of automation is high; the tank body adopts a quick-opening door structure design, easy to operate , Maintenance is very simple.
(2)本实用新型的装置属于中、低压压力容器范围,大幅度降低了装置制造过程的工艺难度和工程造价;且运行成本低廉,相对产量大,适于多种物料的萃取实验和研究,易于在高校、研究所、企业推广应用。(2) The device of the present utility model belongs to the scope of medium and low pressure pressure vessels, which greatly reduces the technical difficulty and engineering cost of the device manufacturing process; and the operating cost is low, the relative output is large, and it is suitable for extraction experiments and research of various materials. It is easy to promote and apply in universities, research institutes and enterprises.
(3)基于本实用新型的方法利用亚临界流体沸点较低的特性,通过提高工艺过程的真空度,使萃取溶剂在10~50℃的温度下快速蒸发,提高了溶媒回收率,减少了溶媒损失,降低了能源消耗;且萃取是在密闭条件下进行,因而“热敏性”成份不变性、不氧化,是天然产物功效成分保质萃取的理想工艺。(3) The method based on the utility model utilizes the lower characteristic of the subcritical fluid boiling point, and by improving the vacuum degree of the process, the extraction solvent is evaporated rapidly at a temperature of 10 to 50° C., which improves the solvent recovery rate and reduces the solvent loss, reducing energy consumption; and the extraction is carried out under airtight conditions, so the "heat-sensitive" ingredients will not be denatured and oxidized, which is an ideal process for the quality-guaranteed extraction of natural product functional ingredients.
(4)基于本实用新型的方法根据萃取对象不同,可以灵活选择不同的亚临界萃取介质;同时也可根据原料目标物质的含量大小,灵活选择多种萃取方式。(4) The method based on the utility model can flexibly select different subcritical extraction media according to different extraction objects; meanwhile, multiple extraction methods can be flexibly selected according to the content of the target substance in the raw material.
(5)基于本实用新型的方法加工流程均处在比较安全的中、低压状态下完成,设备的有效容积受加工工艺的制约小,系统的安全性能指标相对提高,同时,生产中无“三废污染”,属环保工程。(5) The processing flow based on the method of the present utility model is completed under a relatively safe medium and low pressure state, the effective volume of the equipment is less restricted by the processing technology, and the safety performance index of the system is relatively improved. At the same time, there are no "three wastes" in production Pollution" is an environmental protection project.
(6)本发明的装置和方法将亚临界流体萃取技术与超声提取技术相结合,能明显提高萃取率、缩短提取时间、不破坏功效成分,是一种高效、低耗、环保、具有广阔应用前景的天然产物有效成分提取的新技术。(6) The device and method of the present invention combine subcritical fluid extraction technology with ultrasonic extraction technology, which can significantly increase the extraction rate, shorten the extraction time, and not destroy the functional components. Prospects for new techniques for the extraction of active ingredients from natural products.
附图说明:Description of drawings:
图1是本实用新型天然产物有效成分的亚临界流体萃取装置的结构示意图,其中1为萃取罐,2为蒸发罐,3为缓冲罐,4为冷凝器,5为溶剂罐,6为热水箱,7为热水泵,8为压缩机,9为真空泵,10为阻火器,11为超声发生装置,12为萃取罐快开门装置,13~34为调节阀门。Fig. 1 is the structural representation of the subcritical fluid extraction device of the active ingredient of the natural product of the present invention, wherein 1 is an extraction tank, 2 is an evaporation tank, 3 is a buffer tank, 4 is a condenser, 5 is a solvent tank, and 6 is hot water Box, 7 is a hot water pump, 8 is a compressor, 9 is a vacuum pump, 10 is a flame arrester, 11 is an ultrasonic generating device, 12 is a quick opening device for an extraction tank, and 13~34 are regulating valves.
具体实施方式Detailed ways
下面结合实施例对本实用新型作详细说明。Below in conjunction with embodiment the utility model is described in detail.
实施例1 亚临界液化石油气萃取天然青刺果油Example 1 Subcritical Liquefied Petroleum Gas Extraction of Natural Greenthorn Fruit Oil
取天然青刺果2.5kg,原料经预处理后含杂0.3%、胚片厚度0.35mm、含水量为8.5%、温度45℃。然后以亚临界液化石油气为溶酶萃取青刺果油,萃取温度45℃、萃取时间45min、萃取次数5次。混合油减压气化,达到0Mpa(表压)后抽真空脱溶,当表压为-0.09MPa,在温度45℃下保温30min。湿料胚减压气化,压缩回收溶酶。青刺果油主要品质指标测定结果:油中残溶0.85ppm;含杂0.1%;粕中含油2.0%;粕中残溶222ppm。Take 2.5kg of natural green sorrel fruit, the raw material contains 0.3% impurities after pretreatment, the thickness of the embryo sheet is 0.35mm, the water content is 8.5%, and the temperature is 45°C. Then subcritical liquefied petroleum gas was used as the lysozyme to extract the thorn fruit oil, the extraction temperature was 45°C, the extraction time was 45 minutes, and the extraction times were 5 times. The mixed oil is decompressed and gasified, and when it reaches 0Mpa (gauge pressure), it is vacuumed and precipitated. When the gauge pressure is -0.09MPa, it is kept at a temperature of 45°C for 30min. The wet material embryo is decompressed and gasified, and the lysozyme is recovered by compression. Determination results of the main quality indicators of the green thorn fruit oil: 0.85ppm residual solubility in the oil; 0.1% impurity; 2.0% oil content in the meal; 222ppm residual solubility in the meal.
实施例2 超声辅助亚临界丙烷萃取天然青刺果油Example 2 Ultrasonic-assisted subcritical propane extraction of natural green thorn fruit oil
取天然青刺果2.5kg,原料经预处理后含杂0.3%、胚片厚度0.35mm、含水量为8.5%、温度45℃。然后以亚临界丙烷为溶酶,超声辅助萃取青刺果油,萃取温度45℃、萃取时间30min、萃取次数3次、超声功率为1500W、超声频率20KHz。混合油减压气化,达到0Mpa(表压)后抽真空脱溶,当表压为-0.09MPa,在温度45℃下保温30min。湿料胚减压气化,压缩回收溶酶。青刺果油主要指标测定结果:油中残溶0.85ppm;含杂0.1%;粕中含油1.2%;粕中残溶195ppm。Take 2.5kg of natural green sorrel fruit, the raw material contains 0.3% impurities after pretreatment, the thickness of the embryo sheet is 0.35mm, the water content is 8.5%, and the temperature is 45°C. Then subcritical propane was used as the lysozyme, and the thorn fruit oil was extracted with ultrasonic assistance. The extraction temperature was 45°C, the extraction time was 30 minutes, the extraction times were 3 times, the ultrasonic power was 1500W, and the ultrasonic frequency was 20KHz. The mixed oil is decompressed and gasified, and when it reaches 0Mpa (gauge pressure), it is vacuumed and precipitated. When the gauge pressure is -0.09MPa, it is kept at a temperature of 45°C for 30min. The wet material embryo is decompressed and gasified, and the lysozyme is recovered by compression. Determination results of the main indicators of green thorn fruit oil: residual solubility in oil is 0.85ppm; impurity content is 0.1%; oil content in meal is 1.2%; residual solubility in meal is 195ppm.
实施例3 亚临界丙烷和丁烷萃取小麦胚芽油Example 3 Subcritical Propane and Butane Extraction of Wheat Germ Oil
取小麦胚芽2.5kg,经清理、微波干燥等预处理后含杂0.15%、含水量为7.5%。采用亚临界丙烷和丁烷,按逆流三浸工艺进行萃取,第一遍、第二遍分别用上一罐浸出的第二遍、第三遍混合油萃取,每遍浸泡35分钟。第一遍浸出的混合油打到蒸发罐内,其余二遍打到缓存罐。浸出温度为室温,压力为0.4MPa,料溶比1∶2.5,丙烷与丁烷的比例为3∶1。混合油蒸发时循环热水温度控制在50℃以下,达到0Mpa(表压)后抽真空脱溶,当表压为-0.09MPa,在温度45℃下保温30min。湿粕脱溶控制加热温度在50℃以下,所得麦胚蛋白,是一种高级食品添加剂。小麦胚芽油主要指标测定结果:油中残溶0.75ppm;含杂0.2%;粕中含油0.9%;粕中含溶402ppm。Take 2.5kg of wheat germ, after cleaning, microwave drying and other pretreatments, the impurity content is 0.15%, and the water content is 7.5%. Using subcritical propane and butane, the extraction is carried out according to the countercurrent three-immersion process. The first and second times are respectively extracted with the second and third times of mixed oil leached from the previous tank, and each time is soaked for 35 minutes. The mixed oil leached in the first pass is pumped into the evaporation tank, and the other two passes are pumped into the buffer tank. The leaching temperature is room temperature, the pressure is 0.4MPa, the ratio of material to solution is 1:2.5, and the ratio of propane to butane is 3:1. When the mixed oil evaporates, the temperature of the circulating hot water is controlled below 50°C, and when it reaches 0Mpa (gauge pressure), it is vacuumed and precipitated. When the gauge pressure is -0.09MPa, it is kept at a temperature of 45°C for 30min. Control the heating temperature below 50°C for wet meal desolventization, and the obtained wheat germ protein is a high-grade food additive. Measuring results of main indicators of wheat germ oil: residual soluble in oil 0.75ppm; impurity 0.2%; oil in meal 0.9%; soluble in meal 402ppm.
实施例4 亚临界四氟乙烷逆流萃取番茄籽油Example 4 Subcritical tetrafluoroethane countercurrent extraction of tomato seed oil
取番茄籽2.5kg,经清理、软化、轧胚等预处理后含杂0.15%、胚片厚度0.30mm、含水量为9.5%。采用亚临界四氟乙烷,按逆流四浸工艺进行萃取,第一遍、第二遍、第三遍分别用上一罐浸出的第二遍、第三遍、第四遍混合油萃取,每遍浸泡35分钟。第一遍浸出的混合油打到蒸发罐内,其余三遍打到缓存罐。浸出温度为室温,压力为1.25MPa,料溶比1∶1.5,并加入1.5%的无水乙醇。混合油蒸发时循环热水温度控制在60℃以下,达到0Mpa(表压)后抽真空脱溶,当表压为-0.09MPa,在温度45℃下保温30min。湿粕脱溶控制加热温度在50℃以下,所得番茄籽粕是一种高级食品添加剂。番茄籽油主要指标测定结果:油中残溶0.85ppm;含杂0.1%;粕中含油1.2%;粕中含溶314ppm。Take 2.5 kg of tomato seeds, after pretreatments such as cleaning, softening, and embryo rolling, they contain 0.15% impurities, 0.30mm thickness of embryo slices, and 9.5% water content. Subcritical tetrafluoroethane is used to extract according to the countercurrent four immersion process. The first, second and third times are respectively extracted with the second, third and fourth times of mixed oil leached from the previous tank. Soak all over for 35 minutes. The mixed oil leached in the first pass is pumped into the evaporation tank, and the remaining three passes are pumped into the buffer tank. The leaching temperature is room temperature, the pressure is 1.25MPa, the ratio of material to solution is 1:1.5, and 1.5% absolute ethanol is added. When the mixed oil is evaporating, the temperature of the circulating hot water is controlled below 60°C, and when it reaches 0Mpa (gauge pressure), it is vacuumed and precipitated. When the gauge pressure is -0.09MPa, it is kept at a temperature of 45°C for 30min. Control the heating temperature below 50°C for the desolvation of the wet meal, and the obtained tomato seed meal is a high-grade food additive. Determination results of main indicators of tomato seed oil: residual soluble in oil 0.85ppm; impurity 0.1%; oil in meal 1.2%; soluble in meal 314ppm.
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CN200920231157XU Expired - Fee Related CN201578881U (en) | 2009-09-03 | 2009-09-03 | Subcritical Fluid Extraction Device for Active Components of Natural Products |
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Cited By (7)
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CN102634409A (en) * | 2012-04-23 | 2012-08-15 | 湖南宏润绿色油业科技有限公司 | Tea oil leaching production method and special equipment thereof |
CN103694108A (en) * | 2013-12-17 | 2014-04-02 | 河南金丹乳酸科技股份有限公司 | Equipment and method for continuously producing liquid lactic acid by using crystal lactic acid |
CN107348064A (en) * | 2017-07-31 | 2017-11-17 | 福建达利食品科技有限公司 | A kind of processing method of herbal tea |
CN107459838A (en) * | 2017-06-05 | 2017-12-12 | 中国科学院兰州化学物理研究所 | Subcritical abstraction is combined the method for preparing medlar carotenoid class natural pigment with membrane separating and purifying concentration |
CN109536276A (en) * | 2018-12-29 | 2019-03-29 | 江苏大学 | A kind of subcritical multicomponent solvent extraction equipment of continous way and method |
CN110448934A (en) * | 2019-08-07 | 2019-11-15 | 广东药科大学 | The extracting process and ultrasonic coupling dynamic Subcritical Water Extraction device of emblic polyphenol |
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CN102634409A (en) * | 2012-04-23 | 2012-08-15 | 湖南宏润绿色油业科技有限公司 | Tea oil leaching production method and special equipment thereof |
CN102634409B (en) * | 2012-04-23 | 2013-07-17 | 湖南宏润绿色油业科技有限公司 | Tea oil leaching production method and special equipment thereof |
CN103694108A (en) * | 2013-12-17 | 2014-04-02 | 河南金丹乳酸科技股份有限公司 | Equipment and method for continuously producing liquid lactic acid by using crystal lactic acid |
CN103694108B (en) * | 2013-12-17 | 2015-10-28 | 河南金丹乳酸科技股份有限公司 | Utilize equipment and the method for crystal lactic acid continuous seepage liquid lactic acid |
CN107459838A (en) * | 2017-06-05 | 2017-12-12 | 中国科学院兰州化学物理研究所 | Subcritical abstraction is combined the method for preparing medlar carotenoid class natural pigment with membrane separating and purifying concentration |
CN107459838B (en) * | 2017-06-05 | 2019-07-30 | 中国科学院兰州化学物理研究所 | Subcritical abstraction combines the method for preparing medlar carotenoid class natural pigment with membrane separating and purifying concentration |
CN107348064A (en) * | 2017-07-31 | 2017-11-17 | 福建达利食品科技有限公司 | A kind of processing method of herbal tea |
CN109536276A (en) * | 2018-12-29 | 2019-03-29 | 江苏大学 | A kind of subcritical multicomponent solvent extraction equipment of continous way and method |
CN110448934A (en) * | 2019-08-07 | 2019-11-15 | 广东药科大学 | The extracting process and ultrasonic coupling dynamic Subcritical Water Extraction device of emblic polyphenol |
CN110448934B (en) * | 2019-08-07 | 2022-03-04 | 广东药科大学 | Extraction method and ultrasonic coupling dynamic subcritical water extraction device of polyphenols |
RU2738938C1 (en) * | 2019-12-23 | 2020-12-18 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Тамбовский государственный технический университет" (ФГБОУ ВО "ТГТУ") | Universal vacuum extractive-evaporation plant |
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