CN102702139B - 热提取方法和产物 - Google Patents
热提取方法和产物 Download PDFInfo
- Publication number
- CN102702139B CN102702139B CN201210096487.9A CN201210096487A CN102702139B CN 102702139 B CN102702139 B CN 102702139B CN 201210096487 A CN201210096487 A CN 201210096487A CN 102702139 B CN102702139 B CN 102702139B
- Authority
- CN
- China
- Prior art keywords
- taxan
- heat extraction
- rich
- starting material
- heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
- C07D305/14—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms condensed with carbocyclic rings or ring systems
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
- A61K36/13—Coniferophyta (gymnosperms)
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
- C10B49/16—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form
- C10B49/20—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form in dispersed form
- C10B49/22—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form in dispersed form according to the "fluidised bed" technique
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C5/00—Production of pyroligneous acid distillation of wood, dry distillation of organic waste
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Natural Medicines & Medicinal Plants (AREA)
- Materials Engineering (AREA)
- Medical Informatics (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Alternative & Traditional Medicine (AREA)
- Biotechnology (AREA)
- Botany (AREA)
- Public Health (AREA)
- Medicinal Chemistry (AREA)
- Microbiology (AREA)
- Mycology (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- Dispersion Chemistry (AREA)
- Wood Science & Technology (AREA)
- Combustion & Propulsion (AREA)
- Medicines Containing Plant Substances (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Epoxy Compounds (AREA)
- Extraction Or Liquid Replacement (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及植物材料的热提取物及其提取方法。通过原材料的热提取从植物原材料生产热提取物的方法,其中改进之处在于提取和分配步骤所需要的昂贵的和/或有毒的有机溶剂的量更少。
Description
相关申请
本申请是于2007年4月2日向中国国家知识产权局提交的题为“热提取方法和产物”的第200780020439.9号发明专利申请(国际申请号PCT/CA2007/000535)的分案申请。
技术领域
本发明涉及通过热提取生产提取物的方法和热提取产物。
背景技术
从原材料中提取所期望的化合物通常是通过溶剂提取方法进行的。
当今在包括生物质的许多原材料上使用溶剂提取来提取所期望的组分。其一个典型实例是从生物质中提取紫杉烷。
紫杉烷是一组二萜类化合物,其中有一些已经被证明对于癌症及比如多发性硬化和肾病的其他重病的治疗是有用的。特别地,已经证实紫杉烷化合物紫杉醇、多西紫杉醇、浆果赤霉素III、10-O-脱乙酰基巴卡丁III(10-DAB或DAB)、13-乙酰基-9-羟基巴卡丁III(DHB)、三尖杉宁碱和prostratin(12-脱氧佛波醇13-乙酸酯(12-deoxyphorbol13-acetate))在药物应用中有用。例如,目前紫杉醇被用于癌症治疗(由百时美施贵宝以上市)。某些紫杉烷,比如紫杉醇和多西紫杉醇,能够在没有额外化学改性的情况下被直接用在药物应用中,而其它紫杉烷(例如DAB和DHB)被认为是生产其它的紫杉烷比如紫杉醇和多西紫杉醇的母体。
紫杉烷的主要来源是属于紫杉属的紫杉(铁杉)树的树皮、针叶和剪取物(clipping)。令人遗憾的是,即使紫杉烷在紫杉中的浓度高于在其它树种中的浓度,其绝对浓度也是非常低的。例如,已经有报道在一般样品中,从紫杉树的树皮中仅获得0.01%的紫杉醇产量,而从剪取物和针叶中获得的紫杉醇产量在0.003~0.015%(折干计算)的范围内(Huang等人,J.Nat.Prod.,49:665,1986),其中第一提取是溶剂提取。此外,紫杉树相对稀少并且生长相当慢,引起对重新造林和资源管理不能跟上需求的合理忧虑。虽然已经设计了生产紫杉醇的合成和半合成渠道,但是它们对于商业生产而言过于复杂并且通常太不经济。生产多西紫杉醇的半合成方法也已经设计出来。
目前商业的紫杉醇及其它紫杉烷的生产方法是复杂和昂贵的。其单元操作主要是物理方法,包括:收割/采集、研磨、覆盖、初级溶剂提取和分离以得到粗紫杉烷产物。当生产出粗紫杉烷产物后,在另外的溶剂提取和其它精制步骤中可以回收和纯化紫杉醇。在许多情况下,通过化学方法将其它天然紫杉烷转变为额外产量的紫杉醇或者多西紫杉醇。
目前从原材料中分离其它的化合物的方法也常常包括溶剂提取的初始步骤,其在去除大量杂质的同时也去除了所期望的化合物。因此,经常进行一个或多个液体分配步骤以浓缩在提取液中所期望的化合物的浓度,在一些情况中随后是几个色谱步骤。
这些方法的一个缺点是为了提取和分配步骤它们需要大量昂贵并且有时有毒的有机溶剂。在商业上,这意味着要为材料、合格的专门技术、合格的技术人员和基础设施付出非常高的资金和生产成本。
因此,需要一种分离化合物的方法,该方法可以减少或者消除对大量有毒和昂贵有机溶剂的需求。
发明内容
根据本发明的一个广的方面,提供了一种通过原材料的热提取生产热提取物的方法,包括:将原材料加热至一定温度和一段时间,其足够从原材料中提取出一定量的所需化合物且相当大量的所需化合物没有转化为一种或多种其它的化合物。
根据本发明的另一方面,提供了一种通过热提取获得富含紫杉烷的提取物的方法。
在本发明的一个示例性实施方式中,提供了一种通过生物质原材料的热提取从含有二萜类化合物的生物质原材料中生产富含紫杉烷的热提取物的方法,包括:将生物质原材料加热至一定温度和一段时间,其足够提取出一定量的紫杉烷且相当大量的紫杉烷没有转化为一种或多种其它的化合物。
在本发明的一个示例性实施方式中,提供了一种生产包含所需化合物的热提取物的方法,包括:将原材料加入包括封闭容器、热源和至少一个回收装置的热提取体系中;在该热提取体系中将原材料加热至一定温度和一段时间,其足够生产含有一定量的所需化合物的产物流且相当大量的所需化合物没有转化为一种或多种其它的化合物;在至少一个回收装置的至少一个装置中从富含所需化合物的产物流中收集至少一个馏分以获得热提取物。
在本发明的一个进一步的示例性实施方式中,提供了一种从含有二萜类化合物的生物质原材料中生产富含紫杉烷的热提取物的方法,包括:将生物质原材料加入包括封闭容器、热源和至少一个回收装置的热提取体系中;在该热提取体系中将生物质原材料加热至一定温度和一段时间,其足够生产含有一定量的紫杉烷的产物流且相当大量的紫杉烷没有转化为一种或多种其它的化合物;在至少一个回收装置的至少一个装置中从产物流中收集至少一个含有紫杉烷的馏分以获得富含紫杉烷的热提取物。
根据本发明的另一个示例性实施方式,提供了一种富含紫杉烷的提取物。
根据本发明的另一个示例性实施方式,提供了一种通过本发明方法获得的富含萜烯或者萜类化合物的热提取物。
根据本发明的又一个进一步的示例性实施方式,提供了一种通过本发明方法获得的富含紫杉烷的热提取物。
根据本发明的一个进一步的示例性实施方式,提供了一种通过本发明方法获得的富含类黄酮化合物的热提取物。
根据本发明的另一个示例性实施方式,提供了一种通过本发明方法获得的富含表儿茶素的热提取物。
根据本发明的另一个示例性实施方式,提供了一种通过本发明方法获得的富含儿茶素的热提取物。
根据本发明的另一个示例性实施方式,提供了一种通过本发明方法获得的富含咖啡因的热提取物。
根据本发明的还一个示例性实施方式,提供了一种通过本发明方法获得的富含香草醛的热提取物。
根据本发明的又一个示例性实施方式,提供了一种通过本发明方法获得的富含β-谷甾醇的热提取物。
根据本发明的再一个进一步的示例性实施方式,提供了一种含有紫杉醇和10-O-脱乙酰基巴卡丁III的提取物,其中基于重量比,在该提取物中存在的10-O-脱乙酰基巴卡丁III的量比紫杉醇的量多大约10倍。
根据本发明的又一个进一步的示例性实施方式,提供了一种含有紫杉醇和13-乙酰基-9-羟基巴卡丁III的提取物,其中基于重量比,在该提取物中存在的13-乙酰基-9-羟基巴卡丁III的量比紫杉醇的量多大约10倍。
根据本发明的再一个进一步的示例性实施方式,提供了一种含有紫杉醇和7-表-紫杉醇的提取物,其中基于重量比,在该提取物中存在的7-表-紫杉醇的量比紫杉醇的量多大约10倍。
附图说明
图1是根据本发明的一个实施方式的适合的热提取体系的一个实例的示意图。
图2是图示根据实施例1C的本发明方法的流程图。
具体实施方式
人们已经注意到热提取能够被用作溶剂提取的替代的提取方法。
热提取意味着不需要目前与溶剂提取方法相关的原料溶剂提取的初始步骤。
在本文中使用的术语“热提取”(其也可以被称为“热蒸馏”或者“快速热蒸馏”)指的是一种提取方法,其中使用热来从适合的原材料中分离出一种或多种所需化合物。通过在封闭环境中以控制方式向适当的原材料施加热,可以将一种或多种所需化合物释出、保持、回收并基本上保持未被破坏的状态。因此热提取可以用于从原材料中提取天然存在的所需化合物而没有化学转化,所述天然存在的化合物是在原材料中发现的。虽然热提取可能将原材料中的某些化合物破坏或者化学转化,但是相当大量的所需化合物没有被降解或者以其它的方式被化学改变。通过热提取获得的“天然存在的所需化合物”或“所需化合物”指的是存存于原材料中的化合物,并且其中相当大量的该化合物没有被本发明的热提取方法降解或者以其它的方式被化学转变为另一种化合物。
可以用在本发明中的原料没有特别限制,只要它提供一种或者多种所需化合物的来源并且可以经受热提取。例如,生物质是用于溶剂提取方法的普通原材料,而它也可以是用于本发明方法的适合原材料。例如,生物质可以源自植物。植物的任何馏分都可能适用于热提取,包括树皮、针叶、茎、根、叶子、种子、在培养中的植物细胞等;或其混合物。用在本发明中的源于植物的生物质材料可以是,例如,刚采集状态、干状态的或者含水状态。
如果一种或多种紫杉烷是所需化合物,那么比如那些源自紫杉树的含有二萜类化合物的生物质材料通常被认为是极好的紫杉烷的来源。例如,紫杉属或澳洲红豆杉(Austrotaxus)属的种的所有或多种组分都可以用作紫杉烷来源。
在另一个发明实施方式中,热提取可以用来从适合的原材料中提取类黄酮化合物。从多种植物中已经表征了超过五千种天然存在的类黄酮化合物(包括异类黄酮化合物和新类黄酮化合物)。本发明的热提取方法可用于从生物质材料中提取这些化合物中的一个馏分。这些化合物中的一个馏分非限制性地包括五羟黄酮、表儿茶素、原花色素、柑橘属生物类黄酮、儿茶素、白藜芦醇、莰非醇、香草醛和β-谷甾醇。例如,在本发明的一个实施方式中,从可可或含有可可的原材料中提取出表儿茶素。例如,类黄酮化合物可以用作抗氧化剂以及其它的用途,比如用在治疗或防治癌症、心脏病等。例如并且非限制性的,类黄酮化合物的另一个来源为亚麻或者含有亚麻的原材料。可以使用亚麻来获得包含包括儿茶素和表儿茶素的一种或多种类黄酮化合物的根据本发明的热提取物。其它从生物质提取出的天然产物也可以通过利用热提取获得,并且可以用作药物、天然添加剂等。作为另一个非限制性实例,含有咖啡的原材料可用于获得包含咖啡因的热提取物。
显而易见,对本领域中的技术人员来说,许多其它材料都可能为用于获得包含一种或多种所需化合物的热提取物的适合的原材料。
用在本发明中的原材料也可以减小尺寸。例如,在热提取之前,可以用在本领域中已知的方法将其切碎或者磨碎。
在本发明的一个示例性实施方式中,首先将要进行热提取的材料的尺寸减小至在其最小尺寸上的平均直径小于约2cm。在本发明的另一个示例性实施方式中,首先将原材料的尺寸减少至在其最小尺寸上的平均直径小于约1cm。
根据本发明的热提取可以在热提取体系中进行,对该体系没有特别限制。在本发明的热提取中,可以在控制的和封闭环境中将原材料的全部或者一个馏分受热。例如,如果原材料是生物质材料,则可以使用木质素的、纤维素的或者半纤维素的馏分或者其组合物。控制的环境指的是这样一种环境,其中以促使原材料发生相变或化学转化的方式施加热,而不是以引起相当大量的存在于原材料中的所需化合物被有害地改变、降解、破坏等的方式施加热。例如,在一个实施方式中,所述热提取物包含从所需化合物以化学或者其它方式转化为另一种化合物得到的约0~10%w/w(或其任何子范围)的杂质。
在本发明的一个示例性实施方式中,所述热提取是在包括封闭容器、热源和一个或多个回收装置的热提取体系中进行的。然后可以通过传热至原材料和任何所得到的中间产物来完成热提取。这样可以将原材料和任何所得到的中间产物加热至足够的温度和足够的时间以生产产物流,然后其馏分可以在一个或多个回收装置中回收并收集以得到提取物。
例如,所述热提取体系可以包括标准干馏体系(standretortsystem)(即,在真空或在压力下的固定床或移动床)、鼓泡流化床、上流式热提取装置、循环流化床、传送床、烧蚀性热提取装置、气流床热提取装置、回转炉或机械传送热提取装置(例如,加热螺旋体系)。
收集在热提取过程中生产的产物蒸汽和液体的任何装置都可以用作回收装置。回收装置可以包括冷凝器。该冷凝器可以是从蒸汽冷却并收集液体产物的接触或表面冷凝器,或者也可以从蒸汽冷却并收集液体产物的液体骤冷。回收装置也可以包括除雾器、纤维过滤床或其它用在本领域中来从蒸汽流收集液体产物的装置。回收装置可以包含一个或多个组件,例如,一个或多个可以以串联连接的冷凝器。
在本发明的一个示例性实施方式中,在热提取体系中供应足够的热以产生约250℃~650℃范围内的温度,或其任何子范围的温度,包括,例如,约300℃~550℃,或者约320℃~400℃。材料在热提取体系中的总停留时间可以为,例如,少于约30秒,例如,在约0.1~约30秒的范围内,或者其任何子范围。例如,在一个示例性实施方式中,总停留时间为约0.2~约5秒。在另一个示例性实施方式中,总停留时间为约2秒或更少。在热提取体系中的材料的停留时间是以从在热提取体系中的原材料的加热到淬灭(例如冷却)之间的时间间隔来测量的。
热提取可以产生包括固体、液体和/或蒸汽的产物流。该产物流可以被分馏以得到馏分,所述馏分可以被收集得到一种或多种提取物。馏分可以是例如焦的固体、液体和/或蒸汽,或其组合。可以获得含有所需化合物的浓缩提取物的馏分或其组合。液体和/或蒸汽馏分通常会比固体馏分包含更高浓度的所需化合物。但是,也可以获得固体馏分。例如,在紫杉生物质的热提取过程中,紫杉烷可能集中并浓缩在任何固体副产物,比如碳副产物的表面、基体或者孔隙上,这可能导致富含紫杉烷的固体馏分,其可以被收集以获得本发明富含紫杉烷的提取物。
在本发明的一个实施方式中,通过冷凝根据本发明的热提取方法获得的蒸汽得到液体馏分。在从液体中除去例如焦的固体之后并收集液体也可以获得液体馏分以得到根据本发明的提取物。在基于植物的生物质材料的提取之后获得的液体馏分可能是,例如,焦油、沥青、焦木酸混合物等。
在本发明的热提取方法中,液体和/或蒸汽馏分可以被进一步分馏。这样产生的各个进一步的馏分可以被分别收集以得到多个提取物,或者被收集并合并成一个或多个提取物。分馏也可以用于选择性生产富含选定的化合物,例如选定的紫杉烷的提取物。
本发明的提取物(本文也称为“热提取物”)可以是例如所收集的固体、液体和/或蒸汽馏分,或其任何组合。其也可以所收集的固体、液体和/或蒸汽馏分的馏分,或所选定的收集的馏分的组合。通过收集单个馏分或者收集并合并多个馏分可以获得单个提取物。通过收集多个馏分或者通过收集多个合并的馏分也可以获得多个提取物。而且,该提取物可能包含或不包含从原材料的相变(例如,从固体到液体等)。
人们已经注意到热提取可以提供比在文献中报道的用其它方法,包括传统的溶剂回收提取和提纯方法及其他非溶剂方法的产率更高的所提取的化合物的产率。
例如,人们已经注意到可以通过热提取方法得到更高产率的总紫杉烷和包括紫杉醇的特定的紫杉烷。人们还进一步注意到,通过热提取方法获得的富含紫杉烷的提取物在给定体积中比等体积的紫杉属或者澳洲红豆杉属固体生物质原材料中或者等体积的紫杉属或者澳洲红豆杉属生物质材料的初始(第一步)溶剂提取物中具有更高浓度的紫杉烷。
更浓缩的提取物的一个含义为,为了达到可比量的成品,在随后的提纯、分离和回收步骤中需要处理的材料的体积比使用固体原料材料或者从常规溶剂回收工艺中获得的提取物的情况要更小。为了得到可比产率,已经观察到在后续提纯步骤中要被处理的本发明富集后的提取物的初始体积可以比在常规溶剂提取方法中需被处理的初始材料的体积更小,例如小一个数量级。例如,对于紫杉烷提取,当与为获得可比产率的纯化紫杉烷在常规溶剂提取方法中需被处理的初始生物质材料的体积相比,热提取可以生产出减少了例如10倍、15倍、25倍或50倍、或更大倍数、或在其中间倍数体积的富含紫杉烷的提取物。
在本发明的富含紫杉烷的提取物中可能存在的紫杉烷包括一种或多种下面的紫杉烷化合物:紫杉醇、三尖杉宁碱、浆果赤霉素III、10-脱乙酰基紫杉醇、10-脱乙酰基三尖杉宁碱、10-脱乙酰基巴卡丁III(又名10-DAB或者DAB)、13-乙酰基-9-羟基巴卡丁III(又名DHB)、7-木糖基紫杉醇、7-木糖基三尖杉宁碱、7-木糖基巴卡丁III、及其衍生物和类似物。该列举并非穷举。其它的紫杉烷也可能存在于本发明的富含紫杉烷的提取物中。
除了不止一种紫杉烷化合物外,通过热提取生产的馏分和富含紫杉烷的提取物也可能包含许多其它组分,包括解聚木质素、成碎片的纤维素-衍生产物和半纤维素-衍生产物,和包括酚类化合物的其它反应组分,以及许多其它组分。
已经观察到热提取比已知的紫杉烷回收或者生产方法提供了更高的紫杉烷总产率,以及更高的具有目前商业价值的紫杉烷产率。在通过热提取获得的提取物中观察到的主要紫杉烷组分的“指纹”或相对分布,和在所述提取物中的紫杉烷的浓度也不同于通过目前方法获得的提取物。例如,与在文献中报道的从紫杉针叶和剪取物的溶剂提取中获得的平均产率相比,已经观察到紫杉醇产率可以增加约3至约5倍(即约300至约500%),DHB产率可以增加约2至约3倍(即约200至约300%),DAB增加约8倍(即约800%),并且总的紫杉烷产率可以增加约20倍(即约2000%)。
根据本发明的一个理论,其不被认为限制本发明的范围,认为热提取释放了可能被化学结合或者物理隔离(例如,在细胞结构中)因而不能通过溶剂方法回收的化合物。在这些情况下,在提取自由和可得到的所需化合物的同时,本发明的热提取可以同时通过使弱化学键断裂和/或使任何可能隔离或者阻止用常规方法提取的物理结构破裂来释放和提取结合的或者隔离的化合物。例如,当原材料是生物质时,所需化合物可能包含在液泡中,该液泡可以被热提取破裂以释放全部内容物,通过使用常规提取方法通常不会发生这种破裂和释放。
包括但并不限于液体、液体馏分、固体和固体馏分的本发明的提取物可以用本领域技术人员已知的各种方法进行进一步处理来为商业用途纯化、离析和回收所需化合物。
例如,当回收紫杉烷时,本发明方法可以进一步包含将所获得的富含紫杉烷的提取物与水或者一些其它适当的分配溶剂相接触的步骤以进一步分离、离析和浓缩紫杉烷组分,所述富含紫杉烷的提取物包括,例如通过合并收集的所有馏分、合并收集的选定液体馏分和合并收集的固体碳馏分获得的整个提取物。水或一些其它适当的分配溶剂的加入可以直接在热提取体系中发生(即,原位),特别是在生物质的处理过程中的产物回收装置中,或者作为在将产物从热提取工艺回收后的单独的步骤或几个步骤。
而且,为了从其它较少需要的组分中离析和浓缩某些所需化合物馏分,本发明的热提取方法还可以包含分馏步骤。(例如,当提取紫杉烷时,某些所需紫杉烷可以从较少需要的紫杉烷、酚类化合物、木质纤维素、抑制剂和其它污染物中分离出来。)可以进行非需要组分的去除以简化后续提纯步骤或者增加中间物的经济价值。
使用目前有机溶剂提取技术从紫杉树皮中获得的紫杉醇的离析产率一般约为0.01%,而从剪取物和针叶中为约0.003至约0.015%。但是,用本发明方法已经获得约0.031至0.049%的离析产率。如通过目前有机溶剂提取技术从剪取物和针叶中得到DHB的离析产率一般为约0.04%。但是,用本发明方法已经获得在约0.08至0.12%之间的离析DHB产率。如通过目前有机溶剂提取技术从剪取物和针叶中得到DAB的离析产率一般为约0.06%。但是,用本发明方法已经获得在约0.46至0.53%之间的离析DAB产率。如通过目前有机溶剂提取技术从剪取物和针叶中回收得到的总紫杉烷的产率一般为约0.25%。但是,用本发明方法已经测量到了在5至7%的总紫杉烷产率。
热提取也可以用在可能已经被包括通过溶剂提取的初步处理过的原材料上。例如,已经观察到可以从新的来源中或者在溶剂提取之后热提取出咖啡因。
适于制备根据本发明的一个或多个提取物的热提取体系的一个实例描述在美国专利第6,844,420号(Freel和Graham)中,其公开内容在此引入作为参考,并且图示在图1中。简要而言,该体系包括进料***(10)、封闭容器(20)、颗粒状无机加热载体再加热***(30),和为了在本文中描述的本发明目的,至少一个回收装置,其如在图1中所示,并且并其不被认为以任何方式限制本发明,可以包含初级(40)和次级(50)冷凝器,经过这些冷凝器将在热提取过程中生产的产物蒸汽流例如利用液体骤冷(80)冷却并收集。回收装置也可以包括除雾器(60)和纤维过滤床(70)或其它装置以收集液体产物。本发明的热提取产物成分可以源自从至少一个回收装置,例如初级或次级回收装置或者其组合中获得的选定的产物馏分,或者其可以是从包括去雾器和纤维过滤床的一级和二级回收装置或者其组合中获得的所有的油(即,所有的热液体产物)。但是,应当理解,类似的包含不同数目或尺寸的回收装置、或者不同冷凝装置的热提取体系可以用作为本发明目的的提取物的选择性制备。
在图1中简略画出的在热提取反应器体系中使用的回收装置体系,其不被认为以任何方式限制本发明,可以包括使用直接液体接触冷凝器(80)来冷却热提取产物。但是,应当理解,包括表面冷凝器的任何适合的回收装置都可以使用。在一个实施方式中,在这些冷凝器(80)中使用的用于冷却热提取产物的液体是从相应地冷却后的初级或者次级冷凝器产物(90)获得的。但是,如同对本领域中的技术人员是显而易见的那样,任何在初级和次级回收装置或者其组合中用于冷却产物的其它相容液体也可以用于这个目的。并且,其它洗涤器或者包括包含固体表面的热交换器等的冷却装置也可用于冷却产物蒸汽,这也被认为在本发明的范围内。
实施例1和2
A.原材料-加拿大紫杉的描述
加拿大紫杉(TaxuscanadensisMarsh、Canadayew、groundhemlock)灌木是在2004年7~9月间从加拿大安大略省苏圣玛丽周围地区(北纬46.34度,西经84.17度)收集的。压制的凭证标本以红豆杉-紫杉科的加拿大紫杉(TaxuscanadensisMarsh)(2004-4001-10CFS-SSM#s)存放在加拿大***-苏圣玛丽植物标本室中。新鲜的加拿大紫杉(T.Canadensis)针叶和小枝(twig)在室温22-24℃下风干。干燥后的样品在Thomas-Wiley实验室磨机,Model4(ThomasScientific,美国)中研磨成~0.5mm颗粒大小。
B.分析方法和程序
紫杉烷产物的分析
使用配备有电脑和Empower软件、自动扫描光电二极管阵列分光光度检测仪和分析柱的WatersDeltaPrep4000液相色谱仪来进行高效液相色谱。在如下所述的实验中使用的分析柱为Curosil-PFPPhenomenox(内径250x4.60mm)。使用乙腈/水溶剂体系在室温下采用改进的梯度色谱技术(Phenomenex)。但是,也使用了其它的溶剂体系。使用乙腈/水的适当梯度,例如25/75至65/35梯度在超过40分钟的一段时间以1.0ml/min的流速将样品洗脱。在波长228nm处检测化合物并且通过光电二极管阵列检测器从200至400nm扫描可分辨峰。
将提取物的稀释溶液(10mg/mL)通过13mmGHP0.45μmMinispike(Waters,EDGE)过滤,并在加入和没有加入标准品的情况下将10μl注入到HPLC柱中。根据保留时间和UV光谱确认峰。使用由市售紫杉烷标准品获得的换算系数将以在228nm处的吸光度测量的峰高转换为mg/ml。这样的HPLC分析重复进行三次。
在紫外-可见BeckmanDU系列640分光光度计上记录UV光谱。利用TLC和HPLC通过与标准样品(ChromaDex,圣塔安那,加利福尼亚,美国)的共-色谱分析法来鉴定紫杉烷。
实施例1:利用热提取生产热提取物
基本上如在美国专利第6,844,420号(其公开内容在此引入作为参考)中所描述的那样将根据上述方法制备的铁杉原料在热提取体系中进行处理。如下所述,在热提取体系中,焦产物与产物蒸汽/气流快速分离,并在初级回收装置内利用直接液体接触冷凝器或者液体骤冷将产物蒸汽和释放出的液体快速骤冷。保留在产物蒸汽中的化合物被转送至以串联方式与初级回收装置连接的次级回收装置。然后在该次级回收装置中利用直接液体接触冷凝器或者液体骤冷将产物蒸汽骤冷,并收集冷凝的产物。在产物蒸汽中的任何剩余产物在除雾器和过滤床中收集(见图1)。收集初级回收装置产物以及次级回收装置产物。从回收装置得到的液体产物的产率在约40至约60%(w/w)的范围内,并且一般为约49%(见图1)。
实施例1A:热提取试验1
在采用表面冷凝器的490℃的上流式反应器(见图1)中将含有2.52wt%灰分和8.73wt%水分的铁杉原料(4,715g)进行热提取来生产生物油样品。基于“无灰(ashfree)”进料的液体产率为55.49wt%。进行紫杉烷分析的热提取物样品包括水馏分(1024.5g)、焦油馏分(440.5g)和从在除雾器中的玻璃纤维过滤材料挤出的纯液体馏分(170g)。
实施例1B:热提取试验2
在以表面冷凝模式运行的398℃的上流式反应器(见图1)中将含有1.80wt%灰分和5.20wt%水分的铁杉原料(7,996g)进行热提取来生产液体热提取物。基于“无灰”进料的液体产率为45.12wt%,焦为28.54wt%而气体为17.41wt%。
取含有紫杉烷的热提取物的样品并进行紫杉烷分析。
在这个实施例中,与生产提取物的生物质的初始体积相比,热提取物的体积减少了约25倍(不需要任何固体生物质的初始溶剂提取)。
实施例1C:热提取试验3(见图2)
在397℃下并以液体骤冷模式运行的上流式反应器(见图1)中将含有1.80wt%灰分和5.20wt%水分的铁杉原料(5,641g)进行热提取来生产液体热提取样品。所述骤冷液体为从实施例1A的试验中得到的水产物和软化水的约50/50混合物。基于“无灰”进料的液体产率为46.77wt%,焦为25.87wt%而气体为19.0wt%。这个试验的目的是比较利用液体骤冷得到的产物产率和表面冷凝得到的产物产率。
取含有紫杉烷的热提取产物的样品并进行紫杉烷分析。
在这个实施例中,与生产提取物的生物质的初始体积相比,热提取物的体积减少了约50倍(不需要任何固体生物质的初始溶剂提取)。
实施例1D:在回收***中的紫杉烷的选择性分馏
在回收***中的紫杉烷的选择性分馏和浓缩的实例示范在1B中描述的热提取实施例中。在这个实例中,在从纤维床过滤回收装置中回收的热提取物馏分中检出约50%的可识别紫杉烷含量,虽然该馏分仅占在热提取试验2过程中生产的总热提取物的22%。
实施例1E:在回收***中的紫杉烷的进一步选择性分馏
通过加入水或其它分配溶剂的进一步选择性分馏和浓缩的实施例示范在1C中描述的热提取实施例中。在这个实例中,地在回收***中原位加入水,而结果,从纤维床过滤回收装置中回收的热提取物馏分中检出约50%的可识别紫杉烷含量,虽然该馏分仅占在热提取试验3过程中生产的总热提取物的24%。除了加入水和直接冷凝热提取物产物外,试验3的热提取条件在温度和处理时间方面与试验2相同。因此,当与如在试验2的情况下没有水分配的紫杉烷的选择性分馏相比时,在试验3中利用水分配的紫杉烷的选择性分馏显示为更有效。
实施例1A、1B和1C的分析:在得到紫杉烷的定性分析中使用利用硅胶和用95∶5的二氯甲烷∶甲醇作为溶剂的热提取物的薄层色谱法(TLC)并证明是有益的(即,证实在样品中存在紫杉烷)。TLC分析的结果列在表1的最后一列中(也即,将紫杉烷报道为“测出”或“未测出”)。
实施例2:通过凝胶色谱法和HPLC的紫杉烷的离析和定量分析
离析方法1:将如在实施例1A、1B和1C中概述的那样获得的热提取物样品(1g)混合并吸附在1g的聚乙烯聚吡咯烷酮,PVPP(西格玛化学公司,P-6755[25249-54-1])上,并应用于strata-X33μmPolymericSorbentlg/20mlGigaTubes(Phenomenex,8B-S100-JEG)中。在装载上述样品之前用20mL甲醇适应strata-X并用20mL去离子水平衡。利用下列溶剂体系以慢速进行洗脱。
A)甲醇-去离子水(7∶3)[5x12mL]
B)甲醇∶乙腈∶去离子水(6∶3∶1)、(6∶2∶2)或者(5∶2∶3)[5x12ml],和
C)甲醇∶乙腈(1∶1)[5x12mL]。
使用TLC和HPLC对富含紫杉烷的馏分进行色谱分析。TLC用于定性分析(表1)而HPLC用于定量分析以测定总紫杉烷和单独紫杉烷的产率(表1、2和3)。溶剂体系“b”(6∶3∶1)被选为定量测定紫杉烷产率的有效溶剂,并且使用该溶剂体系测定在表中报道的产率。
表1:TLC和HPLC分析
溶剂体系A.甲醇∶去离子水(7∶3)
溶剂体系B.甲醇∶乙腈∶去离子水(6∶3∶1)
溶剂体系C.甲醇∶乙腈(1∶1)
N.D.=未测出
痕量=痕量的紫杉烷
如经由热提取生产和利用离析方法1回收的总紫杉烷和单独紫杉烷组分的产率分别报道在表2和3中。在表2中也给出了总“离析方法1”紫杉烷产率与常规溶剂回收方法的文献(例如Daoust,G和Sirois,G.,2003和“CanadaYew(TaxuscanadensisMarsh.)andTaxanes:APerfectSpeciesforFiledProductionandimprovementThroughGeneticSelection”NaturalResourcesCanada,CanadianForestService,Sainte-Foy,Quebec)中报道的产率的比较。在表3中也给出了各个代表性紫杉烷的“离析方法1”产率与溶剂控制试验产率的比较。
从表2和3中的数据可以看出,使用本发明方法的总紫杉烷和各个代表性紫杉烷的产率高于使用常规溶剂提取法获得的产率。
表2:经由热提取得到的总紫杉烷的“离析方法1”产率与常规溶剂产率(如在文献*中报道的那样)的比较
*Daoust,GandSirois,G.,2003,″CanadaYew(TaxuscanadensisMarsh.)andTaxanes:APerfectSpeciesforFiledProductionandimprovementThroughGeneticSelection″NaturalResourcesCanada,CanadianForestService,Sainte-Foy,Quebec
表3:经由热提取得到的紫杉醇及其他其它紫杉烷化合物的“离析方法1”产率与溶剂提取(溶剂对照*)产率的比较
*见实施例3
离析方法2:将如在实施例1A、1B和1C中概述的那样获得的热提取物样品(1g)混合并吸附在1g的聚乙烯聚吡咯烷酮,PVPP(西格玛化学公司,P-6755[25249-54-1])上并应用于strata-X33μmPolymericSorbentlg/20mlGigaTubes(Phenomenex,8B-S100-JEG)中。在装载上述样品之前用20mL甲醇适应strata-X并用20mL去离子水平衡。用20mL水随后用甲醇浓度逐渐增加(20,50,70,100%)的等分部分以慢速进行洗脱。以在用50-70%甲醇洗脱的馏分中发现的最高浓度对所有的馏分进行色谱分析。
实施例3
紫杉烷的溶剂提取(非热解对照试验)
将新鲜的加拿大紫杉针叶(4417.13g鲜重(fr.wt))在室温下以两步骤进行提取:第一步,在100%甲醇(1g鲜重/10ml溶剂)中浸泡24h,随后在市售韦林氏搀合器中切碎并倾析出溶剂;第二步,将切碎后的残渣在60%含水甲醇中再浸泡24h。将合并后的甲醇提取物减压蒸发直至去除大多数或所有的甲醇。冷冻干燥残余物得到713.88g的粗提物。这样从每g鲜重的针叶中得到了162mg的加拿大紫杉粗提物。这个试验结果以“溶剂对照”在表3中给出。
实施例4
在464℃的温度下和以液体骤冷模式运转的上流式反应器(见图1)中将溶剂提取后的咖啡原料进行热提取以生产热提取物样品。基于“无灰”进料的液体产率为55.15wt%,焦产率为16.87wt%而气体产率为24.37wt%。该试验的目的是测定是否可以热提取出剩余在溶剂提取后的咖啡原料中的任何残余咖啡因。
取含有咖啡因的热提取物样品,并使用装有电脑和Chem.Station软件(Chem.32)、Binary泵SL(G1312B)、高效自动取样器SL(G1367C)和自动扫描光电二极管阵列分光光度检测仪安捷伦(AgilentTechnologies)(G1315C)的安捷伦1200液相色谱仪进行咖啡因分析。
结果:
R158A除雾器乙二醇:在1g的油中含有91.2ppm咖啡因
R158A初级冷凝器在1g的油中含有129ppm咖啡因
实施例5
在500℃的温度下和以液体骤冷模式运转的上流式反应器(见图1)中将亚麻硬外皮(flaxshive)原料进行热提取以生产热提取物样品。基于“无灰”进料的液体产率为55.57wt%,焦产率为14.48wt%,而气体产率为23.61wt%。这个试验的目的是测定是否可以热提取出在亚麻硬外皮中的任何表儿茶素和儿茶素。
取收集的液体热提取物产物的样品并使用安捷伦EclipsePlusC-185μm(4.6x150mm内径)反相分析柱进行表儿茶素和儿茶素分析。在室温下使用梯度色谱技术:溶剂A=甲醇/乙腈(95∶5);溶剂B=0.05%HCOOH水溶液;流速为0.9ml/min。使用三个确定的检测波长:270nm、280nm和350nm,而可分辨峰用光电二极管阵列检测器从250至400nm进行扫描。
结果:
■以相当大的量检测出表儿茶素和儿茶素
虽然为了理解清楚的目的,已经通过举例说明和实施例并参照一个或多个实施方式相当详细地描述了上述发明,但是在不偏离如在所附权利要求中描述的本发明的实质和范围的情况下,对于本领域中的普通技术人员来说,根据本发明的教导,显而易见地可以对本发明进行某些变化、改变和改进。
必须指出,除非上下文中另外清楚指明,在本PCT说明书及其所附权利要求的英文版中使用的单数形式“a”、“an”和“the”包括复数含义。
除非另有定义,这里使用的所有的技术和科学术语与本发明所属领域内的普通技术人员的通常理解具有相同的意义。
在本申请文件中引用的所有出版物、专利和专利申请都在此引入作为参考,如同每一个单独的出版物、专利或专利申请都特别和分别指明被引入作为参考一样。在本申请文件中任何出版物、专利或专利申请的引用并非承认该出版物、专利或专利申请为现有技术。
Claims (19)
1.一种通过含有二萜类化合物的生物质原材料的热提取生产富含紫杉烷的热提取物的方法,包括:
将所述含有二萜类化合物的生物质原材料加热至250℃至650℃的温度停留少于30秒的时间,其中该加热工艺足够从原材料中提取出一定量的紫杉烷化合物且紫杉烷化合物没有转化为一种或多种其它的化合物,其中所述富含紫杉烷的热提取物包含少于10重量%的一种或多种其它的化合物,
其中
a)相对于生物质原材料体积,紫杉属或澳洲红豆杉属的种中收集的富含紫杉烷的热提取物的体积浓缩了10倍或更大倍数;且
b)所述热提取方法排除了溶剂提取,且提取的紫杉烷化合物的产率比溶剂回收提取更高。
2.根据权利要求1的方法,其中,所述原材料得自紫杉树。
3.根据权利要求1的方法,其中,所述热提取物包含少于0.5重量%的一种或多种其它的化合物。
4.根据权利要求1的方法,其中,与原材料相比,所述热提取导致热提取物的体积减少10倍、20倍或50倍。
5.一种通过含有二萜类化合物的生物质原材料的热提取从该生物质原材料中生产富含紫杉烷的热提取物的方法,包括:
将所述生物质原材料加热至300℃至550℃的温度停留少于5秒的时间,其中该加热工艺足够从原材料中提取出一定量的紫杉烷化合物且紫杉烷化合物没有转化为一种或多种其它的化合物,其中所述富含紫杉烷的热提取物包含少于5重量%的一种或多种其它的化合物。
6.根据权利要求5的方法,其中,所述生物质原材料包括紫杉属或澳洲红豆杉属的种类。
7.一种生产富含紫杉烷的热提取物的方法,包括:
制备含有二萜类化合物的生物质原材料,其中所述生物质原材料包括紫杉属或澳洲红豆杉属的种类,其中生物质的尺寸减少至在其最小维度上的平均直径小于2cm;
将所述尺寸减少的含有二萜类化合物的生物质原材料加入包含封闭容器、热源和至少一个回收装置的热提取体系中;
在该热提取体系中将所述尺寸减少的含有二萜类化合物的生物质原材料加热至250℃至650℃的温度停留少于30秒的时间,其中该加热工艺足够产生包含一定量的紫杉烷化合物的产物流且紫杉烷化合物没有转化为一种或多种其它的化合物,其中所述富含紫杉烷的热提取物包含少于10重量%的一种或多种其它的化合物;和
在至少一个回收装置的至少一个装置中从富含紫杉烷化合物的产物流收集至少一个馏分以获得富含紫杉烷的热提取物,
其中
a)相对于生物质原材料体积,紫杉属或澳洲红豆杉属的种中收集的富含紫杉烷的热提取物的体积浓缩了10倍或更大倍数;且
b)所述热提取方法排除了溶剂提取,且提取的紫杉烷化合物的产率比溶剂回收提取更高。
8.根据权利要求7的方法,其中,与原材料相比,所述热提取导致热提取物的体积减少10倍、20倍或50倍。
9.根据权利要求7的方法,其中,所述原材料为包括紫杉属或澳洲红豆杉属的种类的含有二萜类化合物的生物质原材料。
10.根据权利要求7的方法,其中,所述热源在热提取体系中产生320℃至400℃的温度。
11.根据权利要求7的方法,其中,所述原材料在热提取体系中的停留时间少于2秒。
12.根据权利要求7的所述方法,其中,所述热提取物包含少于0.5重量%的一种或多种其它的化合物。
13.根据权利要求7的方法,其中,所述从产物流收集的至少一种馏分选自含有紫杉烷的固体焦馏分、含有紫杉烷的液体馏分、含有紫杉烷的蒸汽馏分及它们的混合物,其中当收集不止一种馏分时,合并所收集的馏分以得到富含紫杉烷的热提取物。
14.根据权利要求13的方法,其中,在两个或者更多个回收装置中收集含有紫杉烷的蒸汽馏分,并且任选地,其中所述两个或者更多个回收装置中的至少一个含有从蒸汽馏分收集液体馏分的装置,并且其中所述收集液体馏分的装置为冷凝器、除雾器、纤维床过滤器或其组合。
15.根据权利要求14的方法,其中,所收集的各个馏分都为富含紫杉烷的热提取物。
16.根据权利要求13的方法,其中,所收集的液体馏分为富含紫杉烷的热提取物。
17.根据权利要求13的方法,其包括将所述富含紫杉烷的热提取物进行进一步处理以选择性去除一种或多种紫杉烷,其中该进一步处理任选包括分配溶剂,该分配溶剂可以包含水,以选择性去除一种或多种紫杉烷。
18.根据权利要求7的方法,其中,在收集过程中分馏所述至少一个含有紫杉烷的馏分以得到进一步的馏分,所述进一步的馏分被分别收集,并且其中从至少一个所述进一步的馏分得到富含紫杉烷的热提取物。
19.根据权利要求18的方法,其中,
(a)每一个收集的进一步的馏分都是富含紫杉烷的热提取物;和/或
(b)用分配溶剂,该分配溶剂可以包含水,处理一个或多个所收集的进一步的馏分。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US78804506P | 2006-04-03 | 2006-04-03 | |
US60/788,045 | 2006-04-03 | ||
CNA2007800204399A CN101460473A (zh) | 2006-04-03 | 2007-04-02 | 热提取方法和产物 |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNA2007800204399A Division CN101460473A (zh) | 2006-04-03 | 2007-04-02 | 热提取方法和产物 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102702139A CN102702139A (zh) | 2012-10-03 |
CN102702139B true CN102702139B (zh) | 2016-01-20 |
Family
ID=38563046
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201210096487.9A Expired - Fee Related CN102702139B (zh) | 2006-04-03 | 2007-04-02 | 热提取方法和产物 |
CNA2007800204399A Pending CN101460473A (zh) | 2006-04-03 | 2007-04-02 | 热提取方法和产物 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNA2007800204399A Pending CN101460473A (zh) | 2006-04-03 | 2007-04-02 | 热提取方法和产物 |
Country Status (6)
Country | Link |
---|---|
US (2) | US9127208B2 (zh) |
EP (2) | EP2007744B1 (zh) |
CN (2) | CN102702139B (zh) |
CA (1) | CA2647564C (zh) |
DK (2) | DK2007744T3 (zh) |
WO (1) | WO2007112570A1 (zh) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2007744B1 (en) | 2006-04-03 | 2017-05-17 | Pharmatherm Chemicals Inc. | Thermal extraction method for producing a taxane extract |
US20110284359A1 (en) | 2010-05-20 | 2011-11-24 | Uop Llc | Processes for controlling afterburn in a reheater and for controlling loss of entrained solid particles in combustion product flue gas |
US8499702B2 (en) | 2010-07-15 | 2013-08-06 | Ensyn Renewables, Inc. | Char-handling processes in a pyrolysis system |
US9028696B2 (en) | 2010-07-26 | 2015-05-12 | Sapphire Energy, Inc. | Process for the recovery of oleaginous compounds from biomass |
CN104087350A (zh) | 2010-07-26 | 2014-10-08 | 蓝宝石能源公司 | 用于从生物质回收油质化合物的方法 |
US8906236B2 (en) | 2010-07-26 | 2014-12-09 | Sapphire Energy, Inc. | Process for the recovery of oleaginous compounds and nutrients from biomass |
US9441887B2 (en) | 2011-02-22 | 2016-09-13 | Ensyn Renewables, Inc. | Heat removal and recovery in biomass pyrolysis |
US9347005B2 (en) | 2011-09-13 | 2016-05-24 | Ensyn Renewables, Inc. | Methods and apparatuses for rapid thermal processing of carbonaceous material |
US9109177B2 (en) | 2011-12-12 | 2015-08-18 | Ensyn Renewables, Inc. | Systems and methods for renewable fuel |
US9670413B2 (en) | 2012-06-28 | 2017-06-06 | Ensyn Renewables, Inc. | Methods and apparatuses for thermally converting biomass |
CN103808851A (zh) * | 2012-11-15 | 2014-05-21 | 刘胜远 | 一种红豆杉中10-去乙酰基紫杉醇的薄层色谱检测方法 |
EP3492559A1 (en) | 2013-06-26 | 2019-06-05 | Ensyn Renewables, Inc. | Methods for renewable fuel |
WO2016200262A1 (en) * | 2015-06-12 | 2016-12-15 | Nettenergy B.V. | System and method for the conversion of biomass, and products thereof |
US10337726B2 (en) | 2015-08-21 | 2019-07-02 | Ensyn Renewables, Inc. | Liquid biomass heating system |
CN110366448B (zh) | 2016-12-29 | 2023-05-02 | 安辛可再生能源有限公司 | 液体生物质的脱金属化 |
CA3162672A1 (en) | 2019-12-23 | 2021-07-01 | Barry A. Freel | Methods for formaldehyde control |
CN114773158A (zh) * | 2022-04-26 | 2022-07-22 | 云南七丹药业股份有限公司 | 一种新鲜三七花的有效成分提取工艺及其生产方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6002025A (en) * | 1999-02-24 | 1999-12-14 | Bcm Developement Inc. | Method for the purification of taxanes |
WO2001009243A1 (en) * | 1999-07-29 | 2001-02-08 | Ensyn Group, Inc. | Novel natural resin formulations |
CN1362959A (zh) * | 2000-02-02 | 2002-08-07 | 佛罗里达州立大学研究基金有限公司 | C10氨基甲酰氧基取代的紫衫烷抗肿瘤剂 |
CA2521829A1 (en) * | 2004-09-30 | 2006-03-30 | University Of Ottawa | Process for extracting taxanes |
Family Cites Families (412)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2318555A (en) | 1943-05-04 | Cleansing agent and the | ||
US1252072A (en) | 1916-09-13 | 1918-01-01 | William George Abbott Jr | Apparatus for cleaning the interior of tubular members. |
US2205757A (en) | 1937-09-18 | 1940-06-25 | Standard Oil Dev Co | Coke cleaning apparatus |
US2326525A (en) | 1940-08-28 | 1943-08-10 | Standard Oil Co | Method of preventing deleterious coke deposits |
US2328202A (en) | 1940-12-30 | 1943-08-31 | Henry A Doerner | Process for producing magnesium metal |
FR879606A (fr) | 1941-10-27 | 1943-03-01 | Procédé et appareil de traitement des gaz de gazogènes | |
US2380098A (en) | 1943-01-23 | 1945-07-10 | Henry A Doerner | Automatic reamer |
US2492948A (en) | 1945-10-05 | 1950-01-03 | Universal Oil Prod Co | Controlling catalyst regeneration temperature |
US2566353A (en) | 1948-08-04 | 1951-09-04 | Houdry Process Corp | Purification of oils |
US2696979A (en) | 1951-04-16 | 1954-12-14 | Kennecott Copper Corp | Automatic tuyere punching apparatus |
US2884303A (en) | 1956-03-06 | 1959-04-28 | Exxon Research Engineering Co | High temperature burning of particulate carbonaceous solids |
US3130007A (en) | 1961-05-12 | 1964-04-21 | Union Carbide Corp | Crystalline zeolite y |
GB1019133A (en) | 1962-09-12 | 1966-02-02 | Exxon Research Engineering Co | Hydrocarbon separation process for removal of impurities |
US3313726A (en) | 1963-06-24 | 1967-04-11 | Monsanto Co | Process for regenerating ion exchange resins |
US3309356A (en) | 1965-07-06 | 1967-03-14 | Weyerhaeuser Co | Separating levoglucosan and carbohydrate acids from aqueous mixtures containing the same-by solvent extraction |
FI46091C (fi) | 1966-06-15 | 1972-12-11 | Ahlstroem Oy | Tapa lämpökäsitellä meesaa tai sentapaista ainetta. |
US3467502A (en) | 1966-10-12 | 1969-09-16 | Continental Carbon Co | Feedstock control system for carbon black reactors |
BE759016A (fr) | 1969-12-18 | 1971-04-30 | Deggendorfer Werft Eisenbau | Refroidisseur pour le passage d'une partie reglable d'un vehicule de chaleur maintenu en circulation dans un reacteur |
US3776533A (en) | 1970-01-28 | 1973-12-04 | Dravo Corp | Apparatus for continuous heat processing of ore pellets |
GB1300966A (en) * | 1970-03-10 | 1972-12-29 | Yoshizo Sakamoto | Methods for processing medicinal plants and herbs |
US3696022A (en) | 1970-07-27 | 1972-10-03 | Universal Oil Prod Co | Swing-bed guard chamber in hydrogenerating and hydrorefining coke-forming hydrocarbon charge stock |
US3694346A (en) | 1971-05-06 | 1972-09-26 | Exxon Research Engineering Co | Integrated fluid coking/steam gasification process |
US3925024A (en) | 1971-09-10 | 1975-12-09 | Borden Inc | Grid burner system |
US4039290A (en) | 1972-05-15 | 1977-08-02 | Kureha Kagaku Kogyo Kabushiki Kaisha | Spent activated carbon regenerator |
US3959420A (en) | 1972-05-23 | 1976-05-25 | Stone & Webster Engineering Corporation | Direct quench apparatus |
US3853498A (en) | 1972-06-28 | 1974-12-10 | R Bailie | Production of high energy fuel gas from municipal wastes |
US3814176A (en) | 1973-01-22 | 1974-06-04 | R Seth | Fixed-fluidized bed dry cooling tower |
US3907661A (en) | 1973-01-29 | 1975-09-23 | Shell Oil Co | Process and apparatus for quenching unstable gas |
US3876533A (en) | 1974-02-07 | 1975-04-08 | Atlantic Richfield Co | Guard bed system for removing contaminant from synthetic oil |
US3927996A (en) | 1974-02-21 | 1975-12-23 | Exxon Research Engineering Co | Coal injection system |
US3890111A (en) | 1974-02-21 | 1975-06-17 | Exxon Research Engineering Co | Transfer line burner system using low oxygen content gas |
US4052265A (en) | 1974-07-26 | 1977-10-04 | Kemp Klaus M | Process for the pyrolytic treatment of organic, pseudo-organic and inorganic material |
US4032305A (en) | 1974-10-07 | 1977-06-28 | Squires Arthur M | Treating carbonaceous matter with hot steam |
US4003829A (en) | 1975-02-10 | 1977-01-18 | Atlantic Richfield Company | Method of removing contaminant from a hydrocarbonaceous fluid |
US4064043A (en) | 1975-02-18 | 1977-12-20 | Rohm And Haas Company | Liquid phase adsorption using partially pyrolyzed polymer particles |
US4153514A (en) | 1975-02-27 | 1979-05-08 | Occidental Petroleum Corporation | Pyrolysis process for solid wastes |
US4101414A (en) | 1975-09-02 | 1978-07-18 | Unitech Chemical Inc. | Rerefining of used motor oils |
US4165717A (en) | 1975-09-05 | 1979-08-28 | Metallgesellschaft Aktiengesellschaft | Process for burning carbonaceous materials |
CA1081466A (en) | 1976-03-26 | 1980-07-15 | David S. Mitchell | Countercurrent plug-like flow of two solids |
US4064018A (en) | 1976-06-25 | 1977-12-20 | Occidental Petroleum Corporation | Internally circulating fast fluidized bed flash pyrolysis reactor |
US4145274A (en) | 1976-06-25 | 1979-03-20 | Occidental Petroleum Corporation | Pyrolysis with staged recovery |
US4102773A (en) | 1976-06-25 | 1978-07-25 | Occidental Petroleum Corporation | Pyrolysis with cyclone burner |
US4085030A (en) | 1976-06-25 | 1978-04-18 | Occidental Petroleum Corporation | Pyrolysis of carbonaceous materials with solvent quench recovery |
GB1561237A (en) | 1976-09-22 | 1980-02-13 | Ahlstroem Oy | Method of treating materials in a fluidized bed reactor |
US4210492A (en) | 1977-03-14 | 1980-07-01 | Shell Oil Company | Process for the pyrolysis of coal in dilute- and dense-phase fluidized beds |
JPS53116314A (en) | 1977-03-19 | 1978-10-11 | Mitsui Petrochem Ind Ltd | Separation of acetic acid and water |
US4138020A (en) | 1977-05-13 | 1979-02-06 | Foster Wheeler Energy Corporation | Regeneration flow distribution device |
US4103902A (en) | 1977-08-16 | 1978-08-01 | Foster Wheeler Energy Corporation | Water seal for regenerator |
US4344770A (en) | 1977-11-04 | 1982-08-17 | Wilwardco, Inc. | Method and apparatus for converting solid organic material to fuel oil and gas |
US4298453A (en) | 1977-12-27 | 1981-11-03 | Mobil Oil Corporation | Coal conversion |
US4284616A (en) | 1978-02-15 | 1981-08-18 | Intenco, Inc. | Process for recovering carbon black and hydrocarbons from used tires |
US4245693A (en) | 1978-10-11 | 1981-01-20 | Phillips Petroleum Company | Waste heat recovery |
US4219537A (en) | 1978-10-31 | 1980-08-26 | Foster Wheeler Energy Corporation | Desulfurization and low temperature regeneration of carbonaceous adsorbent |
US4300009A (en) | 1978-12-28 | 1981-11-10 | Mobil Oil Corporation | Conversion of biological material to liquid fuels |
US4233119A (en) | 1979-01-23 | 1980-11-11 | Louis A. Grant, Inc. | Ascension pipe and elbow cleaning apparatus |
IT1112472B (it) | 1979-04-09 | 1986-01-13 | Trojani Ing Benito Luigi | Tubo con alettatura interna ed alettatura o piolinatura esterna,particolarmente per apparecchi scambiatori di calore,e suo metodo di fabbricazione |
US4334893A (en) | 1979-06-25 | 1982-06-15 | Exxon Research & Engineering Co. | Recovery of alkali metal catalyst constituents with sulfurous acid |
US4272402A (en) | 1979-07-16 | 1981-06-09 | Cosden Technology, Inc. | Process for regenerating fluidizable particulate cracking catalysts |
US4225415A (en) | 1979-08-10 | 1980-09-30 | Occidental Petroleum Corporation | Recovering hydrocarbons from hydrocarbon-containing vapors |
US4341598A (en) | 1979-08-14 | 1982-07-27 | Occidental Research Corporation | Fluidized coal pyrolysis apparatus |
ZA807805B (en) | 1979-12-14 | 1982-01-27 | Energy Resources Co Inc | Fluidized-bed process to convert solid wastes to clean energy |
JPS591758B2 (ja) | 1980-01-18 | 1984-01-13 | 工業技術院長 | 熱分解装置のガス処理方法 |
US4456504A (en) | 1980-04-30 | 1984-06-26 | Chevron Research Company | Reactor vessel and process for thermally treating a granular solid |
US4301771A (en) | 1980-07-02 | 1981-11-24 | Dorr-Oliver Incorporated | Fluidized bed heat exchanger with water cooled air distributor and dust hopper |
US4324641A (en) | 1980-08-26 | 1982-04-13 | Occidental Research Corporation | Pyrolysis process utilizing a beneficially reactive gas |
US4324637A (en) | 1980-08-26 | 1982-04-13 | Occidental Research Corporation | Pyrolysis process with feed pretreatment utilizing a beneficially reactive gas |
US4324644A (en) | 1980-08-26 | 1982-04-13 | Occidental Research Corporation | Pyrolysis process for stabilizing volatile hydrocarbons utilizing a beneficially reactive gas |
US4324642A (en) | 1980-08-26 | 1982-04-13 | Occidental Research Corporation | Pyrolysis process for producing condensed stabilized hydrocarbons utilizing a beneficially reactive gas |
US4308411A (en) | 1980-08-28 | 1981-12-29 | Occidental Research Corporation | Process for converting oxygenated hydrocarbons into hydrocarbons |
US4317703A (en) | 1980-12-03 | 1982-03-02 | American Can Company | Pyrolysis process utilizing pyrolytic oil recycle |
US4321096A (en) | 1980-12-16 | 1982-03-23 | John B. Pike & Son, Inc. | Apparatus and method for cleaning an explosion sensing port |
US4325327A (en) | 1981-02-23 | 1982-04-20 | Combustion Engineering, Inc. | Hybrid fluidized bed combuster |
US4336128A (en) | 1981-06-01 | 1982-06-22 | Chevron Research Company | Combustion of pyrolyzed carbon containing solids in staged turbulent bed |
US4415434A (en) | 1981-07-21 | 1983-11-15 | Standard Oil Company (Ind.) | Multiple stage desalting and dedusting process |
US4373994A (en) | 1981-09-28 | 1983-02-15 | Occidental Research Corporation | Pyrolysis process and apparatus |
US4422927A (en) | 1982-01-25 | 1983-12-27 | The Pittsburg & Midway Coal Mining Co. | Process for removing polymer-forming impurities from naphtha fraction |
JPS58150793U (ja) | 1982-04-02 | 1983-10-08 | 日本鋼管株式会社 | 焼結原料サンプラ− |
US4495056A (en) | 1982-04-16 | 1985-01-22 | Standard Oil Company (Indiana) | Oil shale retorting and retort water purification process |
FR2526182B1 (fr) | 1982-04-28 | 1985-11-29 | Creusot Loire | Procede et dispositif de controle de la temperature d'un lit fluidise |
US4931171A (en) | 1982-08-03 | 1990-06-05 | Phillips Petroleum Company | Pyrolysis of carbonaceous materials |
DE3230656A1 (de) | 1982-08-18 | 1984-02-23 | Uhde Gmbh, 4600 Dortmund | Verfahren zur wiederaufheizung und foerderung eines koernigen waermetraegers sowie vorrichtung insbesondere zu dessen durchfuehrung |
US4482451A (en) | 1982-09-16 | 1984-11-13 | Uop Inc. | Process for the separation of particulate solids from vapors using a discharge having a helical twist |
EP0105980B1 (en) | 1982-10-06 | 1986-01-29 | Uop Inc. | Fluid particle backmixed cooling process and apparatus |
US4434726A (en) | 1982-12-27 | 1984-03-06 | Combustion Engineering, Inc. | Fine particulate feed system for fluidized bed furnace |
JPS58150793A (ja) | 1983-01-17 | 1983-09-07 | Hitachi Ltd | 熱回収装置 |
US4443229A (en) | 1983-01-31 | 1984-04-17 | Chevron Research Company | Gasification process for carbonaceous materials |
FR2540739A1 (fr) | 1983-02-11 | 1984-08-17 | Elf France | Dispositif et installations pour la distillation par evaporation en couches minces, en particulier pour hydrocarbures, et procede de mise en oeuvre de ce dispositif |
FR2541435B1 (fr) | 1983-02-21 | 1986-10-17 | Elf France | Generateur thermique pour la realisation du chauffage de fluide par echange thermique au moyen d'un lit fluidise et le procede pour sa mise en oeuvre |
US4897178A (en) | 1983-05-02 | 1990-01-30 | Uop | Hydrocracking catalyst and hydrocracking process |
FR2548208B1 (fr) | 1983-06-30 | 1987-01-09 | Inst Francais Du Petrole | Procede de fabrication de combustibles solides a partir d'huiles lourdes d'hydrocarbures et de matieres vegetales |
BR8304158A (pt) | 1983-07-26 | 1984-07-31 | Cia Agricolas E Florestal Sant | Processo de recuperacao de alcatrao leve,volatizado na pirolise de biomassa em fornos de carbonizacao descontinuos e respectivas instalacao |
US4504379A (en) | 1983-08-23 | 1985-03-12 | Exxon Research And Engineering Co. | Passivation of metal contaminants in cat cracking |
BR8304794A (pt) | 1983-09-02 | 1985-04-09 | Petroleo Brasileiro Sa | Processo para a producao de gasolina de lata octanagem |
FR2563118B1 (fr) | 1984-04-20 | 1987-04-30 | Creusot Loire | Procede et installation de traitement de matiere en lit fluidise circulant |
DE3426080C2 (de) | 1984-07-14 | 1996-09-19 | Basf Ag | Verfahren zur Herstellung konzentrierter, stabiler Wasser-in-Öl-Polymeremulsionen von wasserlöslichen oder wasserquellbaren Polymerisaten |
US4617693A (en) | 1984-08-06 | 1986-10-21 | Meyer Marjorie A | Drain pipe cleaning tool |
FI75504C (fi) | 1984-08-28 | 1988-07-11 | Ahlstroem Oy | Anordning i virvelbaeddsreaktor. |
US4710357A (en) | 1984-12-28 | 1987-12-01 | Uop Inc. | FCC combustion zone catalyst cooling apparatus |
US4595567A (en) | 1984-12-28 | 1986-06-17 | Uop Inc. | Cooling fluidized catalytic cracking regeneration zones with heat pipe apparatus |
US4615870A (en) | 1985-03-11 | 1986-10-07 | The M. W. Kellogg Company | Back-mixed hydrotreating reactor |
US4584947A (en) | 1985-07-01 | 1986-04-29 | Chittick Donald E | Fuel gas-producing pyrolysis reactors |
US4828581A (en) | 1985-09-20 | 1989-05-09 | Battelle Development Corporation | Low inlet gas velocity high throughput biomass gasifier |
US4732091A (en) | 1985-09-30 | 1988-03-22 | G.G.C., Inc. | Pyrolysis and combustion process and system |
US4678860A (en) | 1985-10-04 | 1987-07-07 | Arizona Board Of Regents | Process of producing liquid hydrocarbon fuels from biomass |
US4668243A (en) | 1985-10-23 | 1987-05-26 | Schulz Johann G | Novel fuel |
US4823712A (en) | 1985-12-18 | 1989-04-25 | Wormser Engineering, Inc. | Multifuel bubbling bed fluidized bed combustor system |
US4891459A (en) | 1986-01-17 | 1990-01-02 | Georgia Tech Research Corporation | Oil production by entrained pyrolysis of biomass and processing of oil and char |
SE460146B (sv) | 1986-08-14 | 1989-09-11 | Goetaverken Energy Syst Ab | Anordning vid foerbraenningsanlaeggning med cirkulerande fluidbaedd |
US4849091A (en) | 1986-09-17 | 1989-07-18 | Uop | Partial CO combustion with staged regeneration of catalyst |
US4714109A (en) | 1986-10-03 | 1987-12-22 | Utah Tsao | Gas cooling with heat recovery |
DE3881545T2 (de) | 1987-03-11 | 1993-10-21 | Kansai Paint Co Ltd | Kathodisch abscheidbares teilchenförmiges Polymergel und dieses enthaltende kathodisch elektroabscheidbare Beschichtungszusammensetzung. |
US4968325A (en) | 1987-08-24 | 1990-11-06 | Centre Quebecois De Valorisation De La Biomasse | Fluidized bed gasifier |
US4983278A (en) | 1987-11-03 | 1991-01-08 | Western Research Institute & Ilr Services Inc. | Pyrolysis methods with product oil recycling |
US4876108A (en) | 1987-11-12 | 1989-10-24 | Ensyn Engineering Associates Inc. | Method of using fast pyrolysis liquids as liquid smoke |
US5236688A (en) | 1987-11-13 | 1993-08-17 | Kureha Kagaku Kogyo Kabushiki Kaisha | Method for activating infusibilized pitch beads |
US4881592A (en) | 1988-02-01 | 1989-11-21 | Uop | Heat exchanger with backmix and flow through particle cooling |
US4992605A (en) | 1988-02-16 | 1991-02-12 | Craig Wayne K | Production of hydrocarbons with a relatively high cetane rating |
US4942269A (en) | 1988-03-17 | 1990-07-17 | Midwest Research Institute | Process for fractionating fast-pyrolysis oils, and products derived therefrom |
US4880473A (en) | 1988-04-01 | 1989-11-14 | Canadian Patents & Development Ltd. | Process for the production of fermentable sugars from biomass |
JPH01277196A (ja) | 1988-04-27 | 1989-11-07 | Daikin Ind Ltd | 流動層を用いた熱交換器 |
US4940007A (en) | 1988-08-16 | 1990-07-10 | A. Ahlstrom Corporation | Fast fluidized bed reactor |
US5009770A (en) | 1988-08-31 | 1991-04-23 | Amoco Corporation | Simultaneous upgrading and dedusting of liquid hydrocarbon feedstocks |
US5059404A (en) | 1989-02-14 | 1991-10-22 | Manufacturing And Technology Conversion International, Inc. | Indirectly heated thermochemical reactor apparatus and processes |
US5879650A (en) | 1989-04-06 | 1999-03-09 | Cabot Corporation | Tandem quench |
US5041209A (en) | 1989-07-12 | 1991-08-20 | Western Research Institute | Process for removing heavy metal compounds from heavy crude oil |
US4988430A (en) | 1989-12-27 | 1991-01-29 | Uop | Supplying FCC lift gas directly from product vapors |
CA2009021C (en) | 1990-01-31 | 2001-09-11 | Barry A. Freel | Method and apparatus for a circulating bed transport fast pyrolysis reactor system |
US5792340A (en) | 1990-01-31 | 1998-08-11 | Ensyn Technologies, Inc. | Method and apparatus for a circulating bed transport fast pyrolysis reactor system |
US5961786A (en) | 1990-01-31 | 1999-10-05 | Ensyn Technologies Inc. | Apparatus for a circulating bed transport fast pyrolysis reactor system |
US5225044A (en) | 1990-03-14 | 1993-07-06 | Wayne Technology, Inc. | Pyrolytic conversion system |
US5077252A (en) | 1990-07-17 | 1991-12-31 | Mobil Oil Corporation | Process for control of multistage catalyst regeneration with partial co combustion |
US5011592A (en) | 1990-07-17 | 1991-04-30 | Mobil Oil Corporation | Process for control of multistage catalyst regeneration with full then partial CO combustion |
US5136117A (en) | 1990-08-23 | 1992-08-04 | Battelle Memorial Institute | Monomeric recovery from polymeric materials |
US5018458A (en) | 1990-09-12 | 1991-05-28 | Zimpro Passavant Environmental Systems, Inc. | Furnace combustion zone temperature control method |
US5380916A (en) * | 1990-11-02 | 1995-01-10 | University Of Florida | Method for the isolation and purification of taxane derivatives |
WO1992018492A1 (en) | 1991-04-19 | 1992-10-29 | The University Of Mississippi | Methods and compositions for isolating taxanes |
US5536488A (en) | 1991-07-01 | 1996-07-16 | Manufacturing And Technology Conversion | Indirectly heated thermochemical reactor processes |
FR2683743B1 (fr) | 1991-11-14 | 1994-02-11 | Institut Francais Petrole | Procede et dispositif d'echange thermique de particules solides pour double regeneration en craquage catalytique. |
US5212129A (en) | 1991-12-17 | 1993-05-18 | Uop | Inverted backmix coolers for FCC units |
IT1258838B (it) * | 1992-01-31 | 1996-02-29 | Indena Spa | Processo per l'estrazione di tassolo e derivati da cultivar del genere taxus |
US5395455A (en) * | 1992-03-10 | 1995-03-07 | Energy, Mines And Resources - Canada | Process for the production of anhydrosugars from lignin and cellulose containing biomass by pyrolysis |
SE470213B (sv) | 1992-03-30 | 1993-12-06 | Nonox Eng Ab | Sätt och anordning för framställning av bränslen ur fasta kolhaltiga naturbränslen |
US5239946A (en) | 1992-06-08 | 1993-08-31 | Foster Wheeler Energy Corporation | Fluidized bed reactor system and method having a heat exchanger |
JPH06184560A (ja) | 1992-07-10 | 1994-07-05 | Hiroshi Shimizu | 有機廃棄物の熱分解装置 |
US5243922A (en) | 1992-07-31 | 1993-09-14 | Institute Of Gas Technology | Advanced staged combustion system for power generation from coal |
US5371212A (en) | 1992-09-04 | 1994-12-06 | Midwest Research Institute | Isolation of levoglucosan from pyrolysis oil derived from cellulose |
GB9224783D0 (en) | 1992-11-26 | 1993-01-13 | Univ Waterloo | An improved process for the thermal conversion of biomass to liquids |
US5281727A (en) * | 1992-11-27 | 1994-01-25 | Napro Biotherapeutics, Inc. | Method of using ion exchange media to increase taxane yields |
EP0627010A4 (en) | 1992-12-07 | 1995-05-03 | Univ Michigan | PROCESS FOR ISOLATION AND PURIFICATION OF TAXOL AND TAXANES FROM -i (TAXUS) spp. |
US5343939A (en) | 1992-12-14 | 1994-09-06 | Uop | Offset FCC coolers with improved catalyst circulation |
NO176455B1 (no) | 1992-12-28 | 1995-04-24 | Energos As | Ristovn |
US5426807A (en) | 1993-02-16 | 1995-06-27 | Goodway Tools Corporation | Tube cleaning apparatus |
US5402548A (en) | 1993-03-31 | 1995-04-04 | Adair; Michael A. | Duct cleaning apparatus |
US5376340A (en) | 1993-04-15 | 1994-12-27 | Abb Air Preheater, Inc. | Regenerative thermal oxidizer |
US5423891A (en) | 1993-05-06 | 1995-06-13 | Taylor; Robert A. | Method for direct gasification of solid waste materials |
IT1261667B (it) * | 1993-05-20 | 1996-05-29 | Tassano ad attivita' antitumorale. | |
US5494653A (en) | 1993-08-27 | 1996-02-27 | Battelle Memorial Institute | Method for hot gas conditioning |
US5713977A (en) | 1994-09-12 | 1998-02-03 | Praxair Technology, Inc. | Fixed bed filtering preheater process for high temperature process furnaces |
GB9426066D0 (en) | 1994-12-22 | 1995-02-22 | Radlein Desmond S G | Method of upgrading biomass pyrolysis liquids for use as fuels and as a source of chemicals by reaction with alcohols |
US5584985A (en) | 1994-12-27 | 1996-12-17 | Uop | FCC separation method and apparatus with improved stripping |
CH690790A5 (de) | 1995-01-10 | 2001-01-15 | Von Roll Umwelttechnik Ag | Verfahren zur thermischen Behandlung von Abfallmaterial. |
US5520722A (en) | 1995-01-18 | 1996-05-28 | Exxon Research And Engineering Company | Multiunsaturates removal process |
US6398921B1 (en) | 1995-03-15 | 2002-06-04 | Microgas Corporation | Process and system for wastewater solids gasification and vitrification |
US5662050A (en) | 1995-05-05 | 1997-09-02 | Angelo, Ii; James F. | Process for chemical/thermal treatment without toxic emissions |
DE19524176C1 (de) | 1995-07-03 | 1996-09-26 | Daimler Benz Ag | Verfahren zum Zwischenabschrecken von aus einem Lösungs-Glühofen kommenden Leichtmetall-Gußstücken |
US5654448A (en) * | 1995-10-02 | 1997-08-05 | Xechem International, Inc. | Isolation and purification of paclitaxel from organic matter containing paclitaxel, cephalomannine and other related taxanes |
IT1276116B1 (it) | 1995-11-10 | 1997-10-24 | O E T Calusco S R L | Procedimento ed impianto per la produzione di carbone vegetale mediante pirolisi di prodotti legnosi o biomasse vegetali in genere |
FR2744037B1 (fr) | 1996-01-31 | 1998-02-27 | Gec Alsthom Stein Ind | Lit fluidise externe destine a equiper un foyer a lit fluidise circulant |
US6190542B1 (en) | 1996-02-23 | 2001-02-20 | Hydrocarbon Technologies, Inc. | Catalytic multi-stage process for hydroconversion and refining hydrocarbon feeds |
WO1997031990A1 (fr) | 1996-02-27 | 1997-09-04 | Mitsubishi Heavy Industries, Ltd. | Procede et appareil de recuperation d'huile a partir de dechets plastiques |
EP0823590B1 (en) | 1996-02-29 | 2005-02-02 | Mitsubishi Heavy Industries, Ltd. | Method and apparatus for producing superheated steam using heat generated through incineration of wastes |
US5879642A (en) | 1996-04-24 | 1999-03-09 | Chevron U.S.A. Inc. | Fixed bed reactor assembly having a guard catalyst bed |
CA2255922C (en) | 1996-05-20 | 2009-07-07 | Jan Piskorz | Energy efficient liquefaction of biomaterials by thermolysis |
US5728271A (en) | 1996-05-20 | 1998-03-17 | Rti Resource Transforms International Ltd. | Energy efficient liquefaction of biomaterials by thermolysis |
US5703299A (en) | 1996-06-21 | 1997-12-30 | Corona Energy Partners, Ltd. | Exhaust stack sensor probe |
US6113862A (en) | 1997-04-23 | 2000-09-05 | Union Carbide Chemicals & Plastics Technology Corporation | Fluidized bed polymerization reactor with multiple fluidization grids |
AU750295B2 (en) * | 1997-05-02 | 2002-07-11 | Baxter Biotech Technology S.A.R.L. | Hemoglobin mutants with increased soluble expression and/or reduced nitric oxide scavenging |
US6033555A (en) | 1997-06-10 | 2000-03-07 | Exxon Chemical Patents Inc. | Sequential catalytic and thermal cracking for enhanced ethylene yield |
US5879079A (en) | 1997-08-20 | 1999-03-09 | The United States Of America As Represented By The Administrator, Of The National Aeronautics And Space Administration | Automated propellant blending |
US6193837B1 (en) | 1997-09-19 | 2001-02-27 | Midwest Research Institute | Preparation of brightness stabilization agent for lignin containing pulp from biomass pyrolysis oils |
EP1030128B1 (en) | 1997-10-16 | 2003-07-09 | Toyota Jidosha Kabushiki Kaisha | Catalytic combustion heater |
JPH11148625A (ja) | 1997-11-20 | 1999-06-02 | Hitachi Ltd | 廃棄物燃焼熱回収装置および方法 |
FI104561B (fi) | 1998-02-27 | 2000-02-29 | Fortum Oil And Gas Oy Fortum O | Menetelmä hiilipitoisten lähtöaineiden pyrolysoimiseksi |
US5904838A (en) | 1998-04-17 | 1999-05-18 | Uop Llc | Process for the simultaneous conversion of waste lubricating oil and pyrolysis oil derived from organic waste to produce a synthetic crude oil |
UA45442C2 (uk) | 1998-09-11 | 2002-04-15 | Емануїл Вольфович Прилуцький | Каталізатор низькотемпературного піролізу полімерних матеріалів, що містять вуглеводні |
FI110205B (fi) | 1998-10-02 | 2002-12-13 | Foster Wheeler Energia Oy | Menetelmä ja laite leijupetilämmönsiirtimessä |
FI117512B (fi) | 1998-10-14 | 2006-11-15 | Valtion Teknillinen | Menetelmä ja laite pyrolyysiöljyn valmistamiseksi |
FI116902B (fi) | 1998-10-14 | 2006-03-31 | Valtion Teknillinen | Menetelmä ja laite pyrolyysinesteen laadun parantamiseksi |
US6485841B1 (en) | 1998-10-30 | 2002-11-26 | Ensyn Technologies, Inc. | Bio-oil preservatives |
US6106702A (en) | 1998-12-29 | 2000-08-22 | Uop Llc | Olefinic hydrocarbon separation process |
US5969165A (en) * | 1999-01-07 | 1999-10-19 | 508037 (Nb) Inc. | Isolation and purification of paclitaxel and other related taxanes by industrial preparative low pressure chromatography on a polymeric resin column |
BR0009652B1 (pt) | 1999-04-07 | 2012-04-03 | processo para produzir e transportar uma carga de alimentação lìquida beneficiada a partir de uma carga de alimentação de hidrocarboneto pesado. | |
EP1242563A1 (en) | 1999-05-04 | 2002-09-25 | Commonwealth Scientific And Industrial Research Organisation | Process for carbonizing wood residues and producing activated carbon |
US6875341B1 (en) | 1999-05-24 | 2005-04-05 | James W. Bunger And Associates, Inc. | Process for enhancing the value of hydrocabonaceous natural recources |
CA2299149C (fr) | 1999-06-22 | 2010-09-21 | Chaichem Pharmaceuticals International | Procede d'isolation et de purification du paclitaxel a partir de sources naturelles |
DE19930071C2 (de) | 1999-06-30 | 2001-09-27 | Wolfgang Krumm | Verfahren und Vorrichtung zur Pyrolyse und Vergasung von organischen Stoffen und Stoffgemischen |
US6530964B2 (en) | 1999-07-07 | 2003-03-11 | The Lubrizol Corporation | Continuous process for making an aqueous hydrocarbon fuel |
JP2001083645A (ja) | 1999-07-13 | 2001-03-30 | Fuji Photo Film Co Ltd | ハロゲン化銀写真感光材料 |
US7047894B2 (en) | 1999-11-02 | 2006-05-23 | Consolidated Engineering Company, Inc. | Method and apparatus for combustion of residual carbon in fly ash |
JP2001131560A (ja) | 1999-11-09 | 2001-05-15 | Hitachi Ltd | 炭化水素原料の熱分解方法及び熱分解装置 |
US7202389B1 (en) | 1999-11-11 | 2007-04-10 | Nederlandse Organisatie Voor Toegepast Natuurwetenschappelijk Onderzoek Tno | Flash-pyrolysis in a cyclone |
US6455015B1 (en) | 2000-02-16 | 2002-09-24 | Uop Llc | Fluid-solid contacting chambers having multi-conduit, multi-nozzle fluid distribution |
US6452024B1 (en) * | 2000-02-22 | 2002-09-17 | Chaichem Pharmaceuticals International | Process for extraction and purification of paclitaxel from natural sources |
US6237541B1 (en) | 2000-04-19 | 2001-05-29 | Kvaerner Pulping Oy | Process chamber in connection with a circulating fluidized bed reactor |
WO2001083645A1 (en) | 2000-05-01 | 2001-11-08 | Danmarks Tekniske Universitet | A method and an installation for thermal gasification of solid fuel |
US6339182B1 (en) | 2000-06-20 | 2002-01-15 | Chevron U.S.A. Inc. | Separation of olefins from paraffins using ionic liquid solutions |
US6776607B2 (en) | 2000-06-26 | 2004-08-17 | Exxonmobil Research And Engineering Company | Process for minimizing afterburn in a FCC regenerator |
US6676828B1 (en) | 2000-07-26 | 2004-01-13 | Intevep, S.A. | Process scheme for sequentially treating diesel and vacuum gas oil |
EP1184443A1 (en) | 2000-09-04 | 2002-03-06 | Biofuel B.V. | Process for the production of liquid fuels from biomass |
MXPA03002341A (es) | 2000-09-18 | 2003-10-06 | Ensyn Group Inc | Productos producidos a partir de procesamiento termico rapido de materia de alimentacion de hidrocarburos pesados. |
US6547957B1 (en) | 2000-10-17 | 2003-04-15 | Texaco, Inc. | Process for upgrading a hydrocarbon oil |
CN1098337C (zh) | 2000-11-02 | 2003-01-08 | 中国石油天然气股份有限公司 | 一种采用多金属液体催化剂的常压重油悬浮床加氢新工艺 |
US6680137B2 (en) | 2000-11-17 | 2004-01-20 | Future Energy Resources Corporation | Integrated biomass gasification and fuel cell system |
AUPR221700A0 (en) | 2000-12-20 | 2001-01-25 | Gosfern Pty Limited | Crude oil conditioning apparatus and method |
CN1240810C (zh) | 2001-03-30 | 2006-02-08 | 中国科学院化工冶金研究所 | 循环流态化碳氢固体燃料的四联产工艺及装置 |
US6656342B2 (en) | 2001-04-04 | 2003-12-02 | Chevron U.S.A. Inc. | Graded catalyst bed for split-feed hydrocracking/hydrotreating |
US7241323B2 (en) | 2001-07-10 | 2007-07-10 | Advanced Fuel Research, Inc. | Pyrolysis process for producing fuel gas |
DE60202217T2 (de) | 2001-08-10 | 2005-12-15 | Shell Internationale Research Maatschappij B.V. | Verfahren zum rückgewinnen von heissgas-energie |
US6830730B2 (en) | 2001-09-11 | 2004-12-14 | Spectrolanalytical Instruments | Method and apparatus for the on-stream analysis of total sulfur and/or nitrogen in petroleum products |
US6768036B2 (en) | 2001-12-31 | 2004-07-27 | Exxonmobil Chemical Patents Inc. | Method for adding heat to a reactor system used to convert oxygenates to olefins |
US7244399B2 (en) | 2002-04-26 | 2007-07-17 | Foster Wheeler Energia Oy | Grid construction for a fluidized bed reactor |
US7648544B2 (en) | 2002-07-19 | 2010-01-19 | Shell Oil Company | Swirl tube separator |
US6759562B2 (en) | 2002-07-24 | 2004-07-06 | Abb Lummus Global Inc. | Olefin plant recovery system employing a combination of catalytic distillation and fixed bed catalytic steps |
US6960325B2 (en) | 2002-08-22 | 2005-11-01 | Hydrocarbon Technologies | Apparatus for hydrocracking and/or hydrogenating fossil fuels |
US7026262B1 (en) | 2002-09-17 | 2006-04-11 | Uop Llc | Apparatus and process for regenerating catalyst |
US7572365B2 (en) | 2002-10-11 | 2009-08-11 | Ivanhoe Energy, Inc. | Modified thermal processing of heavy hydrocarbon feedstocks |
US7572362B2 (en) | 2002-10-11 | 2009-08-11 | Ivanhoe Energy, Inc. | Modified thermal processing of heavy hydrocarbon feedstocks |
US7263934B2 (en) | 2003-02-24 | 2007-09-04 | Harris Contracting Company | Methods for generating energy using agricultural biofuel |
FR2851570B1 (fr) | 2003-02-24 | 2007-07-27 | Inst Francais Du Petrole | Installation et procede de gazeification multi-etapes d'une charge comprenant de la matiere organique |
US7022741B2 (en) | 2003-03-28 | 2006-04-04 | Conocophillips Company | Gas agitated multiphase catalytic reactor with reduced backmixing |
FI114115B (fi) | 2003-04-15 | 2004-08-13 | Foster Wheeler Energia Oy | Menetelmä ja laite lämmön talteenottamiseksi leijupetireaktorissa |
JP4050184B2 (ja) | 2003-05-13 | 2008-02-20 | 株式会社日本触媒 | 脂肪族カルボン酸の製造方法 |
US7247233B1 (en) | 2003-06-13 | 2007-07-24 | Uop Llc | Apparatus and process for minimizing catalyst residence time in a reactor vessel |
FI20031113A (fi) | 2003-07-29 | 2005-01-30 | Outokumpu Oy | Menetelmä ja laitteisto leijupetiuunin arinalta poistettavan materiaalin jäähdyttämiseksi |
US7004999B2 (en) | 2003-08-18 | 2006-02-28 | Dynamotive Energy Systems Corporation | Apparatus for separating fouling contaminants from non-condensable gases at the end of a pyrolysis/thermolysis of biomass process |
TW200519072A (en) | 2003-08-21 | 2005-06-16 | Pearson Technologies Inc | Process and apparatus for the production of useful products from carbonaceous feedstock |
BRPI0413811A (pt) | 2003-08-21 | 2006-10-17 | Int Environmental Solutions | suporte de cámara para sistema de tratamento de resìduos pirolìticos |
US7285186B2 (en) | 2003-12-11 | 2007-10-23 | Zbigniew Tokarz | Transverse-flow catalytic reactor for conversion of waste plastic material and scrap rubber |
US20050209328A1 (en) | 2004-03-19 | 2005-09-22 | Allgood Charles C | Alphahydroxyacids with ultra-low metal concentration |
EP2650346A1 (en) | 2004-04-28 | 2013-10-16 | Headwaters Heavy Oil, LLC | Ebullated bed hydroprocessing method for treating heavy hydrocarbons |
EP1781760A1 (en) | 2004-07-07 | 2007-05-09 | California Institute Of Technology | Process to upgrade oil using metal oxides |
US7685737B2 (en) | 2004-07-19 | 2010-03-30 | Earthrenew, Inc. | Process and system for drying and heat treating materials |
US7024800B2 (en) | 2004-07-19 | 2006-04-11 | Earthrenew, Inc. | Process and system for drying and heat treating materials |
EP1642878B1 (en) | 2004-10-01 | 2007-12-26 | Research Institute of Petroleum Industry | An integrated process and apparatus for producing liquid fuels |
FR2879213B1 (fr) | 2004-12-15 | 2007-11-09 | Inst Francais Du Petrole | Enchainement de procedes d'hydroconversion et de reformage a la vapeur en vue d'optimiser la production d'hydrogene sur sur des champs de production |
US7473349B2 (en) | 2004-12-30 | 2009-01-06 | Bp Corporation North America Inc. | Process for removal of sulfur from components for blending of transportation fuels |
US7829030B2 (en) | 2004-12-30 | 2010-11-09 | Exxonmobil Chemical Patents Inc. | Fluidizing a population of catalyst particles having a low catalyst fines content |
NL1027932C2 (nl) | 2004-12-31 | 2006-07-03 | Btg Biomass Technology Group B | Dipleg, werkwijze voor het gebruik ervan en toepassingen van de dipleg. |
US20060163053A1 (en) | 2005-01-21 | 2006-07-27 | Bengt-Sture Ershag | Batch pyrolysis system |
US7476774B2 (en) | 2005-02-28 | 2009-01-13 | Exxonmobil Research And Engineering Company | Liquid phase aromatics alkylation process |
US7964761B2 (en) | 2005-05-02 | 2011-06-21 | University Of Utah Research Foundation | Processes for catalytic conversion of lignin to liquid bio-fuels and novel bio-fuels |
DK1879979T3 (en) | 2005-05-03 | 2018-02-05 | Univ Danmarks Tekniske | Pyrolysis method and apparatus |
US20060264684A1 (en) | 2005-05-19 | 2006-11-23 | Petri John A | Production of diesel fuel from biorenewable feedstocks |
US7868214B2 (en) | 2005-05-19 | 2011-01-11 | Uop Llc | Production of olefins from biorenewable feedstocks |
CN101175547B (zh) | 2005-05-23 | 2011-12-28 | 国际壳牌研究有限公司 | 去除污染物的方法 |
US7491317B2 (en) | 2005-06-07 | 2009-02-17 | China Petroleum & Chemical Corporation | Desulfurization in turbulent fluid bed reactor |
EP1893359A4 (en) | 2005-06-08 | 2011-06-29 | Univ Western Ontario | APPARATUS AND METHOD FOR THE PYROLYSIS OF AGRICULTURAL BIOMASS |
US7727383B2 (en) | 2005-06-30 | 2010-06-01 | Amt International, Inc. | Process for producing petroleum oils with ultra-low nitrogen content |
CN100360248C (zh) | 2005-08-10 | 2008-01-09 | 重庆大学 | 生物质热解液化的工艺方法及其双塔式装置*** |
DE102005037917A1 (de) | 2005-08-11 | 2007-02-15 | Forschungszentrum Karlsruhe Gmbh | Verfahren zur Schnellpyrolyse von Lignocellulose |
US20070051238A1 (en) | 2005-09-07 | 2007-03-08 | Ravi Jain | Process for gas purification |
DE102005049375A1 (de) | 2005-10-15 | 2007-04-26 | Forschungszentrum Karlsruhe Gmbh | Verfahren zur Herstellung und Vorbereitung von Schnellpyrolyseprodukten aus Biomasse für eine Flugstrom Druckvergasung |
WO2007045093A1 (en) | 2005-10-21 | 2007-04-26 | Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Natural Resources Canada, Canadian Forest Service | Preparation of taxanes |
JP2009513771A (ja) | 2005-10-26 | 2009-04-02 | サンパイン・アクチボラゲット | 粗トールオイルから得られる自動車燃料およびファインケミカル |
US7867538B2 (en) | 2005-12-20 | 2011-01-11 | Archer Daniels Midland Company | Processes of improving the quality of oil and products produced therefrom |
JP2007229548A (ja) | 2006-02-27 | 2007-09-13 | Nippon Steel Engineering Co Ltd | バイオマス熱分解ガス化過程で使用する改質用触媒とその製造方法、及びその改質用触媒を用いた改質方法とバイオマス熱分解ガス化装置、並びに触媒再生方法 |
US20070205139A1 (en) | 2006-03-01 | 2007-09-06 | Sathit Kulprathipanja | Fcc dual elevation riser feed distributors for gasoline and light olefin modes of operation |
EP2007744B1 (en) * | 2006-04-03 | 2017-05-17 | Pharmatherm Chemicals Inc. | Thermal extraction method for producing a taxane extract |
EP1852493A1 (en) | 2006-05-05 | 2007-11-07 | BIOeCON International Holding N.V. | Hydrothermal treatment of carbon-based energy carrier material |
JP2009536235A (ja) | 2006-05-05 | 2009-10-08 | バイオイーコン インターナショナル ホールディング エヌ.ブイ. | 炭素に基づいたエネルギー担持物質を転化する改良された方法 |
US20070272538A1 (en) | 2006-05-26 | 2007-11-29 | Satchell Donald P | Flash pyrolosis method for carbonaceous materials |
US20080006520A1 (en) | 2006-07-06 | 2008-01-10 | Badger Phillip C | Method and system for accomplishing flash or fast pyrolysis with carbonaceous materials |
US20080006519A1 (en) | 2006-07-06 | 2008-01-10 | Badger Phillip C | Method and system for accomplishing flash or fast pyrolysis with carbonaceous materials |
WO2008009643A2 (en) | 2006-07-17 | 2008-01-24 | Bioecon International Holding N.V. | Catalytic pyrolysis of fine particulate biomass, and method for reducing the particle size of solid biomass particles |
US20080029437A1 (en) | 2006-08-02 | 2008-02-07 | Exxonmobil Research And Engineering Company | Olefin upgrading process with guard bed regeneration |
US7758817B2 (en) | 2006-08-09 | 2010-07-20 | Uop Llc | Device for contacting high contaminated feedstocks with catalyst in an FCC unit |
GB0616298D0 (en) | 2006-08-16 | 2006-09-27 | Univ Aston | Biomass pyrolysis |
EP1892280A1 (en) | 2006-08-16 | 2008-02-27 | BIOeCON International Holding N.V. | Fluid catalytic cracking of oxygenated compounds |
JP5189981B2 (ja) | 2006-08-18 | 2013-04-24 | Jx日鉱日石エネルギー株式会社 | バイオマスの処理方法、燃料電池用燃料、ガソリン、ディーゼル燃料、液化石油ガス及び合成樹脂 |
US20080051619A1 (en) | 2006-08-25 | 2008-02-28 | Santi Kulprathipanja | Olefin-Separation Process |
US7578927B2 (en) | 2006-08-31 | 2009-08-25 | Uop Llc | Gasoline and diesel production from pyrolytic lignin produced from pyrolysis of cellulosic waste |
US20080081006A1 (en) | 2006-09-29 | 2008-04-03 | Myers Daniel N | Advanced elevated feed distribution system for very large diameter RCC reactor risers |
US7687261B2 (en) | 2006-10-13 | 2010-03-30 | General Atomics | Photosynthetic oil production in a two-stage reactor |
WO2008063485A2 (en) | 2006-11-16 | 2008-05-29 | Archer-Daniels-Midland Company | Process for hydrogen gas production from carbohydrate feedstocks |
FR2910483B1 (fr) | 2006-12-21 | 2010-07-30 | Inst Francais Du Petrole | Procede de conversion de charges issues de sources renouvelables en bases carburants gazoles de bonne qualite. |
US20080171649A1 (en) | 2007-01-12 | 2008-07-17 | Deng-Yang Jan | Modified Y-85 and LZ-210 Zeolites |
DE102007005835A1 (de) | 2007-02-01 | 2008-08-14 | Forschungszentrum Karlsruhe Gmbh | Verfahren und Vorrichtung zur Umwandlung von Biomasse in Kraftstoff |
US7959765B2 (en) | 2007-02-06 | 2011-06-14 | North Carolina State Universtiy | Product preparation and recovery from thermolysis of lignocellulosics in ionic liquids |
US7737314B2 (en) | 2007-02-12 | 2010-06-15 | Exxonmobil Chemical Patents Inc. | Production of high purity ethylbenzene from non-extracted feed and non-extracted reformate useful therein |
ES2303792B1 (es) | 2007-02-15 | 2009-06-12 | Industrias Mecanicas Alcudia S.A. | Un procedimiento para la revalorizacion energetica de la fraccion organica de residuos solidos urbanos, e instalacion. |
GB2446820B (en) | 2007-02-23 | 2011-09-21 | Mark Collins | A Method of Generating Heat |
CA2624746C (en) | 2007-03-12 | 2015-02-24 | Robert Graham | Methods and systems for producing reduced resid and bottomless products from heavy hydrocarbon feedstocks |
GB2447684B (en) | 2007-03-21 | 2011-11-23 | Statoil Asa | Biogasoline |
US20080282606A1 (en) | 2007-04-16 | 2008-11-20 | Plaza John P | System and process for producing biodiesel |
US20080272030A1 (en) | 2007-05-04 | 2008-11-06 | Boykin Jack W | Method for the production of synthetic fuels |
CN101045524B (zh) | 2007-05-04 | 2010-05-19 | 大连理工大学 | 固体燃料催化气化制富氢气体的方法 |
US8153850B2 (en) | 2007-05-11 | 2012-04-10 | The Texas A&M University System | Integrated biofuel production system |
US7914667B2 (en) | 2007-06-04 | 2011-03-29 | Exxonmobil Chemical Patents Inc. | Pyrolysis reactor conversion of hydrocarbon feedstocks into higher value hydrocarbons |
US7425657B1 (en) | 2007-06-06 | 2008-09-16 | Battelle Memorial Institute | Palladium catalyzed hydrogenation of bio-oils and organic compounds |
US8158842B2 (en) | 2007-06-15 | 2012-04-17 | Uop Llc | Production of chemicals from pyrolysis oil |
US20080318763A1 (en) | 2007-06-22 | 2008-12-25 | Greg Anderson | System for production and purification of biofuel |
DE102007031461A1 (de) | 2007-07-05 | 2009-01-08 | Sappok, Manfred, Dipl.-Phys. Dr. | Verfahren zum Stabilisieren von Heizöl oder Dieselöl, insbesondere aus der Depolimerisation von kohlenwasserstoffhaltigen Rückständen |
CN101353582B (zh) | 2007-07-25 | 2010-12-01 | 中国科学院工程热物理研究所 | 固体热载体快速热解方法及装置 |
WO2009017958A1 (en) | 2007-07-31 | 2009-02-05 | Endicott Biofuels Ii, Llc | Production of renewable diesel by pyrolysis and esterification |
WO2009018531A1 (en) | 2007-08-01 | 2009-02-05 | Virginia Tech Intellectual Properties, Inc. | Fractional catalytic pyrolysis of biomass |
HUP0700508A2 (en) | 2007-08-03 | 2010-12-28 | 3R Carbon Capture And Storage Pty Ltd | Appliance for carbon catena development and process for neutralisation of dangerous wastes |
US8217210B2 (en) | 2007-08-27 | 2012-07-10 | Purdue Research Foundation | Integrated gasification—pyrolysis process |
US8217211B2 (en) | 2007-08-27 | 2012-07-10 | Purdue Research Foundation | Process for producing liquid hydrocarbon by pyrolysis of biomass in presence of hydrogen from a carbon-free energy source |
US8003834B2 (en) | 2007-09-20 | 2011-08-23 | Uop Llc | Integrated process for oil extraction and production of diesel fuel from biorenewable feedstocks |
US7999143B2 (en) | 2007-09-20 | 2011-08-16 | Uop Llc | Production of diesel fuel from renewable feedstocks with reduced hydrogen consumption |
US7982075B2 (en) | 2007-09-20 | 2011-07-19 | Uop Llc | Production of diesel fuel from biorenewable feedstocks with lower hydrogen consumption |
US7982078B2 (en) | 2007-09-20 | 2011-07-19 | Uop Llc | Production of diesel fuel from biorenewable feedstocks with selective separation of converted oxygen |
US7982077B2 (en) | 2007-09-20 | 2011-07-19 | Uop Llc | Production of diesel fuel from biorenewable feedstocks with selective separation of converted oxygen |
US7999142B2 (en) | 2007-09-20 | 2011-08-16 | Uop Llc | Production of diesel fuel from biorenewable feedstocks |
FI123180B (fi) | 2007-10-11 | 2012-12-14 | Valtion Teknillinen | Laitteisto pyrolyysituotteen valmistamiseksi |
FI123455B (fi) | 2007-10-11 | 2013-05-15 | Valtion Teknillinen | Menetelmä pyrolysoinnin toteuttamiseksi |
US7905990B2 (en) | 2007-11-20 | 2011-03-15 | Ensyn Renewables, Inc. | Rapid thermal conversion of biomass |
US8241605B2 (en) | 2008-01-31 | 2012-08-14 | Battelle Memorial Institute | Methods and apparatus for catalytic hydrothermal gasification of biomass |
US20090208402A1 (en) | 2008-02-20 | 2009-08-20 | Rossi Robert A | Process and system for producing commercial quality carbon dioxide from fine particle limestone |
CN102015969B (zh) | 2008-03-04 | 2015-05-27 | 马萨诸塞大学 | 固体生物质的催化热解及相关的生物燃料、芳烃化合物和烯烃化合物 |
US8058492B2 (en) | 2008-03-17 | 2011-11-15 | Uop Llc | Controlling production of transportation fuels from renewable feedstocks |
US8039682B2 (en) | 2008-03-17 | 2011-10-18 | Uop Llc | Production of aviation fuel from renewable feedstocks |
EP2105456A1 (en) | 2008-03-25 | 2009-09-30 | KiOR Inc. | Composition comprising solid biomass coated onto a solid catalyst |
EP2105486A1 (en) | 2008-03-25 | 2009-09-30 | KiOR Inc. | Low total acid number bio-crude |
FI122778B (fi) | 2008-03-31 | 2012-06-29 | Metso Power Oy | Pyrolyysimenetelmä kattilan yhteydessä ja pyrolyysilaitteisto |
CN101550347B (zh) | 2008-04-02 | 2013-01-09 | 朱复东 | 生物质浆态雾化热裂解工艺 |
US8329968B2 (en) | 2008-04-06 | 2012-12-11 | Uop Llc | Production of blended gasoline aviation and diesel fuels from renewable feedstocks |
CN102057019B (zh) | 2008-04-06 | 2014-07-02 | 环球油品公司 | 来自生物质衍生热解油的燃料和混合燃料成分 |
US20090253947A1 (en) | 2008-04-06 | 2009-10-08 | Brandvold Timothy A | Production of Blended Fuel from Renewable Feedstocks |
US8324438B2 (en) | 2008-04-06 | 2012-12-04 | Uop Llc | Production of blended gasoline and blended aviation fuel from renewable feedstocks |
US8329967B2 (en) | 2008-04-06 | 2012-12-11 | Uop Llc | Production of blended fuel from renewable feedstocks |
US7897124B2 (en) | 2008-09-18 | 2011-03-01 | Gunnerman Rudolf W | Continuous process and plant design for conversion of biogas to liquid fuel |
CN101294085A (zh) | 2008-04-07 | 2008-10-29 | 赵靖敏 | 一种生物质燃气的制备方法及其装置 |
US8100996B2 (en) | 2008-04-09 | 2012-01-24 | Velocys, Inc. | Process for upgrading a carbonaceous material using microchannel process technology |
CN102056657A (zh) | 2008-04-09 | 2011-05-11 | 万罗赛斯公司 | 使用微通道工艺技术将碳质材料转化为甲烷、甲醇和/或二甲醚的方法 |
US7888540B2 (en) | 2008-04-11 | 2011-02-15 | General Electric Company | Integrated system and method for producing fuel composition from biomass |
US8097090B2 (en) | 2008-04-25 | 2012-01-17 | Ensyn Renewables Inc. | Mitigation of deposits and secondary reactions in thermal conversion processes |
US20090293344A1 (en) | 2008-05-30 | 2009-12-03 | Baker Hughes Incorporated | Process for Removing Water and Water Soluble Contaminants From Biofuels |
US8304592B2 (en) | 2008-06-24 | 2012-11-06 | Uop Llc | Production of paraffinic fuel from renewable feedstocks |
US20090321311A1 (en) | 2008-06-27 | 2009-12-31 | Uop Llc | Production of diesel fuel from renewable feedstocks containing phosphorus |
WO2010002792A2 (en) | 2008-06-30 | 2010-01-07 | Kior, Inc. | Co-processing solid biomass in a conventional petroleum refining process unit |
CN101318622A (zh) | 2008-07-18 | 2008-12-10 | 华东理工大学 | 生物质快速裂解油水蒸气催化重整制氢的方法 |
US8092578B2 (en) | 2008-08-25 | 2012-01-10 | Eisenmann Corporation | Method and apparatus for eliminating or reducing waste effluent from a wet electrostatic precipitator |
CN101381611B (zh) | 2008-10-15 | 2012-04-11 | 中国林业科学研究院林产化学工业研究所 | 生物质裂解油酯化醚化提质改性为改质生物油的方法 |
CN102245170A (zh) | 2008-12-08 | 2011-11-16 | 格雷斯公司 | 使用沸石与基体表面积的比率高的催化剂使生物原料裂化的方法 |
US7960598B2 (en) | 2008-12-08 | 2011-06-14 | Chevron U.S.A. Inc. | Selective, integrated processing of bio-derived ester species to yield low molecular weight hydrocarbons and hydrogen for the production of biofuels |
CN101745349B (zh) | 2008-12-12 | 2013-04-17 | 李群柱 | 一种催化剂取热方法及其装置 |
US8252169B2 (en) | 2008-12-16 | 2012-08-28 | Macarthur James B | Process for upgrading coal pyrolysis oils |
TWI449781B (zh) | 2008-12-17 | 2014-08-21 | Lummus Technology Inc | 包含分段漿料添加之氣化系統及方法 |
US8283506B2 (en) | 2008-12-17 | 2012-10-09 | Uop Llc | Production of fuel from renewable feedstocks using a finishing reactor |
US8246914B2 (en) | 2008-12-22 | 2012-08-21 | Uop Llc | Fluid catalytic cracking system |
US20100162625A1 (en) | 2008-12-31 | 2010-07-01 | Innovative Energy Global Limited | Biomass fast pyrolysis system utilizing non-circulating riser reactor |
CN101544901B (zh) | 2009-05-05 | 2012-05-23 | 江苏大学 | 生物质热裂解制取生物油的方法及装置 |
CN102438969A (zh) | 2009-05-22 | 2012-05-02 | 科伊奥股份有限公司 | 利用氢源处理生物质 |
US20100325954A1 (en) | 2009-06-30 | 2010-12-30 | General Electric Company | Quench chamber assembly for a gasifier |
CN101993712B (zh) | 2009-08-17 | 2013-03-06 | 中国石油大学(北京) | 一种灵活调整催化裂化反应-再生***热量平衡的方法 |
US20110068585A1 (en) | 2009-09-24 | 2011-03-24 | Alstom Technology Ltd | Method and system for capturing and utilizing energy generated in a flue gas stream processing system |
ITMI20091630A1 (it) | 2009-09-24 | 2011-03-24 | Mec Srl | Impianto e procedimento per produrre pellet di anidride carbonica ghiacciata |
WO2011055390A2 (en) | 2009-11-09 | 2011-05-12 | Rohit Joshi | Method and apparatus for processing of spent lubricating oil |
DE102009052282B4 (de) | 2009-11-09 | 2012-11-29 | Thyssenkrupp Uhde Gmbh | Verfahren zur Kompensation von Abgasenthalpieverlusten von Heat-Recovery-Koksöfen |
US8314275B2 (en) | 2009-11-23 | 2012-11-20 | Uop Llc | Methods for producing biomass-derived pyrolysis oils having increased phase stability |
EP2325281A1 (en) | 2009-11-24 | 2011-05-25 | Shell Internationale Research Maatschappij B.V. | Process for the catalytic cracking of pyrolysis oils |
US8404909B2 (en) | 2009-12-09 | 2013-03-26 | Chevron U.S.A. Inc. | Method for capturing carbon dioxide from biomass pyrolysis process |
US8524087B2 (en) | 2009-12-23 | 2013-09-03 | Uop Llc | Low metal, low water biomass-derived pyrolysis oils and methods for producing the same |
US20110146140A1 (en) | 2009-12-23 | 2011-06-23 | Brandvold Timothy A | Low water biomass-derived pyrolysis oil and processes for preparing the same |
US8864999B2 (en) | 2009-12-23 | 2014-10-21 | Uop Llc | Methods for regenerating acidic ion-exchange resins and reusing regenerants in such methods |
US8715490B2 (en) | 2009-12-23 | 2014-05-06 | Uop Llc | Low metal biomass-derived pyrolysis oils and processes for producing the same |
US8471081B2 (en) | 2009-12-28 | 2013-06-25 | Uop Llc | Production of diesel fuel from crude tall oil |
US8519203B2 (en) | 2010-02-17 | 2013-08-27 | Uop Llc | Low oxygen biomass-derived pyrolysis oils and methods for producing the same |
US8404910B2 (en) | 2010-02-17 | 2013-03-26 | Uop Llc | Low oxygen biomass-derived pyrolysis oils and methods for producing the same |
US8575408B2 (en) | 2010-03-30 | 2013-11-05 | Uop Llc | Use of a guard bed reactor to improve conversion of biofeedstocks to fuel |
US20110239530A1 (en) | 2010-03-30 | 2011-10-06 | Uop Llc | Use of well mixed, backmixed reactors for processing of unstable bio feedstocks |
US8251227B2 (en) | 2010-04-16 | 2012-08-28 | Kellogg Brown & Root Llc | Methods and apparatus for separating particulates from a particulate-fluid mixture |
US20110284359A1 (en) | 2010-05-20 | 2011-11-24 | Uop Llc | Processes for controlling afterburn in a reheater and for controlling loss of entrained solid particles in combustion product flue gas |
EP2404983A1 (en) | 2010-07-06 | 2012-01-11 | Total Raffinage Marketing | Hydroconversion process for heavy hydrocarbonaceous feedstock |
US8499702B2 (en) | 2010-07-15 | 2013-08-06 | Ensyn Renewables, Inc. | Char-handling processes in a pyrolysis system |
US8057641B2 (en) | 2010-07-19 | 2011-11-15 | Kior Inc. | Method and apparatus for pyrolysis of a biomass |
US8519205B2 (en) | 2010-07-23 | 2013-08-27 | Ensyn Renewables, Inc. | Low water biomass-derived pyrolysis oils and processes for producing the same |
US9222044B2 (en) | 2010-07-26 | 2015-12-29 | Uop Llc | Methods for producing low oxygen biomass-derived pyrolysis oils |
US20120023809A1 (en) | 2010-07-28 | 2012-02-02 | Uop Llc | Methods for producing phase stable, reduced acid biomass-derived pyrolysis oils |
US8083900B2 (en) | 2010-08-09 | 2011-12-27 | Kior Inc. | Removal of water from bio-oil |
CA2816353A1 (en) | 2010-11-12 | 2012-05-18 | Johannes Antonius Hogendoorn | Process for the preparation of a biofuel and/or biochemical |
US20120137939A1 (en) | 2010-12-06 | 2012-06-07 | Uop Llc | Processes and systems for producing heat for rapid thermal processing of carbonaceous material |
AU2011348031A1 (en) | 2010-12-24 | 2013-06-27 | Sapphire Energy, Inc. | Production of aromatics from renewable resources |
US8829258B2 (en) | 2010-12-27 | 2014-09-09 | Phillips 66 Company | Integrated FCC biomass pyrolysis/upgrading |
US20120167454A1 (en) | 2010-12-30 | 2012-07-05 | Uop Llc | Pretreatment of fats and oils in the production of biofuels |
RU2013135471A (ru) | 2010-12-30 | 2015-02-10 | Кайор Инк. | Производство возобновляемого биотоплива |
US8716522B2 (en) | 2010-12-30 | 2014-05-06 | Uop Llc | Acetic acid production from biomass pyrolysis |
US9441887B2 (en) | 2011-02-22 | 2016-09-13 | Ensyn Renewables, Inc. | Heat removal and recovery in biomass pyrolysis |
US8236173B2 (en) | 2011-03-10 | 2012-08-07 | Kior, Inc. | Biomass pretreatment for fast pyrolysis to liquids |
US8100990B2 (en) | 2011-05-15 | 2012-01-24 | Avello Bioenery, Inc. | Methods for integrated fast pyrolysis processing of biomass |
US9193924B2 (en) | 2011-06-16 | 2015-11-24 | Uop Llc | Methods and apparatuses for forming low-metal biomass-derived pyrolysis oil |
US9475960B2 (en) | 2011-07-29 | 2016-10-25 | Inaeris Technologies, Llc | Coating composition |
US9347005B2 (en) | 2011-09-13 | 2016-05-24 | Ensyn Renewables, Inc. | Methods and apparatuses for rapid thermal processing of carbonaceous material |
US9109174B2 (en) | 2011-09-20 | 2015-08-18 | Phillips 66 Company | Advanced cellulosic renewable fuels |
US9044727B2 (en) | 2011-09-22 | 2015-06-02 | Ensyn Renewables, Inc. | Apparatuses and methods for controlling heat for rapid thermal processing of carbonaceous material |
US10041667B2 (en) | 2011-09-22 | 2018-08-07 | Ensyn Renewables, Inc. | Apparatuses for controlling heat for rapid thermal processing of carbonaceous material and methods for the same |
WO2013049665A2 (en) | 2011-09-30 | 2013-04-04 | Chevron U.S.A., Inc. | Process for producing a refinery stream-compatible bio-oil from a lignocellulosic feedstock |
US9168500B2 (en) | 2011-10-26 | 2015-10-27 | Res Usa, Llc | Gasifier fluidization |
EP2748283A1 (en) | 2011-10-31 | 2014-07-02 | Shell Internationale Research Maatschappij B.V. | A method for upgrading an oil, a fuel product and a hydrocarbon product fraction |
IN2014DN03435A (zh) | 2011-11-14 | 2015-06-05 | Shell Int Research | |
US9109177B2 (en) | 2011-12-12 | 2015-08-18 | Ensyn Renewables, Inc. | Systems and methods for renewable fuel |
US9068126B2 (en) | 2011-12-14 | 2015-06-30 | Uop Llc | Methods for deoxygenating biomass-derived pyrolysis oil |
US8940060B2 (en) | 2011-12-15 | 2015-01-27 | Uop Llc | Methods and apparatuses for forming low-metal biomass-derived pyrolysis oil |
US8877995B2 (en) | 2011-12-16 | 2014-11-04 | Uop Llc | Pyrolysis fuels and methods for processing pyrolysis fuels |
US9242219B2 (en) | 2012-01-30 | 2016-01-26 | PHG Energy, LLC | Fluidized bed biogasifier and method for gasifying biosolids |
US8546635B1 (en) | 2012-04-04 | 2013-10-01 | Uop Llc | Methods and apparatuses for preparing upgraded pyrolysis oil |
US9670413B2 (en) | 2012-06-28 | 2017-06-06 | Ensyn Renewables, Inc. | Methods and apparatuses for thermally converting biomass |
BR112015003952B1 (pt) | 2012-08-24 | 2021-11-23 | Ensyn Renewables, Inc | Método para processar uma matéria-prima de fração de petróleo e um produto de líquido desvolatilizado em um sistema de refinaria |
US9150466B2 (en) | 2012-11-20 | 2015-10-06 | Uop Llc | Counter-current fluidized bed reactor for the dehydrogenation of olefins |
US9023285B2 (en) | 2012-11-20 | 2015-05-05 | Uop Llc | Counter-current fluidized bed reactor for the dehydrogenation of olefins |
EP3492559A1 (en) | 2013-06-26 | 2019-06-05 | Ensyn Renewables, Inc. | Methods for renewable fuel |
-
2007
- 2007-04-02 EP EP07719465.2A patent/EP2007744B1/en active Active
- 2007-04-02 US US12/295,916 patent/US9127208B2/en active Active
- 2007-04-02 WO PCT/CA2007/000535 patent/WO2007112570A1/en active Application Filing
- 2007-04-02 EP EP17165988.1A patent/EP3252128B1/en active Active
- 2007-04-02 DK DK07719465.2T patent/DK2007744T3/en active
- 2007-04-02 CN CN201210096487.9A patent/CN102702139B/zh not_active Expired - Fee Related
- 2007-04-02 DK DK17165988.1T patent/DK3252128T3/en active
- 2007-04-02 CA CA2647564A patent/CA2647564C/en active Active
- 2007-04-02 CN CNA2007800204399A patent/CN101460473A/zh active Pending
-
2015
- 2015-07-29 US US14/812,711 patent/US9809564B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6002025A (en) * | 1999-02-24 | 1999-12-14 | Bcm Developement Inc. | Method for the purification of taxanes |
WO2001009243A1 (en) * | 1999-07-29 | 2001-02-08 | Ensyn Group, Inc. | Novel natural resin formulations |
CN1362959A (zh) * | 2000-02-02 | 2002-08-07 | 佛罗里达州立大学研究基金有限公司 | C10氨基甲酰氧基取代的紫衫烷抗肿瘤剂 |
CA2521829A1 (en) * | 2004-09-30 | 2006-03-30 | University Of Ottawa | Process for extracting taxanes |
Non-Patent Citations (2)
Title |
---|
A review of modern sample-preparation techniques for the extraction and analysis of medicinal plants;Carmen W. Huie;《Anal Bioanal Chem》;20020531;第373卷(第1-2期);第24-26页 * |
E xtractions with superheated water;Roger M. Smith;《Journal of Chromatography A》;20021031;第975卷(第1期);第33、35页左栏、第44页右栏 * |
Also Published As
Publication number | Publication date |
---|---|
EP3252128A3 (en) | 2018-03-28 |
CA2647564C (en) | 2016-08-30 |
DK2007744T3 (en) | 2017-08-28 |
US9127208B2 (en) | 2015-09-08 |
DK3252128T3 (en) | 2019-04-01 |
WO2007112570A1 (en) | 2007-10-11 |
CN101460473A (zh) | 2009-06-17 |
EP3252128A1 (en) | 2017-12-06 |
CA2647564A1 (en) | 2007-10-11 |
EP2007744B1 (en) | 2017-05-17 |
CN102702139A (zh) | 2012-10-03 |
US20090298927A1 (en) | 2009-12-03 |
US20160024037A1 (en) | 2016-01-28 |
EP3252128B1 (en) | 2019-01-02 |
US9809564B2 (en) | 2017-11-07 |
EP2007744A4 (en) | 2014-03-26 |
EP2007744A1 (en) | 2008-12-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102702139B (zh) | 热提取方法和产物 | |
WO2007045093A1 (en) | Preparation of taxanes | |
CN106831353B (zh) | 一种从***中提取***二酚的方法 | |
CA3027108C (en) | Purification and separation techniques for cannabinoids | |
CN1055087C (zh) | 从原料中提取紫杉醇的方法和设备 | |
CA2521829A1 (en) | Process for extracting taxanes | |
WO2019023751A1 (en) | CANNABIS MEDICINAL | |
CN1342155A (zh) | 从含紫杉醇物质生产紫杉醇的高产率提取方法 | |
JP2015509979A (ja) | 針葉樹の材種からフラボノイドであるジヒドロケルセチン(タキシホリン)を単離するための方法 | |
US20060043020A1 (en) | Process for the extraction of paclitaxel and 9-dihydro-13-acetylbaccatin III from Taxus | |
CN1244566C (zh) | 一种从种植红豆杉叶枝中制备紫杉醇的方法 | |
CN1166656C (zh) | 一种从红豆杉叶枝残渣中制备10-去乙酰基巴卡丁ⅲ的方法 | |
Li et al. | Two new quinoline alkaloid mannopyranosides from Solidago canadensis | |
CN114685268B (zh) | 一种***二酚酸的提取方法及纯化方法 | |
CN101624331B (zh) | 反式橙花叔醇对照品的制备方法及其产品 | |
Cass et al. | Challenges in the isolation of taxanes from Taxus canadensis by fast pyrolysis | |
CN100564371C (zh) | 一种从雷公藤属植物中提取儿茶素及表儿茶素的方法 | |
CN100546986C (zh) | 从红豆杉属植物中获得紫杉醇的方法 | |
CN107647399B (zh) | 一种女贞子多酚及其生产方法 | |
CN112915122A (zh) | 一种同时制备***萜烯和***萜烯酚的方法 | |
CN1183216A (zh) | 含竹红菌甲素的新型生物农药杀虫剂原药的制法 | |
Başar et al. | Chemical structure and characterization of bio-oils isolated from walnut shells by different processes | |
CN117986093A (zh) | 一种零thc工业***素油的制备方法 | |
CN117925320A (zh) | 一种具有高保湿舒缓功效的红豆杉油及其制备方法和应用 | |
CN113717139A (zh) | 一种从石榴皮中提取槲皮素的方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160120 Termination date: 20190402 |
|
CF01 | Termination of patent right due to non-payment of annual fee |