CN106794430A - 碳分子筛(cms)中空纤维膜和其始于预氧化聚酰亚胺的制备 - Google Patents
碳分子筛(cms)中空纤维膜和其始于预氧化聚酰亚胺的制备 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D67/0039—Inorganic membrane manufacture
- B01D67/0067—Inorganic membrane manufacture by carbonisation or pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0076—Pretreatment of inorganic membrane material prior to membrane formation, e.g. coating of metal powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/08—Specific temperatures applied
- B01D2323/081—Heating
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Abstract
由具有至少400℃的玻璃态化温度且包括桥连苯基化合物的聚酰亚胺(例如6FDA/BPDA‑DAM聚酰亚胺)制备用于使氢气与乙烯(不论是作为氢气与乙烯的纯混合物存在,还是作为裂解气体的组分存在)彼此分离的碳分子筛膜。制备包含两个依序步骤a)和b)。在步骤a)中,将由所述聚酰亚胺的无缺陷纤维制成的膜与含氧气氛在足以产生预氧化且预碳化的聚合物膜的时间和温度条件下接触放置,所述聚合物膜不溶于热(110℃)N‑甲基吡咯烷酮中且至少基本上不发生子结构塌陷。在步骤b)中,使预氧化且预碳化的膜在冲洗气体存在下、在足以产生碳分子筛膜的时间和温度条件下热解,所述碳分子筛膜具有氢气渗透性和氢气/乙烯选择性大于由相同膜仅使用如步骤b)中的热解所制备的碳分子筛膜的氢气渗透性和氢气/乙烯选择性中的至少一种。
Description
技术领域
本申请要求2014年9月24日所提交的美国临时申请第62/054,427号的权益。
本发明大体上涉及碳分子筛(CMS)中空纤维膜、其始于预氧化聚酰亚胺的制备,以及其用于分离气体、尤其是从裂解气体中分离氢气CMS(H2)的用途。
背景技术
在热解期间,多种不对称的聚合物纤维经历了某种程度的多孔子结构塌陷,这又导致分离层(CMS)厚度增加和随之而来的渗透性降低。可商购的聚合物MatrimidTM(BTDA-DAPI,3,3',4,4'-二苯甲酮四甲酸二酐(BTDA)与5(6)-氨基-1-(4'-氨基苯基)-1,3,3'-三甲基茚满(DAPI)的缩合产物,其玻璃态化温度(Tg)为305摄氏度(℃))是在处于或高于其Tg的温度下经历此类多孔子结构塌陷的聚酰亚胺实例。
一种抗击在热解期间发生的子结构塌陷的尝试是对聚合物前驱物纤维采用预处理。美国专利申请公开(USPAP)2013/0152793教示了乙烯基三甲氧基硅烷处理(V-处理),以试图在聚酰亚胺前驱物(如MatrimidTM5218以及6FDA/BPDA-DAM)热解期间使亚结构稳定。
欧洲专利公开(EP)0 459 623(Yoshinaga等人)教示了一种利用热稳定化聚酰亚胺纤维制造供分离氢气/甲烷用的不对称中空纤丝碳膜的方法。芳香族酰亚胺聚合物是芳香族四羧酸组分、其盐类和酯类与芳香族二胺组分的聚合和酰亚胺化产物,所述芳香族四羧酸组分包含至少一个选自联苯四羧酸和二酐的成员,所述芳香族二胺组分是至少一个选自二氨基二烷基二苯砜、二氨基二苯基甲烷和4,4'-二氨基二苯醚的成员。
Meha Rungta等人在“膜基乙烯/乙烷分离:上限和超越”(Membrane-basedEthylene/Ethane Separation:The Upper Bound and Beyond)”《美国化学工程师协会杂志(AIChE Journal)》(2013年9月,第59卷,第9期,第3475-3489页)中呈现了关于利用多种聚酰亚胺前驱物(其中三种是6FDA/BPDA-DAM、6FDA-DAM和MatrimidTM)执行乙烯/乙烷分离的教示内容。Matrimid共聚物得自两种单体的聚合:3,3',4,4'-二苯甲酮四甲酸二酐(BTDA)和5(6)-氨基-1-(4'-氨基苯基)-1,3-三甲基茚满(DAPI)。教示内容包括氧掺杂(热解期间,氧气和氩气的混合物)和“后氧掺杂”(在超过热解期间所用温度的温度下热解后,再次暴露于氧气)。
Rachana Singh等人在“通过双重温度二次氧掺杂(DTSOD)实现的碳分子筛膜性能调节(Carbon molecular sieve membrane performance tuning by dual temperaturesecondary oxygen doping(DTSOD))”《膜科学杂志(Journal of Membrane Science)》(427(2013),第472-478页)中揭露了热解气氛中存在痕量的氧气能够对CMS膜(6FDA/BPDA-DAM)的分离性能进行调节。还参见Mayumi Kiyono等人,“聚合物前驱物对碳分子筛结构和分离性能特性的影响(Effect of polymer precursors on carbon molecular sievestructure and separation performance properties)”《碳(Carbon)》(48(2010),第4432-4441页);和Mayumi Kiyono等人,“氧气暴露对碳分子筛膜的形成和性能的影响概括(Generalization of effect of oxygen exposure on formation and performance ofcarbon molecular sieve membranes)”《碳(Carbon)》(48(2010),第4442-4449页)。
Liren Xu等人在“混合膜蒸馏工艺中用于分离烯烃/石蜡的烯烃选择性不对称碳分子筛中空纤维膜(Olefins-selective asymmetric carbon molecular sieve hollowfiber membranes for hybrid membrane-distillation processes for olefin/paraffin separations)”《膜科学杂志》(423-424(2012),第314-323页)中论述了不对称CMS中空纤维膜的研发,其中关注点是由6FDA-DAM和6FDA/BPDA-DAM前驱物制备的膜。
Keisha M.Steel等人在“热解参数对碳材料的气体分离特性的影响的调查(Aninvestigation of the effects of pyrolysis parameters on gas separationproperties of carbon materials)”《碳》(43(2005),第1843-1856页)中对6FDA/BPDA-DAM与MatrimidTM聚合物前驱物的各种热解参数进行了比较。
Cheryl W.Jones等人在“碳分子筛气体分离膜-I.基于聚酰亚胺前驱物的制备和表征(Carbon Molecular Sieve Gas Separation Membranes-I.Preparation andCharacterization Based on Polyimide Precursors)”《碳》(第32卷,第8期,第1419-1425页,1994)中教示了通过使中空纤维聚酰亚胺前驱物(例如6FDA/BPDA-DAM)热解来制备CMS膜以及此类膜用于分离气体对(如H2/CH4)的用途。
下文式1展示了6FDA/BPDA-DAM的化学结构,其中X和Y各自是1以便提供1:1比率。
Yoshihiro Kusuki等人在“通过使不对称聚酰亚胺中空纤维膜热解所制备的不对称碳膜的气体渗透特性和表征(Gas permeation properties and characterization ofasymmetric carbon membranes prepared by pyrolyzing asymmetric polyimidehollow fiber membrane)”《膜科学杂志》(134(1997),第245-253页)中揭露了通过使不对称聚酰亚胺中空纤维膜在600℃到1000℃范围内的温度下、在氮气下热解3.6分钟所制备的碳膜。
尽管在避免子结构在热解期间塌陷方面获得了改进,但是所属领域的技术人员应继续寻求进一步的改进。
发明内容
本发明的一个方面是一种由聚酰亚胺制备用于将氢气和乙烯彼此分离的碳分子筛膜的方法,所述方法包含如下依序步骤:a)将由聚酰亚胺纤维制成的膜与含氧气氛或如纯氧气或空气的气体在大于300℃到小于400℃范围内的温度下接触放置,在那个温度范围内放置的时间为大于或等于五(5)分钟直到200小时(hr)以产生不溶于热(110℃)N-甲基吡咯烷酮中且基本上不发生、优选完全不发生子结构塌陷的预氧化且预碳化聚合物膜,所述聚酰亚胺选自由以下组成的群组:((5,5'-[2,2,2-三氟-1-(三氟甲基)亚乙基]双-1,3-异苯并呋喃二酮(6FDA)、3,3',4,4'-联苯四甲酸二酐(BPDA)、2,4,6-三甲基-1,3-苯二胺(DAM))(6FDA/BPDA-DAM)聚酰亚胺和a)玻璃态化温度(Tg)为至少400℃且b)包括桥连苯基化合物(例如其中被取代的甲基部分安置于两个苯基之间且键结到两个苯基)的聚酰亚胺;以及b)使预氧化且预碳化的聚合物膜在冲洗气体存在下、在450℃到1000℃范围内的温度下热解,热解的时间在1分钟到100小时(优选两个(2)小时到八个(8)小时)范围内,以产生碳分子筛膜,所述碳分子筛膜具有氢气渗透性和氢气/乙烯选择性大于由相同膜仅使用如步骤b)中的热解所制备的碳分子筛膜的氢气渗透性和氢气/乙烯选择性中的至少一种。步骤a中在所述温度范围内的时间优选大于或等于30分钟到两小时。冲洗气体宜包含、主要由以下组成或由以下组成:氩气或另一种惰性气体以及任选的痕量的氧气,其中痕量小于100重量份/百万重量份冲洗气体(ppm),优选小于50ppm。
优选的膜是由“无缺陷”的纤维制成。如本文中所用,“无缺陷”意味着聚合物中空纤维相对于气体对的选择性是使用由相同聚合物制成的致密膜针对相同气体对的选择性的至少90%(也称为“固有选择性”)。
适用于上述方法中的聚酰亚胺包括单芳香族二胺部分,而非二芳香族胺部分。
如Mayumi Kiyono等人在上文所引用的《膜科学杂志》中所述来制备6FDA/BPDA-DAM聚合物。还参见Wulin Qiu等人在上文所引用的《聚合物》中的论文。简言之,通过以下三种单体的热或化学酰亚胺化来制备此类聚合物:5,5'-[2,2,2-三氟-1-(三氟甲基)亚乙基]双-1,3-异苯并呋喃二酮(6FDA)、3,3',4,4'-联苯四甲酸二酐(BPDA)和2,4,6-三甲基-1,3-苯二胺(DAM)。此类聚合物具有424℃的玻璃态化温度和约450℃的分解温度。根据Qiu等人,所述方法是两步法。在步骤一中,在低于5℃的温度下,通过使化学计算量的二酐与二胺单体在20重量%NMP溶液中、在氮气冲洗下、在搅拌下反应24小时来产生聚酰胺酸。在步骤二中,通过将聚酰胺酸溶液与β-甲吡啶和乙酸酐在环境温度(标称为25℃)下、在氮气冲洗下接触放置24小时来实现化学酰亚胺化。使所得聚酰亚胺从溶液中沉淀析出,用甲醇洗涤,并且然后在210℃、在真空下干燥24小时。
根据这种方案处理Matrimid,未使得子结构稳定化。Matrimid具有约305℃的Tg。在约300℃的空气中处理产生如下文所示的塌陷结构。
在300℃或更低或400℃或更高的温度下处理6FDA/BPDA-DAM聚酰亚胺未能使子结构稳定化。如下文所示,在300℃或更低的温度下处理由于交联不足而未产生稳定化。在400℃或更高的温度下处理产生部分塌陷的形态。人们相信通过所述方法实现的交联减少了聚合物链迁移,从而观察到纤维粘性降低。这种粘性是应避免的,因为当纤维在热解步骤期间粘在一起时,其倾向是容易在粘着点变得更脆。
上述方法制备的CMS膜应用于使仅含有H2和CH4的混合物或使除其它气体之外还含有此类气体的裂解气体混合物中的气态H2与气态乙烯(C2H4)实现分离。此类CMS膜还潜在地应用于烯烃/石蜡分离,如乙烷/乙烯分离。
相对于Matrimid和未处理(未经预氧化处理)的6FDA/BPDA-DAM聚酰亚胺膜,上述方法制备的CMS膜还展示出生产率(H2渗透性)增加。本发明CMS膜的H2渗透性在一(1)个气体渗透单位(GPU)(1×10-6立方厘米(在标准温度和压力(273.15K,100kPa)))/平方厘米-秒-厘米汞(cm3/cm2-s-cm Hg))到5000GPU(优选100GPU到1000GPU)范围内。
上述方法制备的CMS膜还具有不对称形态,如根据分离层厚度所证明,所述分离层厚度保持预氧化处理之前的不对称形态基本上不变。适用于通过上述方法制备CMS膜的热解条件包括450℃到1000℃、优选500℃到800℃并且更优选550℃到700℃范围内的温度,以及惰性气体冲洗气氛,优选氩气、氦气、氮气、二氧化碳或除氩气之外的稀有气体。热解条件还包括一(1)分钟到一百(100)小时、优选一(1)小时到八(8)小时并且更优选1小时到两(2)小时范围内的时间。
虽然6FDA与BPDA的1:1摩尔比是优选的比率,但是10:1到1:10范围内的其它比率为H2/CH4分离提供了令人满意的结果(尽管程度不同于1:1比率),以及一些其它应用。
具体实施方式
实例(Ex)1、比较例(CEx)A和CEx B
通过干喷射/湿淬灭纤维纺丝方法形成无缺陷的Matrimid、6FDA-DAM和6FDA/BPDA-DAM前驱物纤维。纤维纺丝装置和条件描述于Liren Xu等人的“混合膜蒸馏工艺中用于分离烯烃/石蜡的烯烃选择性不对称碳分子筛中空纤维膜(Olefins-selectiveasymmetric carbon molecular sieve hollow fiber membranes for hybrid membrane-distillation processes for olefin/paraffin separations)”,《膜科学杂志》(423-424(2012),第314-323页)。在那种方法中,首先将聚合物前驱物在按110℃设定点温度操作的真空烘箱中干燥整夜以除去水分和残余有机物。如下制备纺丝原液:在室温下通过将以盖密封的玻璃瓶放置在滚筒上来形成目测均相的聚合物溶液(MatrimidTM=26.2wt%聚合物、53wt%N-甲基-2-吡咯烷酮(NMP)、14.9wt%乙醇(EtOH)和5.9wt%四氢呋喃(THF);6FDA-DAM=22wt%聚合物、43wt%NMP、25wt%EtOH、10wt%THF;以及6FDA/BPDA-DAM=25wt%聚合物、43wt%NMP、22wt%EtOH、10wt%THF)。将聚合物溶液放置于500毫升(mL)注射泵中且允许其脱气整夜。利用注射泵将纺丝原液和孔液通过纺丝头共挤出而进入气隙中,通过输送泵与纤维纺丝头之间的管线内过滤构件过滤,并且然后置于水淬灭浴液中,随后经若干个TeflonTM导引件传送后使用旋转的聚乙烯卷筒卷取所得纤维。利用卷带筒收集纤维后,在48小时期间用至少四个单独的水浴液冲洗纤维,然后在金属管容器中使用三个20分钟的单独甲醇浴液,随后使用三个20分钟的单独己烷浴液使纤维发生溶剂交换。使溶剂交换纤维在真空下、在约110℃干燥约1小时。
在下表1中所示的温度下,在空气中处理无缺陷前驱物Matrimid纤维(305℃的Tg)(CEx A)、无缺陷6FDA-DAM聚酰亚胺纤维(CEx B)(395℃的Tg)和无缺陷6FDA/BPDA-DAM聚酰亚胺纤维(Ex 1)(424℃的Tg),以形成预氧化纤维。使用扫描电子显微法(SEM)检查预氧化纤维形态以确定是否存在多孔层塌陷的证据(是(Y)或否(N))且将预氧化纤维浸入热(110℃)N-甲基吡咯烷酮(NMP)中以评价其溶解性(是(Y)或否(N))。溶解性是聚合物交联的指示,溶解性降低表明聚合物交联程度出现相应的增加,且反之,溶解性增加表明聚合物交联程度出现相应的降低。结果显示于下表1中。
表1处理温度对预氧化的影响
表1中的数据表明,6FDA/BPDA-DAM纤维在空气中、在350℃预氧化一小时提供了足够的交联,使得此类纤维不溶于热NMP中,同时避免了多孔层致密化(也称为“多孔子结构塌陷”)。在空气中、在300℃预氧化一小时未能提供足够的交联,如根据预氧化纤维的溶解性所证明。6FDA/BPDA-DAM纤维在空气中、在400℃预氧化一小时导致了多孔子结构塌陷。换句话说,当6FDA/BPDA-DAM纤维在空气中预氧化一小时时,预氧化发生的温度必须大于300℃,但小于400℃。为了对比,在300℃到400℃范围内的任何温度下,Matrimid纤维(CEx A,其中子结构在所有温度下均发生塌陷)或6FDA-DAM纤维(CEx B,其中其变得不可溶或无子结构塌陷,而非两者)在空气中预氧化一小时未能得到不可溶性(足够交联)与结构稳定性(未发生多孔子结构塌陷)。
利用Ex 1的预氧化6FDA/BPDA-DAM纤维以及未经预氧化处理的6FDA/BPDA-DAM纤维制备膜。使所述膜经历如下表2中所示的热解条件且评价热解膜的纯氢气渗透性((PH2/l)于GPU中)和选择性(氢气相对于乙烷的渗透性((PH2/l)/(PC2H4/l))。
评价热解膜的纯气体渗透特性时,将膜装入中空纤维膜测试模块中。在恒定压力气体渗透系统(氩气吹扫)中,通过将膜上游一侧暴露于66.7磅/平方英寸绝对压力(psia)(459,880帕斯卡),同时使下游一侧压力从16.7psia(115,142帕斯卡)开始来收集纯氢气和乙烷渗透数据。利用流量计测量渗透物和吹扫气混合物的流速且利用气相色谱仪(GC)测量组成。利用流速和组成计算气体渗透性和选择性。
两种特性可以用于评价膜材料的分离性能:其“渗透性”(膜固有生产率的量度);以及其“选择性”(膜分离效率的量度)。典型地用巴若(Barrer)确定“渗透性”(1巴若=10-10[cm3(STP)cm]/[cm2s cmHg]),其计算是将通量(ni)除以膜上游与下游之间的分压差(Δpi),且乘以膜厚度(l)。
另一术语“渗透性”在本文中定义为不对称中空纤维膜的生产率。其典型地是用GPU量度且通过将渗透性除以有效膜分离层厚度来测定。
最后,“选择性”在本文中定义为一种气体渗透通过膜的能力或相对于另一种气体的相同特性来说的渗透性。其是作为无单位比值来量度。
表2由6FDA/BPDA-DAM和预氧化6FDA/BPDA-DAM制备的CMS膜的输送特性
表2中的数据表明,预氧化6FDA/BPDA-DAM纤维产生的CMS纤维膜的H2/CH4分离性能优于由未经预氧化处理的6FDA/BPDA-DAM纤维制成的膜。
Claims (10)
1.一种由聚酰亚胺制备用于使氢气与乙烯彼此分离的碳分子筛膜的方法,所述方法包含如下依序步骤:a)将由聚酰亚胺纤维制成的膜与含氧气氛或气体在大于300℃到小于400℃范围内的温度下接触放置,在那种温度范围内,所述接触放置的时间是大于或等于五分钟直到200小时,以产生预氧化且预碳化的聚合物膜,所述聚合物膜不溶于热(110℃)N-甲基吡咯烷酮中且基本上不发生子结构塌陷,所述聚酰亚胺选自由以下组成的群组:((5,5'-[2,2,2-三氟-1-(三氟甲基)亚乙基]双-1,3-异苯并呋喃二酮(6FDA)、3,3',4,4'-联苯四甲酸二酐(BPDA)、2,4,6-三甲基-1,3-苯二胺(DAM))(6FDA/BPDA-DAM)聚酰亚胺和i)具有至少400℃的玻璃态化温度(Tg)且ii)包括桥连苯基化合物的聚酰亚胺;以及b)使所述预氧化且预碳化的聚合物膜在冲洗气体存在下、在450℃到1000℃范围内的温度下热解,所述热解的时间在1分钟到100小时范围内,以产生碳分子筛膜,所述碳分子筛膜具有氢气渗透性和氢气/乙烯选择性大于由所述相同膜仅使用如步骤b)中的热解所制备的碳分子筛膜的氢气渗透性和氢气/乙烯选择性中的至少一种。
2.根据权利要求1所述的方法,其中所述含氧气氛或气体是选自纯氧气和空气。
3.根据权利要求1或2所述的方法,其中所述冲洗气体包含氩气或另一种惰性气体以及任选的痕量的氧气。
4.根据权利要求1或2所述的方法,其中在所述温度范围内,时间是大于或等于30分钟到两小时。
5.根据权利要求1所述的方法,其中步骤a)中的所述温度是在340℃到380℃范围内。
6.根据权利要求1或2所述的方法,其中步骤b.中的所述时间是在两小时到八小时范围内。
7.根据权利要求1或2所述的方法,其中步骤b)中的所述温度是在500℃到800℃范围内。
8.根据权利要求1或2所述的方法,其中使用步骤a)和b)制备的所述碳分子筛的氢气渗透性比仅使用步骤b)制备的所述碳分子筛的氢气渗透性大10%。
9.根据权利要求1或权利要求2中任一权利要求所述的方法,其中所述聚酰亚胺是6FDA/BPDA-DAM且6FDA和BPDA是按10:1到1:10范围内的摩尔比存在。
10.根据权利要求9所述的方法,其中所述摩尔比是1:1。
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CN106794430A8 (zh) | 2017-07-14 |
WO2016048612A1 (en) | 2016-03-31 |
ES2798126T3 (es) | 2020-12-09 |
US10150840B2 (en) | 2018-12-11 |
BR112017004963B1 (pt) | 2022-01-04 |
EP3197592A1 (en) | 2017-08-02 |
US20170247512A1 (en) | 2017-08-31 |
CN106794430B (zh) | 2020-11-06 |
BR112017004963A2 (pt) | 2018-02-20 |
EP3197592B1 (en) | 2020-05-13 |
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