CN108352493A - 由天然气制造炭黑 - Google Patents
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Abstract
在一步工艺中制造碳纳米颗粒。描述炭黑纳米颗粒的制造方法,包括将碳氢化合物添加至加热的气体从而生产具有小于1微米的体积等效球直径并且具有大于3.0nm的Lc的碳纳米颗粒。还描述包含这样的颗粒的弹性体复合物。
Description
相关申请的交叉参考
本申请要求2015年9月14日提交的美国临时申请No.62/218,137的根据35U.S.C.§119(e)的权益,其公开的内容通过引用以其整体特意地并入本文中。
技术领域
本发明通常属于的技术领域是利用电能来实现化学变化的方法和设备的技术领域。
背景技术
许多年来有很多可以使用和一直使用的工艺用来生产炭黑。许多年来用于生产该炭黑的能源已在很大程度上与用于将含有碳氢化合物的材料转化成炭黑的原材料紧密地连接。精炼残油和天然气一直是用于生产炭黑的资源。举例来说,在诸如炭黑生产等的化学工艺中,能源已经随着时间从简单的燃烧发展到油炉、发展到等离子体。如在所有的制造中,不断在寻找更有效率和更有效的方式来生产此类产品、以及新的和改善的产品。改变能源的流量和其它条件、改变原材料的流量和其它条件、增加生产的速度、增加产量、减少制造设备磨耗特性等均一直是并且继续是许多年来此寻求的一部分。
本文说明的实施方案满足了上述挑战,并且还获得了更有效率的和更有效的制造工艺。
发明内容
描述一种碳纳米颗粒,其包括具有小于1微米的体积等效球直径并且具有大于3.0纳米(nm)的Lc的碳纳米颗粒。
另外的实施方案包括:上述的碳纳米颗粒中,体积等效球直径为小于700nm;上述的碳纳米颗粒中,d002为小于0.35nm;上述的碳纳米颗粒包括类富勒烯表面结构;上述的碳纳米颗粒中,所生产的颗粒具有0.2重量%以下的氢;上述的碳纳米颗粒中,所生产的颗粒具有0.4重量%以下的氧;上述的碳纳米颗粒中,所生产的颗粒具有0.3重量%以下的硫。
还描述一种弹性体复合物,其包含配混于其中的上述的碳纳米颗粒,并且还包含硫。
另外的实施方案包括:上述的复合物中,将弹性体复合物拉伸原始长度的300%需要的应变为参考炭黑弹性体复合物的值的至少90%;上述的复合物中,0℃的tanδ为参考炭黑弹性体复合物的值的至少90%;上述的复合物中,60℃的tanδ为小于参考炭黑弹性体复合物的值的110%;上述的复合物中,60℃的tanδ为小于参考炭黑弹性体复合物的值的95%。
还描述在一步工艺中制造碳纳米颗粒的方法,其包括将碳氢化合物添加至加热的气体,从而生产具有小于1微米的体积等效球直径并且具有大于3.0nm的Lc的碳纳米颗粒。
另外的实施方案包括:上述的方法中,碳氢化合物与热气体混合,从而实现氢从碳氢化合物中的脱除;上述的方法中,碳纳米颗粒在无氧气氛中生产;上述的方法中,碳氢化合物是天然气;上述的方法中,碳纳米颗粒的产率为至少90%;上述的方法还包括热交换器、过滤器、脱气室和/或后端设备的一个或多个的使用;上述的方法中,后端设备包括造粒机、连接至造粒机的粘结剂混合罐和/或连接至造粒机的干燥器中的一个或多个。
以下进一步描述这些和另外的实施方案。
附图说明
图1示出本文描述的工艺的流程图。
图2、3和4示出用于进行本文描述的工艺的各种设备。
图5和6示出通过本文的工艺生产的碳纳米颗粒的典型的透射电子显微镜(TEM)图像。
具体实施方式
本文中示出的细节通过实施例的方式且仅是出于说明性讨论本发明的各种实施方案的目的,并且为了提供认为是本发明的原理和概念方面的最有用且容易理解的说明而提出。就这点而言,没有进行尝试显示比本发明的基本理解所必要的更详细的本发明的详情,该说明使得如何使本发明的几个形式在实践中体现对于本领域技术人员是显而易见的。
现在将通过参考更详细的实施方案来描述本发明。然而,本发明可以以不同形式来体现,而不应被解释为局限于本文中所述的实施方案。当然,提供这些实施方案,以致本公开将是全面且完整的,并且将本发明的范围完全地传达给本领域技术人员。
除非另有定义,否则本文中所使用的所有技术和科学术语具有与本发明所属的领域普通技术人员通常理解的相同的含义。本文中,本发明的说明书中所使用的术语仅是用于描述特定的实施方案,而不意欲限制本发明。如在本发明的说明书和所附权利要求书中使用的,单数形式“一(a)”、“一个(an)”和“所述(the)”意欲也包括复数形式,除非上下文中另外清楚地说明。本文中提及的所有出版物、专利申请、专利和其它参考文献通过参考将其整体明确地引入。
除非另有说明,否则说明书和权利要求书中所使用的表示成分的量和反应条件等的所有数字理解为在所有情况下通过术语“约”修改。因此,除非相反地表示,否则在以下说明书和所附权利要求书中所阐述的数值参数是可以根据寻求通过本发明获得的期望的性能而改变的近似值。至少,不试图限制等同原则在权利要求范围中的应用,各数值参数应当解释为基于有效数字的位数和普通的四舍五入法。
尽管本发明的宽泛范围所阐述的数值范围和参数是近似值,但是具体实例中阐述的数值被尽可能精确地报告。然而,任何数值固有地包含由在它们各自的试验测量中求得的标准偏差必然导致的误差。遍及本说明书给出的每个数值范围将包括落在该较宽数值范围内的每个较窄的数值范围,就如这些较窄的数值范围全都明确地写入本文中。
本发明的另外的优点将部分在以下说明中阐述一部分、且一部分将从说明中显而易见、或可以通过本发明的实践得知。应当理解的是,前述总体说明和以下详细说明两者均仅是示例性和说明性的而不是如要求保护地限制本发明。
图1示出工艺通过将碳氢化合物添加至热气体开始。图2、3和4示出将热气体与碳氢化合物前体合并的不同方法。热气体典型地为在超过2200℃的平均温度下的热气体的流。热气体典型地包括大于50体积%的氢气。
所使用的碳氢化合物原料包括在式CnHx或CnHxOy内的任意化学品,其中n为整数,x在1n和2n+2之间,并且y在0和n之间。例如,可以使用简单的碳氢化合物如甲烷、乙烷、丙烷、丁烷等。可以使用芳香族原料如苯、甲苯、甲基萘、裂解燃料油、煤焦油、煤、重油、石油(oil)、生物油(bio-oil)、生物柴油(bio-diesel)、或其它生物来源的碳氢化合物等。另外,还可以使用不饱和碳氢化合物原料,如乙烯、乙炔、丁二烯和苯乙烯等。氧化的碳氢化合物如乙醇、甲醇、丙醇、酚类、酮类、醚类、酯类,和类似的化合物也是可接受的原料。上述应当看作是可接受的碳氢化合物原料的非限制性实例,其还可与其它可接受的组分组合和/或混合。本文中的术语碳氢化合物原料的使用是指大部分原料实质上是碳氢化合物的原料。例如,天然气会是用于本文描述的工艺中的优选的碳氢化合物原料。
热也可通过来自反应器壁的潜在的辐射热来提供。这可以通过经由外部热源加热壁或者通过从热气体加热壁来发生。将热从热气体传递至碳氢化合物原料。这将在反应器或反应区(102)中在将碳氢化合物原料添加至热气体中之时即刻发生。碳氢化合物在完全转变为炭黑之前将开始裂解和分解。
本文描述的工艺基本上没有大气氧。该工艺设计成包括加热包括50体积%以上的氢气的气体,然后将该热气体添加至碳氢化合物(101)。该工艺包括加热气体、将碳氢化合物添加至热气体的一个或多个步骤,并且还可以包括热交换器(103)、过滤器(104)、脱气室(105)和后端(106)中的一个或多个的使用。后端可任选地包括造粒机、连接至造粒机的粘结剂混合罐和连接至造粒机的干燥器中的一个或多个。这些组件示意性示于图1中。除了脱气单元,可以使用用于炭黑工业的仪器的常规部件以执行这些功能,如通过例如美国专利3,981,659;3,309,780;和3,307,923证明的,其公开的内容通过引用并文本文中。在共同转让、共同待审中的美国临时专利申请序列号62/111,346—Carbon Black GeneratingSystem(炭黑生成系统)中,还描述可以使用的脱气单元,其整体通过引用并文本文中。
图2示出本文描述的典型设备的实施方案的示意性代表。将等离子体气体(201)如氧气、氮气、氩气、氦气、空气、氢气、一氧化碳、烃(例如,甲烷、乙烷)等(单独或以两种以上的混合物使用的)注入由以同轴方式位于上部室的两个电极创建的环(annulus)中。等离子体形成电极设置有内电极(202)和外电极(203),并且在两个电极之间施加充分大的电压。电极典型地由铜、钨、石墨、钼、银等制成。然后由此形成的等离子体进入反应区,在其中它与在碳氢化合物注入器(205)处进料的碳氢化合物原料反应/相互作用从而生成炭黑产物。容器壁可以耐受等离子体形成温度,石墨为结构的优选材料。而且,一个或多个碳氢化合物注入器(205)可以位于在汇聚区域(207)下方的喉部(206)或喉部(206)附近的平面上的任意位置、或在反应器的发散区域(208)中在喉部的进一步下游。碳氢化合物注入器前端同轴地设置在注入平面周围,并且作为非限制性实例,可以是至少6个注入器并且多至18个这种前端、或狭缝(slot)。
图3示出本文描述的典型设备的另一实施方案。这是利用由导电性材料、优选石墨的同轴环构成的内电极(301)和外电极(302)的反应器的二维断流器(cutout)。等离子体气体(307)可以流动通过两个电极之间的环,然后在所述环中电弧将激发气体成等离子体状态。电弧通过使用磁场控制,该磁场使电弧以圆形的方式围绕电极前端快速移动。在该实例中,在通过同轴电极的中央的碳氢化合物注入器(303)的前端(304)经由可以任选地水冷却的碳氢化合物注入器注入碳氢化合物。碳氢化合物注入器前端可以放置在电极的底平面上方的点处,或者它可以位于该平面下方、或者与该平面相同高度。任选地,存在导致反应器变窄的汇聚区域(305),然后是汇聚区域下游的发散区域(306)。
图4示出本文描述的设备的另一实施方案。通过使用三个以上的交流电极、通过使用如图2和3示出的同轴直流电极、或通过使用电阻加热器在反应器的上部生成热气体,其更详细内容可在共同转让、共同待审中的美国专利申请序列号62/209,017—HighTemperature Heat Integration Method Of MakingCarbon Black(制造炭黑的高温热集成方法)中找到,其公开的内容通过引用并文本文中。热气体(401)包括至少2400℃的至少50体积%的氢气。碳氢化合物注入器(402)可以水冷却,并且从反应器的侧部进入,然后变为相对于热气体流的轴向位置。碳氢化合物注入器前端(403)可以为一个开口或多个开口,其可以以顺时针或逆时针流动模式注入碳氢化合物,从而优化混合。任选地,存在导致反应器变窄的汇聚区域(404),然后是汇聚区域下游的发散区域(405)。
图5和6为通过上述方法生产的典型碳纳米颗粒的透射电子显微镜(TEM)图像。表面活性位点(501和601)对于这些高温技术是独特的,并且在炉法炭黑样品中未发现。仅标注一些代表性的表面活性位点。
早期,炭黑从石油和焦油经由灯法或热裂法制造。十九世纪中期,利用天然气对热的铁槽的冲击的槽法(channel process)变成制造炭黑的主要方法。在二十世纪40年代初期,炉法(furnace process)走到前列,其利用重油如热解燃料油(PFO)在贫氧燃烧环境中制造炭黑,炭黑产率为大约40-50%。
利用天然气的炭黑的等离子体类合成与炉法相比具有成本和污染均减少的两个优势。与生产每一吨炭黑就要排放多吨CO2和几十公斤NOx和SOx的炉法相比,该方法清洁、排放几乎为零的局部CO2(local CO2)和为零的SOx。尽管等离子体技术在整个上世纪已经尝试了很多次,但是仍没有基于此方法的长期可行的商业生产企业。
如本文描述的一步工艺包含反应物和产物,直到完成脱气步骤以去除从例如甲烷的裂解产生的氢气。氢气是高度可燃的气体,必须与如此生产的碳纳米颗粒分离,以便操控碳纳米颗粒。如果氢气水平已经减少至小于20体积%,则认为脱气完成。
对于本文所述的实例而言,无氧气氛认为是具有小于5体积%氧气。优选地,无氧气氛为小于3%或小于1%的氧气。
过去,等离子体发生器设计由于诸如它们的基本组件的不足的单位功率和当暴露于氢等离子体时这些组件的腐蚀等事项,不能满足生产炭黑的电力、耐腐蚀性和连续的操作要求,在其它事项中,还导致损失的反应器时间,增加的资本成本,和不经济地生产的炭黑。对于快速加热碳氢化合物以形成碳纳米颗粒和氢气的方法的更详细内容,请参见以下共同转让、共同待审中的美国专利申请,其公开的内容通过引用并入本文:序列号62/111,317—Carbon Black Combustible Gas Separation(炭黑可燃气体分离);序列号14/591,541—Use Of Feedstock In Carbon Black Plasma Process(炭黑等离子体工艺中的原料的使用);序列号14/601,761—Plasma Gas Throat Assembly And Method(等离子体气体喉部组件和方法);序列号14/601,793—Plasma Reactor(等离子体反应器);序列号62/198,431—DC Plasma Torch Electrical Power Design Method And Apparatus(直流等离子体炬电源设计方法和设备);序列号14/591,528—Integration Of Plasma AndHydrogen Process With Combined Cycle Power Plant,Simple Cycle Power Plant,AndSteam Reformer(等离子体和氢气工艺与联合循环发电厂、简单循环发电厂和蒸汽重整器的集成);序列号62/202,498—Method Of Making Carbon Black(炭黑的制造方法);序列号14/610,299—Plasma Torch Design(等离子体炬设计);序列号14/591,476—SystemFor High Temperature Chemical Processing(高温化学处理用系统);序列号62/198,486—Method Of Making Carbon Black Including Thermal Transfer Gas(包括传热气体的炭黑制造方法);序列号62/111,341—Regenerative Cooling Method And Apparatus(再生冷却方法和设备)。
另外,一直没有以等离子体生产的碳纳米颗粒的满意的橡胶性能结果。当配混进橡胶中时,等离子体类碳纳米颗粒当与炉法类炭黑相比时其性能不合标准。这是一直没有采用和大量生产等离子体生产的碳纳米颗粒的部分原因。本文描述的工艺和系统可以成功地生成可增强弹性体配混物的有品质的碳纳米颗粒。
如本文定义的弹性体是指涉及具有粘性和弹性二者或具有粘弹性的天然橡胶的一类聚合物。一些弹性体实例是天然橡胶(NR)、丁苯橡胶(SBR)、聚丁二烯、聚异丁烯、聚异戊二烯、丁腈橡胶、乙丙橡胶(EPM)、三元乙丙橡胶(EPDM)、硅橡胶、氟弹性体,以及其它类别,其可以在“The Science and Technology of Rubber”(Mark,Erman,and Roland,第四版,Academic Press,)中找到。
弹性体的增强定义为拉伸强度、耐撕裂性、耐磨耗性和模量的增加,以增加超过从简单的颗粒-基体理论预期的值。换言之,其为炭黑或一些其它碳纳米颗粒的碳纳米颗粒能够使胶质的弹性体变硬,以致它可以在诸如轮胎、门封、橡胶软管等应用中更为有用。
碳纳米颗粒是具有90%以上的碳的任意的颗粒,具有大于5m2/g(平方米每克)的表面积,并且体积等效球具有小于1微米的直径(每个颗粒的液体排量相当于1微米以下的球)。它可包括许多不同的形状,作为非限制性实例,包括盘形、碗形、锥形、聚集的盘形、多层石墨烯(FLG)、椭圆形、聚集的椭圆形、球形和聚集的球形(例如,炭黑)。碳纳米颗粒也可包括多种的这些颗粒形状。当使用碳纳米颗粒的定义时,假设在任何给出的样品中以数量计的至少90%的颗粒落在该定义的界限内。
邻苯二甲酸二丁酯(DBP)吸收量通过测定给定质量的炭黑在达到规定的粘性的糊状物之前可以吸收的DBP的量来测量炭黑的相对结构。在任意炭黑中热裂炭黑具有最低的DBP数值(32-47ml/100g)(毫升每克),表明非常少的颗粒聚集或结构。DBP通常按照ASTMD2414-12来测量。氮吸附比表面积(N2SA)和统计厚度表面积(STSA)通过ASTM D6556-10测量。
碳纳米颗粒的结晶性可以经由X-射线晶体衍射法(XRD)测量。对于本文描述的测量具体而言,在40kV(千伏)的电压和44mA(毫安)的电流下使用CuKα射线。扫描速度从2θ等于12度到90度为1.3度/分钟。石墨的002峰使用Scherrer公式分析,从而得到本文报道的Lc(晶格常数)和d002(石墨的002峰的晶格间距)的值。简单来说,Lc值越大对应于结晶性的程度越大。晶格间距(d002)值越小对应于结晶性越高,或者类石墨晶格结构越多。0.36nm以上的较大的晶格间距(d002)是乱层碳(turbostratic carbon)的指标,所述乱层碳对于经由炉法生产的炭黑样品很普遍。元素分析经由Leco制造的装置测量,并且结果作为总样品的百分率给出。
丁苯橡胶样本根据ASTM D3191来制备。ASTM D412和ASTM D2240用于测量拉伸性能和肖氏A硬度。Tanδ使用TA Instruments RSA G2装置以4℃/分钟的加热速率在-100℃~100℃的温度范围内、0.5%的应变和10Hz的频率下测量。
表1.样品的物理特性
表2.弹性体复合物性能值
名称 | 300%(psi) | 拉伸强度(psi) | 断裂伸长率(%) | 肖氏硬度计硬度 |
N234 | 3265 | 3507 | 326 | 75 |
N234@1200℃ | 1235 | 3036 | 589 | 68 |
N762 | 1527 | 2870 | 496 | 63 |
M762 | 1547 | 2609 | 437 | 64 |
N550 | 2101 | 3161 | 450 | 58 |
M550 | 2136 | 3033 | 401 | 58 |
表3.弹性体复合物的Tanδ值
Tanδ | Tanδ | Tanδ | |
样品 | 60℃ | 40℃ | 0℃ |
N762 | 0.1197 | 0.1329 | 0.1745 |
M762 | 0.1106 | 0.1226 | 0.1747 |
N550 | 0.1416 | 0.1553 | 0.2028 |
M550 | 0.1325 | 0.1456 | 0.1995 |
得到N234、N550和N762炭黑竞争者级别的样品。这些样品用重油经由炉法制造。将N234在1200℃的惰性气氛下热处理,并且在表中标记为“N234@1200℃”。M550和M762是给予如本文描述的经由混合热气体与天然气而制造的巨石(Monolith)的碳纳米颗粒的命名。
实施例1:M762的制造
使用与图3中示出的类似的装置制造样品,其中将碳氢化合物注入器插入两个同轴电极的中央。注入器前端在电极平面上方14英寸,并且电极在650kW下操作。等离子体温度为2900℃,并且完全混合的反应温度为2100℃。电极之间的环中的氢气流速为90Nm3/hr(标准立方米/小时),在电极外部周围的屏蔽气流量(shield flow)为242Nm3/小时。天然气以88kg/小时的速率注入。基于甲烷转化率的碳纳米颗粒的产率为大于95%。
实施例2:M550的制造
使用与图3中示出的类似的装置制造样品,其中将碳氢化合物注入器插入两个同轴电极的中央。注入器前端在电极平面上方14英寸,并且电极在850kW下操作。等离子体温度为2900℃,并且完全混合的反应温度为2100℃。电极之间的环中的氢气流速为235Nm3/hr(标准立方米/小时),在电极外部周围的屏蔽气流量为192Nm3/小时。天然气以103kg/小时的速率注入。基于甲烷转化率的碳纳米颗粒的产率为大于94%。
如目前通过炉法制造的通常的炭黑在世界范围内以非常相似的方式制造。氢含量、氧含量、硫含量和结晶性的变化在不同的工厂和不同的制造商之间是非常小的。级别由N2SA值和DBP值确定。可以确定由于表面活性或结晶性的差异导致的仅非常小的差异,因为全部的炉黑在这些特性方面非常类似。参考炭黑为炉法制造的炭黑材料,其N2SA和DBP的值在通过本文描述的工艺生产的碳纳米颗粒的20%内。表1中,可以发现参考炉法炭黑的具体值(以前缀“N”标注),并且与以前缀“M”标注的试验级别进行对比。
如可以从表1和2中的实例看到的,结晶性和表面活性的重要性是最高的。通过将N234热处理至仅1200℃,炭黑的增强能力已完全消失。氢含量较低并且结晶性较高。根据各种文献来源(例如,上述引用的“The Science and Technology of Rubber”和“CarbonBlack Elastomer Interaction”,Rubber Chemistry and Technology,1991,第19-39页—其公开的内容都通过引用并入文本中),这两个因素都指向炭黑作为增强剂的更低的性能。
具体地,300%的模量从3265psi下降至1235psi(磅每平方英寸)。断裂伸长率从326%增加至589%,表明具有热处理的N234的橡胶复合物试验样本表现几乎与没有炭黑填料存在时一样。该样本不是坚硬的,并且在拉伸能力和牵拉样本至3倍原始长度需要的力方面表现为生胶胶料(raw rubber gum)将会表现的一样。增加的结晶性、降低的d002、减少的氢含量全都指向更不活性的表面,即便N2SA和DBP几乎未改变。该复合物还通常含有约0.5重量%~约4重量%的硫。
对于巨石的样品,即使结晶性超过炉黑对应物的2倍,氢含量仍为炉黑对应物的三分之一,并且具有少大于10倍的硫存在,但是样品相当良好地使橡胶增强。
这是出乎意料的结果,与炭黑增强科学中目前的想法背道而驰。这些有力结果的一个可能性是在以本文描述的工艺生产的炭黑中“类富勒烯”部分的存在。这些种类的表面活性物种(surface active species)在图5和6中观察到。对于关于类富勒烯部分的更多信息,请参见“The Impact of a Fullerene-Like Concept in Carbon Black Science”,Carbon,2002,第157-162页,其公开的内容通过引用并入本文中。在该文章中,提出了将已经制造的炭黑用等离子体气体辐射,然而,直到现在,还认为类富勒烯部分(图5和6中称为“表面活性位点”(501和601))可以从碳氢化合物前体以一步制造是不可能的。
增加0℃下的tanδ与改进的湿路面抓地性相关,而降低60℃下的tanδ与改进的滚动阻力相关。通常,在一个温度下优化tanδ的常规的胎面橡胶配混物,在另一个温度下则负面影响tanδ。因此,出乎意料的是,当与参考炉法炭黑相比时,M550和M762(上述在表3中给出的)对于tanδ显示0℃下相同的性能和60℃下改进的性能。这应当对应于轮胎胎面级别的炭黑中更好的滚动阻力,同时保持湿路面抓地性能。
因此,本发明的范围应当包括可能落在所附权利要求的范围内的所有修改和变化。通过考虑本文公开的本发明的说明书和实践,本发明的其它实施方案对于本领域技术人员将是显而易见的。意图在于说明书和实施例被认为仅是示例性的,本发明的真实范围和实质由所附权利要求书表明。
Claims (19)
1.一种碳纳米颗粒,其具有小于1微米的体积等效球直径并且具有大于3.0纳米(nm)的Lc。
2.根据权利要求1所述的碳纳米颗粒,其中所述体积等效球直径为小于700nm。
3.根据权利要求1所述的碳纳米颗粒,其中d002为小于0.35nm。
4.根据权利要求1所述的碳纳米颗粒,其包括类富勒烯表面结构。
5.根据权利要求1所述的碳纳米颗粒,其中所生产的所述颗粒具有0.2重量%以下的氢。
6.根据权利要求1所述的碳纳米颗粒,其中所生产的所述颗粒具有0.4重量%以下的氧。
7.根据权利要求1所述的碳纳米颗粒,其中所生产的所述颗粒具有0.3重量%以下的硫。
8.一种弹性体复合物,其包含配混于其中的根据权利要求1所述的碳纳米颗粒并且还包含硫。
9.根据权利要求8所述的复合物,其中将所述弹性体复合物拉伸原始长度的300%需要的应变为参考炭黑弹性体复合物的值的至少90%。
10.根据权利要求8所述的复合物,其中0℃下的tanδ为参考炭黑弹性体复合物的值的至少90%。
11.根据权利要求8所述的复合物,其中60℃下的tanδ为小于参考炭黑弹性体复合物的值的110%。
12.根据权利要求8所述的复合物,其中60℃下的tanδ为小于参考炭黑弹性体复合物的值的95%。
13.一种在一步工艺中制造碳纳米颗粒的方法,其包括将碳氢化合物添加至加热的气体,从而生产具有小于1微米的体积等效球直径并且具有大于3.0nm的Lc的碳纳米颗粒。
14.根据权利要求13所述的方法,其中所述碳氢化合物与热气体混合,从而实现氢从所述碳氢化合物中的脱除。
15.根据权利要求13所述的方法,其中所述碳纳米颗粒在无氧气氛中生产。
16.根据权利要求13所述的方法,其中所述碳氢化合物是天然气。
17.根据权利要求13所述的方法,其中所述碳纳米颗粒的产率为至少90%。
18.根据权利要求13所述的方法,其还包括热交换器、过滤器、脱气室和/或后端设备的一个或多个的使用。
19.根据权利要求18所述的方法,其中所述后端设备包括造粒机、连接至所述造粒机的粘结剂混合罐和/或连接至所述造粒机的干燥器中的一个或多个。
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JP2018534221A (ja) | 2018-11-22 |
WO2017048621A1 (en) | 2017-03-23 |
CA3034212C (en) | 2023-08-01 |
KR20180094843A (ko) | 2018-08-24 |
CA3034212A1 (en) | 2017-03-23 |
JP6974307B2 (ja) | 2021-12-01 |
US10808097B2 (en) | 2020-10-20 |
EP3350855A1 (en) | 2018-07-25 |
CN108352493B (zh) | 2022-03-08 |
EP3350855A4 (en) | 2019-08-07 |
US20170073522A1 (en) | 2017-03-16 |
MX2018003122A (es) | 2018-06-19 |
KR102385213B1 (ko) | 2022-04-08 |
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