CN102295284B - 将碳转化为碳的氧化物的方法和烃类裂解的方法及装置 - Google Patents
将碳转化为碳的氧化物的方法和烃类裂解的方法及装置 Download PDFInfo
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Abstract
本发明涉及一种将碳转化为碳的氧化物的方法,其包括:在有分子式为(Na2O)xNa2[Al2Si2O8](其中0<x≤1)的类三斜霞石物质存在的情况下使碳和水蒸气接触。本发明也涉及烃类裂解的方法及装置。
Description
技术领域
本发明涉及一种碳转化方法和烃裂解方法及装置。具体而言,本发明涉及将碳转化为碳的氧化物的方法以及不希望焦炭沉积的烃类裂解的方法及装置。
背景技术
在石化工业,如乙烷、丙烷、丁烷、庚烷、液化石油气、石脑油和柴油等烃类在水蒸汽重量百分比为约30%到约70%,温度约为700℃到870℃时于反应装置中裂解以制取如乙烯和丙烯等低碳烯烃。诸如原油经过常压或减压分馏获得的底层物质等烃类有时也在反应装置中裂解,反应温度为约480℃到约600℃,蒸汽重量百分比为约1%到约2%。
在烃类裂解过程中,通常会在反应装置各部件的接触表面,如裂解炉管的内表面,发生含碳物质的堆积。辐射管内表面逐渐覆盖了一层炭,导致辐射管金属温度升高,并提高了经过辐射炉管后温度的下降幅度。此外,积炭还会破坏机械性能,例如造成应力断裂、热疲劳、软化,从而对如辐射管等反应装置部件的物理特性产生不利影响。
为去除反应装置部件上的积炭,反应装置必须定期关闭。通常的去炭作业为使积炭在高达1000℃的水蒸汽和空气混合物中燃烧。根据运行模式、涉及的烃的种类的不同,此种作业须每10到80日进行一次,并且由于作业时烃类的进料必须停止,将导致产量损失。
为了克服反应装置部件(例如炉管的内表面)上焦炭堆积的缺陷,人们考虑了各种各样的方法。这些方法包括:例如催化气化焦炭,使其产生碳的氧化物(CO/CO2)和氢气。但是,至今人们仍在寻找一种有效的使焦炭气化的方法,即将碳转化为碳的氧化物(CO/CO2)的方法。
因此,有必要提供一种可以有效将碳转化为碳的氧化物的方法以及一种减少或消除焦炭沉积的烃类裂解的方法和装置。
三斜霞石是Na[AlSiO4]-霞石在高温下的形态,可以通过将Na[AlSiO4]-霞石从超过1530K(约1256.85℃)时退火并随后淬火至室温来制备。在一篇发表在JOURNALOF SOLID STATE CHEMISTRY《固体化学杂志》61,40-46(1986)上的题为Interstitial Cristobalite-type Compounds(Na2O)≤0.33Na[AlSiO4]《间质性方石英型化合物(Na2O)≤0.33Na[AlSiO4]》的文章中曾经提到在Na[AlSiO4]-三斜霞石中嵌入氧化钠以获得(Na2O)≤0.33Na[AlSiO4]。Na8Al4Si4O18也在Beitrage zur Beaktionsfahigkeit der silicate bei niedrigentemperaturen,II.Mitteilung.,Die Strukturen Na2O-reicher carnegieite.,VonWerner Borchert und Jurgen Keidel,Heidelberg,Mit 6 Textabbildungen,(Eingegangen am 17,Marz 1947)中被提及。但是,似乎没有(即使有也相当的少的)关于如何使用这种Na2O-嵌入或富有的类三斜霞石物质的报道。
发明内容
本发明的目的是提供一种有效将碳转化为碳的氧化物的方法,以及一种减少或消除焦炭沉积的烃类裂解的方法和装置。
本发明涉及的将碳转化为碳的氧化物的方法包括:在有分子式为(Na2O)xNa2[Al2Si2O8](其中0<x≤1)的类三斜霞石物质存在的情况下使碳和水蒸汽接触。
本发明涉及的烃类裂解的方法包括:使至少一种烃类在反应装置中与水蒸汽接触,该反应装置有可被所述至少一种烃类接触的接触表面,该接触表面含有分子式为(Na2O)xNa2[Al2Si2O8](其中0<x≤1)的类三斜霞石物质。
本发明涉及的烃类裂解的装置,其有可被至少一种烃类接触的接触表面,所述接触表面含有分子式为(Na2O)xNa2[Al2Si2O8](其中0<x≤1)的类三斜霞石物质。
附图说明
通过结合附图对于本发明的实施例进行描述,可以更好地理解本发明,在附图中:
图1所示为在不同温度下,样本1和样本2暴露于氦-水蒸汽混合物后,与暴露前的样本1和样本2相比炭黑重量减少的百分比。
图2所示为在不同温度下,样本1和样本2暴露于氦-水蒸汽混合物后产生的二氧化碳浓度。
具体实施方式
本发明涉及一种将碳转化为碳的氧化物的方法,其包括:在有分子式为(Na2O)xNa2[Al2Si2O8](其中0<x≤1)的类三斜霞石物质存在的情况下使碳和水蒸汽接触。
在一些实施例中,所述接触在约400℃到约1000℃之间发生,或者约450℃到约950℃之间,或者约500℃到约950℃之间,或者约750℃到约950℃之间。碳的氧化物包括二氧化碳和/或一氧化碳。
本发明涉及一种烃类裂解的方法,包括:使至少一种烃类在反应装置中与水蒸汽接触,该反应装置有可被所述至少一种烃类接触的接触表面,该接触表面含有分子式为(Na2O)xNa2[Al2Si2O8](其中0<x≤1)的类三斜霞石物质。
在一些实施例中,所述至少一种烃类在反应装置中与水蒸汽的接触在约500℃到约870℃之间发生,或者在约800℃到约860℃之间发生。上述至少一种烃类包括乙烷、丙烷、丁烷、庚烷、液化石油气、石脑油和柴油中的至少一种。
本发明涉及一种烃类裂解装置,其有可被至少一种烃类接触的接触表面,所述接触表面含有分子式为(Na2O)xNa2[Al2Si2O8](其中0<x≤1)的类三斜霞石物质。
在一些实施例中,所述类三斜霞石材料涂覆在接触表面上。
在一些实施例中,所述接触表面包含类三斜霞石Na4Al2Si2O9涂层。
类三斜霞石涂层可以采用不同方法涂在反应装置接触烃类的表面,从而存在于接触烃类的表面涂层中,涂覆方法包括空气等离子喷涂、浆料涂层、溶胶凝胶涂层以及浸液涂层。在一些实施例中,类三斜霞石材料使用浆料涂层的方法涂覆。
该装置可以是任何可用于烃类裂解的装置。在一些实施例中,该装置包含裂解炉管、管路接头、反应容器和辐射管中至少一个。
在一些实施例中,类三斜霞石物质的分子式为Na4Al2Si2O9。
在一些实施例中,类三斜霞石物质为分子式为(Na2O)xNa2[Al2Si2O8]的物质的混合物。
本发明所称“装置或反应装置”包括但不限于石化流程中使用的裂解炉管、管路接头、反应容器和辐射管中至少一个。
本发明所称“烃类裂解”包括但不限于如乙烷、丙烷、丁烷、庚烷、液化石油气、石脑油和柴油等烃类在水蒸汽重量百分比为约30%到约70%,温度为约700℃到约870℃时于反应装置中裂解以制取如乙烯和丙烯等低碳烯烃。诸如原油经过常压或减压分馏获得的底层物质等烃类有时也在反应装置中裂解,反应温度为约480℃到约600℃,水蒸汽重量百分比为约1%到约2%。
本发明所称“焦炭或炭”包括但不限于来自煤、石油、木材、烃及其他含碳物质的含碳固体或液体或者形成含碳固体或液体的微粒或高分子,例如,烃类裂解炉里存在的炭黑、焦油及热解碳。
本发明中所提及的数值包括从低到高一个单元一个单元增加的所有数值,此处假设任何较低值与较高值之间间隔至少两个单元。举例来说,如果说了一个组分的数量或一个工艺参数的值,比如,温度,压力,时间等等,是从1到90,20到80较佳,30到70最佳,是想表达15到85,22到68,43到51,30到32等数值都已经明白的列举在此说明书中。对于小于1的数值,0.0001,0.001,0.01或者0.1被认为是比较适当的一个单元。前述只是想要表达的特别示例,所有在列举的最低到最高值之间的数值组合均被视为以类似方式清楚地列在本说明书中。
说明书和权利要求中的近似用语用来修饰数量,表示本发明并不限定于该具体数量,还包括与该数量接近的可接受的修正的部分,而不会导致相关基本功能的改变。相应的,用“大约”、“约”等修饰一个数值,意为本发明不限于该精确数值。在某些例子中,近似用语可能对应于测量数值的仪器的精度。
实验示例
以下实验示例可以为本领域中具有一般技能的人实施该发明提供参考。但是,这些例子并不用于限制权利要求的范围。
高岭土从美国密苏里州St Louis的Sigma-Aldrich Corp.获得,并且在使用前没有进行进一步的处理。NaNO3、Na2CO3、柠檬酸,三乙烯乙二醇和乙醇从中国上海国药集团化学试剂有限公司获得。炭黑(含碳量99.99%,ACEBlack,AB 50)从美国德克萨斯州休斯顿synthetic oil and lubricant of Texas,Inc.获得。材料组成通过波长色散X射线荧光(WD XRF)分析仪(来自日本东京Rigaku Industrial Corporation的Rigaku ZSX 100e)分析。晶体结构用X射线衍射仪(XRD)(来自德国Karlsruhe的Bruker Axs GmbH的Bruker D8 Advance)来分析。
例1
类三斜霞石物质Na4Si2Al2O9通过下述的固体反应来制备。12.9克高岭土、10.6克Na2CO3和20克乙醇混合在一起,然后以500转每分的速度球磨24个小时,使其变成糊状。
该糊状物在80℃下烘干获得粉末。该粉末在850℃下煅烧6个小时,温度上升速率为5℃/分钟。
煅烧之后,用WD XRF分析仪和XRD分析获得的粉末。如表1WD XRF分析结果所示,该物质的元素成分比例为Na∶Si∶Al=2∶1∶1。经XRD分析仪确定,所得粉末为具有Na2O-稳定(或嵌入或富有)的类高三斜霞石相的Na4Si2Al2O9。
表1
元素 | Na | Si | Al |
数量(mol) | 1.00 | 0.50±0.01 | 0.50±0.01 |
例2
例1中获得的类高三斜霞石相Na4Si2Al2O9粉末(300毫克)在玛瑙研钵中碾碎,然后与炭黑粉末(30毫克)充分混合作为样本1使用。炭黑粉末(30毫克)作为样本2使用。样本1和样本2分别被放入石英坩埚中,坩埚垂直悬挂在热重分析仪(TGA)锅炉(TG 151,来自美国加州Cerritos的CahnInstruments,Inc.的反应区域中。持续的氦气流流经700℃的预热锅炉,并将50wt%的蒸馏水蒸汽带入TGA锅炉中。TGA锅炉中的温度从25℃起以10℃/分钟的速率线性上升并保持在400℃直至水蒸汽导致的平衡紊乱消失并获得稳定的重量记录。然后,温度以5℃/分钟的速率继续升高至950℃。
获得稳定的重量记录后,记录不同温度下样本的重量,从而计算得出的升温过程中样本中炭黑重量减轻百分比如图1所示。在图1中,虚线1表示不同温度下样本1中炭黑重量减轻百分比,实线2表示不同温度下样本2中炭黑重量减轻百分比。来自于TGA锅炉的气体流经一个与冷却装置和干燥容器(装满CaCl2)相连的气室。该气室安装在一个傅立叶变换红外光谱(FT-IR)光谱仪(NicoletTM 380 FT-IR光谱仪,来自美国威斯康星州麦迪逊的ThermoElectron Scientific Instruments Corp.)中。通过FT-IR光谱仪获得的不同温度下气体中二氧化碳的浓度如图2所示。在图2中,虚线1表示不同温度下样本1产生的二氧化碳浓度,实线2表示不同温度下样本2产生的二氧化碳浓度。
如图1所示,样本1(Na4Si2Al2O9和炭黑的混合物)中炭黑重量减轻百分比随着温度上升逐渐增加,尤其是当温度范围位于约500℃到约950℃之间时。而样本2(纯炭黑)重量减少百分比始终在0附近,即,实验过程中,样本2的重量几乎没有减少。如图2所示,在温度范围为约400℃到约950℃之间时,尤其是当温度范围为约450℃到约950℃之间时,从样本1中产生的二氧化碳浓度则随温度上升而增大,而样本2产生的二氧化碳浓度始终接近于0。从图1和图2可以看出,样本1中炭黑重量减少百分比和产生的二氧化碳浓度在约750℃到约950℃之间随着温度上升而急剧增大。
本实验表明,Na2O-稳定(或嵌入或富有)类高三斜霞石相Na4Si2Al2O9可以有效催化约400℃至约950℃的温度范围内碳和水蒸汽之间的反应,从而使碳转化为碳的氧化物。
例3
用例1中获得的Na2O-稳定(或嵌入或富有)的类高三斜霞石相Na4Si2Al2O9粉末压制的两个厚度为1毫米、直径为10毫米的圆盘和一片Al2O3片(5毫米x5毫米x1毫米)作为样本,放入一个充满了庚烷和水蒸汽混合气体(重量比为1∶1)的实验室规模的裂解炉中,在800℃+/-5℃下放置8个小时。庚烷和水蒸汽混合物在裂解炉中的停留时间为1.5秒。在两个Na4Si2Al2O9圆盘的表面上没有观察到焦炭沉积,而在Al2O3片上可以观察到焦炭沉积。该实验表明,Na2O-稳定(或嵌入或富有)的类高三斜霞石相Na4Si2Al2O9可以用于不希望焦炭沉积的烃类裂解。
实验前后Na4Si2Al2O9圆盘的XRD结果表明,此物质的Na2O-稳定(或嵌入或富有)的类高三斜霞石相在实验过程中相当稳定。
例4
将一条由310S不锈钢(物质组成如表2所示)制成的、大小为10x30x1立方毫米的金属条用作基片。在涂覆之前,用下述方法将基片仔细清洁:分别在丙酮和乙醇中做超声波震荡30分钟以去除有机污染物,在盐酸(质量浓度3.3%)中做超声波震荡30分钟以侵蚀基片表面,再在去离子水中做超声波清洗,最后用压缩空气将其彻底干燥。
表2
Cr(质量%) | Ni(质量%) | Fe(质量%) | Mn(质量%) | Si(质量%) | S(质量%) | P(质量%) | Cu(质量%) | Mo(质量%) | Al(质量%) | Ti(质量%) | C(质量%) | |
310S不锈钢 | 25.6 | 18.9 | 52 | 1.6 | 0.4 | - | - | - | - | - | - | 1.5 |
将例1中获得的Na2O-稳定(或嵌入或富有)的类高三斜霞石相Na4Si2Al2O9粉末(2克)球磨成平均粒径为1.7um的粉末,并与2.5克去离子水相混合。将甘油(0.4克)加入混合物中。然后,用高速搅拌器(来自美国南卡罗来纳州Landrum的Flacktek Inc.的SpeedmixerTM DAC 150FVC)将混合物以4000转每分的转速混合1分钟,使其变成浆状。将基片浸在上述浆状物中,使基片的部分表面覆盖上浆状物。在空气中风干2个小时,然后将金属条在800℃的氩气中煅烧2个小时。XRD分析确认了金属条上覆盖的薄膜中Na4Si2Al2O9的Na2O-稳定(或嵌入或富有)的类高三斜霞石相。
例4
例3中获得的涂覆后的金属条被用来作为样本,其被放入860℃的实验室规模裂解炉中,在庚烷和水蒸汽的混合物中(重量比1∶1)放置5个小时。庚烷和水蒸汽的混合物在裂解炉中的停留时间为1.5秒。实验完成后,在Na4Si2Al2O9膜上没有观察到焦炭沉积物,用能谱仪(EDS,来自英国Oxfordshire的Oxford Instruments的Inca X-sight)进行分析,也确认Na4Si2Al2O9膜的表面上没有碳。但是,在金属条上没有涂覆Na4Si2Al2O9膜的空白部分可以观察到焦炭沉积物。本实验表明当庚烷在水蒸汽存在的情况下裂解时,Na4Si2Al2O9膜有效地消除了焦炭沉积物。
虽然结合特定的实施例对本发明进行了说明,但本领域的技术人员可以理解,对本发明可以作出许多修改和变型。因此,要认识到,权利要求书的意图在于覆盖在本发明真正构思和范围内的所有这些修改和变型。
Claims (16)
1.一种将碳转化为碳的氧化物的方法,其包括:在有分子式为(Na2O)xNa2[Al2Si2O8]的类三斜霞石物质存在的情况下使碳和水蒸汽接触,其中0<x≤1。
2.如权利要求1所述的将碳转化为碳的氧化物的方法,其特征在于:所述接触发生在约400℃到约1000℃的温度范围。
3.如权利要求1所述的将碳转化为碳的氧化物的方法,其特征在于:所述接触发生在约450℃到约950℃的温度范围。
4.如权利要求1所述的将碳转化为碳的氧化物的方法,其特征在于:所述接触发生在约500℃到约950℃的温度范围。
5.如权利要求1所述的将碳转化为碳的氧化物的方法,其特征在于:所述接触发生在约750℃到约950℃的温度范围。
6.如权利要求1至5中任一权利要求所述的将碳转化为碳的氧化物的方法,其特征在于:所述类三斜霞石物质的分子式为Na4Al2Si2O9。
7.如权利要求6所述的将碳转化为碳的氧化物的方法,其特征在于:所述碳的氧化物包括二氧化碳。
8.一种烃类裂解的方法,包括:使至少一种烃类在反应装置中与水蒸汽接触,该反应装置有可被所述至少一种烃类接触的接触表面,该接触表面含有分子式为(Na2O)xNa2[Al2Si2O8]的类三斜霞石物质,其中0<x≤1。
9.如权利要求8所述的烃类裂解的方法,其特征在于:所述类三斜霞石物质的分子式为Na4Al2Si2O9。
10.如权利要求8或9所述的烃类裂解的方法,其特征在于:所述至少一种烃类在反应装置中与水蒸汽的接触在约500℃到约870℃之间发生,所述至少一种烃类包括乙烷、丙烷、丁烷、庚烷、液化石油气、石脑油和柴油中的至少一种。
11.一种烃类裂解的装置,其有可被至少一种烃类接触的接触表面,所述接触表面含有分子式为(Na2O)xNa2[Al2Si2O8]的类三斜霞石物质,其中0<x≤1。
12.如权利要求11所述的烃类裂解的装置,其特征在于:所述类三斜霞 石物质的分子式为Na4Al2Si2O9。
13.如权利要求11或12所述的烃类裂解的装置,其特征在于:所述类三斜霞石物质涂覆在所述接触表面上。
14.如权利要求11或12所述的烃类裂解的装置,其特征在于:其包括炉管、管路接头、反应容器和辐射管中至少一个。
15.如权利要求11或12所述的烃类裂解的装置,其特征在于:所述接触表面含有类三斜霞石Na4Al2Si2O9涂层。
16.如权利要求11所述的烃类裂解的装置,其特征在于:所述类三斜霞石物质是分子式为(Na2O)xNa2[Al2Si2O8]的物质的混合物。
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JP5709992B2 (ja) | 2015-04-30 |
ES2539971T3 (es) | 2015-07-07 |
RU2012152275A (ru) | 2014-08-10 |
KR101903798B1 (ko) | 2018-10-02 |
CN102295284A (zh) | 2011-12-28 |
KR20130096225A (ko) | 2013-08-29 |
SG186394A1 (en) | 2013-01-30 |
US9708545B2 (en) | 2017-07-18 |
MX2012014826A (es) | 2013-01-29 |
CA2802677A1 (en) | 2012-01-05 |
US20170283712A1 (en) | 2017-10-05 |
CA2802677C (en) | 2018-04-03 |
US9074147B2 (en) | 2015-07-07 |
RU2573833C2 (ru) | 2016-01-27 |
US10119078B2 (en) | 2018-11-06 |
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