CN102260519A - 烃类裂解方法和反应装置 - Google Patents

烃类裂解方法和反应装置 Download PDF

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CN102260519A
CN102260519A CN2010101925124A CN201010192512A CN102260519A CN 102260519 A CN102260519 A CN 102260519A CN 2010101925124 A CN2010101925124 A CN 2010101925124A CN 201010192512 A CN201010192512 A CN 201010192512A CN 102260519 A CN102260519 A CN 102260519A
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combination
hydrocarbon cracking
reaction unit
hydro carbons
bazr
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CN102260519B (zh
Inventor
王世忠
彭文庆
傅琪佳
邓志刚
吴召平
林川
古彦飞
张晓�
L·B·库尔
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BL Technology Co., Ltd.
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General Electric Co
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Priority to CN201010192512.4A priority Critical patent/CN102260519B/zh
Priority to ES11167508.8T priority patent/ES2597580T3/es
Priority to US13/115,610 priority patent/US9499747B2/en
Priority to EP11167508.8A priority patent/EP2390302B1/en
Publication of CN102260519A publication Critical patent/CN102260519A/zh
Priority to US15/289,301 priority patent/US10138431B2/en
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    • C10G2400/20—C2-C4 olefins

Abstract

烃类裂解方法包括：提供蒸汽和烃类；将蒸汽和烃类输入接触烃类的表面含有化学式为AaBbCcDdO3-δ的钙钛矿材料的反应装置，其中0＜a＜1.2，0≤b≤1.2，0.9＜a+b≤1.2，0＜c＜1.2，0≤d≤1.2，0.9＜c+d≤1.2，-0.5＜δ＜0.5；A从钙(Ca)、锶(Sr)、钡(Ba)及其组合选取；B从锂(Li)、钠(Na)、钾(K)、铷(Rb)及其组合选取；C从铈(Ce)、锆(Zr)、锑(Sb)、镨(Pr)、钛(Ti)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、镓(Ga)、锡(Sn)、铽(Tb)及其组合选取；D从镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)、钪(Sc)、钛(Ti)、钒(V)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、锌(Zn)、钇(Y)、锆(Zr)、铌(Nb)、钼(Mo)、锝(Tc)、钌(Ru)、铑(Rh)、钯(Pd)、银(Ag)、镉(Cd)、铪(Hf)、钽(Ta)、钨(W)、铼(Re)、锇(Os)、铱(Ir)、铂(Pt)、金(Au)、镓(Ga)、铟(In)、锡(Sn)、锑(Sb)及其组合选取。

Description

烃类裂解方法和反应装置
技术领域
本发明涉及烃类裂解方法和反应装置。具体而言，本发明涉及不希望积炭的烃类裂解方法和反应装置。
背景技术
在石化工业，如乙烷、丙烷、丁烷和石脑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内表面发生含碳物质的堆积，如裂解炉管的内表面。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、涉及的烃的种类和产出的不同，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。
为克服例如裂解炉管内表面等反应装置部件上积炭的缺陷，人们考虑了各种方法。这些方法有：从冶金角度入手，提高裂解炉金属基层中铬的含量；在原料中加入诸如硫、二甲基硫(DMS)、二甲基二硫(DMDS)或硫化氢等添加剂；用蒸汽对原料提高稀释倍数，并改善过程控制；有选择地对管道内表面作预处理；惰性表面镀层；将炭催化气化，使其反应生成一氧化碳、二氧化碳和氢气。
虽然部分上述方法和系统已在石化工业中普遍应用，但是一种可以避免或弥补前述工艺之不足，并能有效减少或消除积炭的烃类裂解方法和反应装置，仍然是大家所期望的。
发明内容
本发明的目的是提供一种能有效减少或消除积炭的烃类裂解方法和反应装置。
本发明烃类裂解方法包括：提供水蒸汽和烃类；将水蒸汽和烃类输入反应装置，所述反应装置接触烃类的表面含有化学式为AaBbCcDdO3-δ的钙钛矿材料，其中0＜a＜1.2，0≤b≤1.2，0.9＜a+b≤1.2，0＜c＜1.2，0≤d≤1.2，0.9＜c+d≤1.2，-0.5＜δ＜0.5；A从钙(Ca)、锶(Sr)、钡(Ba)及其组合中选取；B从锂(Li)、钠(Na)、钾(K)、铷(Rb)及其组合中选取；C从铈(Ce)、锆(Zr)、锑(Sb)、镨(Pr)、钛(Ti)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、镓(Ga)、锡(Sn)、铽(Tb)及其组合中选取；D从镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)、钪(Sc)、钛(Ti)、钒(V)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、锌(Zn)、钇(Y)、锆(Zr)、铌(Nb)、钼(Mo)、锝(Tc)、钌(Ru)、铑(Rh)、钯(Pd)、银(Ag)、镉(Cd)、铪(Hf)、钽(Ta)、钨(W)、铼(Re)、锇(Os)、铱(Ir)、铂(Pt)、金(Au)、镓(Ga)、铟(In)、锡(Sn)、锑(Sb)及其组合中选取。
本发明烃类裂解反应装置，其接触烃类的表面含有化学式为AaBbCcDdO3-δ的钙钛矿材料，其中0＜a＜1.2，0≤b≤1.2，0.9＜a+b≤1.2，0＜c＜1.2，0≤d≤1.2，0.9＜c+d≤1.2，-0.5＜δ＜0.5；A从钙(Ca)、锶(Sr)、钡(Ba)及其组合中选取；B从锂(Li)、钠(Na)、钾(K)、铷(Rb)及其组合中选取；C从铈(Ce)、锆(Zr)、锑(Sb)、镨(Pr)、钛(Ti)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、镓(Ga)、锡(Sn)、铽(Tb)及其组合中选取；D从镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)、钪(Sc)、钛(Ti)、钒(V)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、锌(Zn)、钇(Y)、锆(Zr)、铌(Nb)、钼(Mo)、锝(Tc)、钌(Ru)、铑(Rh)、钯(Pd)、银(Ag)、镉(Cd)、铪(Hf)、钽(Ta)、钨(W)、铼(Re)、锇(Os)、铱(Ir)、铂(Pt)、金(Au)、镓(Ga)、铟(In)、锡(Sn)、锑(Sb)及其组合中选取。
附图说明
参照附图阅读下文对发明的详细说明，将会更好地理解本发明，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。
图3所示为不同温度下，样本3～13暴露于氦-水蒸汽混合物中后，与暴露前的样本3～13相比炭黑重量减少的百分比。
具体实施方式
本发明包括涉及一种烃类裂解方法，其包括：提供水蒸汽和烃类；将水蒸汽和烃类输入反应装置，所述反应装置接触烃类的表面含有化学式为AaBbCcDdO3-δ的钙钛矿材料，其中0＜a＜1.2，0≤b≤1.2，0.9＜a+b≤1.2，0＜c＜1.2，0≤d≤1.2，0.9＜c+d≤1.2，-0.5＜δ＜0.5；A从钙(Ca)、锶(Sr)、钡(Ba)及其组合中选取；B从锂(Li)、钠(Na)、钾(K)、铷(Rb)及其组合中选取；C从铈(Ce)、锆(Zr)、锑(Sb)、镨(Pr)、钛(Ti)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、镓(Ga)、锡(Sn)、铽(Tb)及其组合中选取；D从镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)、钪(Sc)、钛(Ti)、钒(V)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、锌(Zn)、钇(Y)、锆(Zr)、铌(Nb)、钼(Mo)、锝(Tc)、钌(Ru)、铑(Rh)、钯(Pd)、银(Ag)、镉(Cd)、铪(Hf)、钽(Ta)、钨(W)、铼(Re)、锇(Os)、铱(Ir)、铂(Pt)、金(Au)、镓(Ga)、铟(In)、锡(Sn)、锑(Sb)及其组合中选取。
本发明也涉及一种烃类裂解反应装置，其接触烃类的表面含有化学式为AaBbCcDdO3-δ的钙钛矿材料，其中0＜a＜1.2，0≤b≤1.2，0.9＜a+b≤1.2，0＜c＜1.2，0≤d≤1.2，0.9＜c+d≤1.2，-0.5＜δ＜0.5；A从钙(Ca)、锶(Sr)、钡(Ba)及其组合中选取；B从锂(Li)、钠(Na)、钾(K)、铷(Rb)及其组合中选取；C从铈(Ce)、锆(Zr)、锑(Sb)、镨(Pr)、钛(Ti)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、镓(Ga)、锡(Sn)、铽(Tb)及其组合中选取；D从镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)、钪(Sc)、钛(Ti)、钒(V)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、锌(Zn)、钇(Y)、锆(Zr)、铌(Nb)、钼(Mo)、锝(Tc)、钌(Ru)、铑(Rh)、钯(Pd)、银(Ag)、镉(Cd)、铪(Hf)、钽(Ta)、钨(W)、铼(Re)、锇(Os)、铱(Ir)、铂(Pt)、金(Au)、镓(Ga)、铟(In)、锡(Sn)、锑(Sb)及其组合中选取。
在一些实施例中，A从锶(Sr)和钡(Ba)中选取。C从铈(Ce)、锆(Zr)和锰(Mn)中选取。D从铈(Ce)和钇(Y)中选取。
在一些实施例中，钙钛矿材料从SrCeO3、SrZr0.3Ce0.7O3、BaMnO3、BaCeO3、BaZr0.3Ce0.7O3、BaZr0.3Ce0.5Y0.2O3、BaZr0.1Ce0.7Y0.2O3、BaZrO3、BaZr0.7Ce0.3O3、BaCe0.5Zr0.5O3、BaCe0.9Y0.1O3、BaCe0.85Y0.15O3和BaCe0.8Y0.2O3中选取。例如，对于SrCeO3，A为Sr，C为Ce，a＝1，b＝0，c＝1，d＝0，δ＝0。对于SrZr0.3Ce0.7O3，A为Sr，C为Zr，D为Ce，a＝1，b＝0，c＝0.3，d＝0.7，δ＝0。对于BaMnO3，A为Ba，C为Mn，a＝1，b＝0，c＝1，d＝0，δ＝0。对于BaCeO3，A为Ba，C为Ce，a＝1，b＝0，c＝1，d＝0，δ＝0。对于BaZr0.3Ce0.7O3，A为Ba，C为Zr，D为Ce，a＝1，b＝0，c＝0.3，d＝0.7，δ＝0。对于BaZr0.3Ce0.5Y0.2O3，A为Ba，C为Zr，D为Ce和Y的组合，a＝1，b＝0，c＝0.3，d＝0.7，δ＝0。鉴于该领域一般技术人员通过上述例子已经可以理解，此处不再更多举例，以免不必要的繁琐细节使得本发明难以理解。
在一些实施例中，本发明涉及的方法在约700℃到约870℃的温度范围内进行，水蒸汽和烃类的质量比约在3∶7到7∶3之间，烃类则包含乙烷、庚烷、液化石油气、石脑油、石油和天然气中的至少一种。
在一些实施例中，本发明涉及的方法在约480℃到约600℃的温度范围内运行，其中的烃类包含原油经过常压或减压分馏获得的底层物质等，且水蒸汽占水蒸汽和烃类总重量的百分比在约1％到约2％之间。
在一些实施例中，钙钛矿材料为SrZr0.3Ce0.7O3。
在一些实施例中，钙钛矿材料为BaZr0.3Ce0.7O3。
在一些实施例中，钙钛矿材料为BaZr0.1Ce0.7Y0.2O3。
在一些实施例中，钙钛矿材料为BaCe0.8Y0.2O3。
钙钛矿材料可以采用不同方法喷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，喷涂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，钙钛矿材料的喷涂采用空气等离子喷涂法进行。
本发明所涉及的反应装置可以是任何可用于裂解烃类的反应装置。在一些实施例中，该反应装置包含裂解炉管、管路接头、反应容器和辐射管中至少一个。
定义
本发明所称“反应装置”是指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、丁烷和石脑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“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”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。
除非特别说明，裂解实验在实验室规模的烃类裂解炉中进行。由于庚烷与石脑油结构近似，因此选用了庚烷作为烃类来源。
裂解实验中，将样本放在石英进样管支架上后置于裂解炉中的恒温部分。然后将炉门关闭。以100标准立方厘米每分钟(sccm)的流速将氩气注入裂解炉中。以20℃每分钟的变温速率将裂解炉加热至880℃。加热汽化器30分钟至350℃。
当裂解炉温度达到880℃，并且汽化器温度达到350℃时，用活塞泵将水以1.58毫升每分钟的流速输入汽化器，并且停止注入氩气。5分钟后，用活塞泵将庚烷以2.32毫升每分钟的流速输入汽化器使之汽化，并使之在汽化器中以1∶1的质量比与水蒸汽混合后进入裂解炉。在停止输入庚烷和水以前，始终保持裂解炉具有期望的温度，如800+/-5℃或860+/-5℃。除非另有说明，庚烷和水蒸汽在裂解炉中的停留时间为1.5秒。停止输入庚烷和水后，裂解炉和汽化器关闭前，再次以100sccm的流速注入氩气。裂解炉冷却后，停止注入氩气，打开裂解炉的炉门，并取出样本。
对比示例
此处采用310S不锈钢、耐热镍铬铁合金800HT、耐热镍铬铁合金825、Al2O3、SiNx、SiC和SiO2等制成的6x6x1立方毫米的方形片体作为样本。310S不锈钢、耐热镍铬铁合金800HT、耐热镍铬铁合金825等合金片体中各成分质量百分比如表1所示。每个片体在800℃烃类裂解实验前、后的质量用电子天平称量，计算得出积炭的质量。如表2所示，片体上积炭的质量随片体在裂解反应环境下所处的时间变化而改变。
表1
  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
  耐热镍铬铁合金800HT 20.62 30.76 45.57 0.89 0.65 0.005 - 0.29 - 0.57 0.56 0.082
  耐热镍铬铁合金800HT 20.80 41.07 31.22 0.51 0.32 0.003 0.02 2.02 2.95 0.20 0.89 0.015
表2
时间(小时)   310S不锈钢(克)   耐热镍铬铁合金800HT(克)   耐热镍铬铁合金800HT(克) Al2O3(克) SiNx(克) SiC(克) SiO2(克)
  0   0.00   0.00   0.00   0.00   0.00   0.00   0.00
  2   0.23   0.35   0.29
  2.5   0.17   0.18   0.16   0.17
  4   0.38   0.50   0.45
  4.5   0.31   0.34   0.30   0.29
  6   0.59   0.74   0.80
  8   0.81   0.98   0.75   0.56   0.58   0.62
  10   0.90   1.05   0.97   0.65   0.77   0.70
例1
钙钛矿材料通过固相反应法制备。以BaZr0.3Ce0.5Y0.2O3为例，在乙醇中混合高纯度碳酸钡、氧化锆、氧化铈和氧化钇粉末(均来自中国上海国药集团化学试剂有限公司)，并球磨12小时。然后将制得的混合物在1100℃下空气中烘干并煅烧6小时，从而制得钙钛矿BaZr0.3Ce0.5Y0.2O3粉末。该粉末在274.6Mpa压强下等静压成型10分钟，制成一个圆盘。该圆盘在1400℃下空气中烧结6小时。打磨烧结后的圆盘，使其厚度为1毫米。该钙钛矿材料经X射线衍射仪(D8Advance，BrukerAXS GmbH，Karlsruhe，德国)确定，形态无误。
例2
将分别由BaCO3、BaTiO3、CeO2和BaCO3的混合物及Al2O3制成、厚度为1毫米、直径为10毫米的圆盘作为样本，在800℃于前述裂解炉中质量比为1∶1的庚烷和水蒸汽混合物环境里放置2小时。在由BaCO3制成的圆盘表面发现少量炭，在分别由BaTiO3和Al2O3制成的圆盘上出现的积炭则相对更多，在由CeO2和BaCO3混合物制成的圆盘上没有发现炭沉积物。XRD分析显示CeO2和BaCO3混合物在实验过程中形成了钙钛矿材料BaCeO3。
例3
将分别由SrCeO3、SrZr0.7Ce0.7O3、BaMnO3、BaCeO3、BaZr0.3Ce0.7O3和Al2O3制成、厚度为1毫米、直径为10毫米的圆盘作为样本，在800℃+/-5℃下于前述裂解炉中质量比为1∶1的庚烷和水蒸汽混合物环境里放置2小时。在分别由SrCeO3、SrZr0.7Ce0.7O3、BaMnO3、BaCeO3、BaZr0.3Ce0.7O3制成的圆盘上，没有发现积炭，但在以Al2O3制成的圆盘上可以观察到积炭。
BaZr0.3Ce0.7O3圆盘在实验前后的X光衍射(XRD)分析结果表明，该材料在实验中相当稳定。
例4
将一条由310S不锈钢制成的、大小为10x30x1立方毫米的金属条用作基片。在喷涂之前，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。采用球磨和颗粒化方法，制得平均直径为20微米的BaZr0.1Ce0.7Y0.2O3粉末，将粉末加入空气等离子喷涂系统，在彻底清洁后的310S基片上喷涂BaZr0.1Ce0.7Y0.2O3涂层。涂层中的BaCe0.7Zr0.1Y0.2O3钙钛矿形态用XRD分析得到确认。
例5
将例4中所制得的有涂层的合金金属条作为样本，在860℃下于裂解炉中放置8小时，裂解炉中庚烷和水蒸汽质量比为1∶1。结果BaZr0.1Ce0.7Y0.2O3涂层上并未发现炭。能谱仪(EDS)分析也确定BaZr0.1Ce0.7Y0.2O3涂层的表面不存在炭。然而，合金基片上未涂有BaZr0.1Ce0.7Y0.2O3的空白部分发现存在炭。该实验表明BaZr0.1Ce0.7Y0.2O3涂层可有效防止烃类裂解过程中的炭沉积。
例6
用热重量分析仪(TG 151，Cahn Instruments，Inc.，Cerritos，美国加利福尼亚州)在氦-水蒸汽混合物(氦与水蒸气体积比为50∶50)中对样本1(炭黑粉末和BaZr0.3Ce0.7O3粉末混合物，二者质量比为1∶10，总质量330mg)和样本2(炭黑粉末，30mg)进行测试。热重量分析仪的加热速率为5℃每分钟，温度范围为400℃到950℃。在不同温度下测量样本质量。由此计算出样本中炭黑重量减轻的百分比如图1所示。用NicoletTM 380 FT-IR光谱仪(美国威斯康辛州Madison，Thermo Electron Scientific Instruments Corp.)分析不同温度下样本所产生的二氧化碳的浓度。不同温度下二氧化碳的浓度如图2所示。图1和图2中的曲线1和2分别对应样本1和2。
如图1所示，样本1中所消耗炭黑的量比样本2中的多，尤其当温度在800℃左右或高于800℃时更是如此。如图2所示，样本1所产生的二氧化碳比样本2中的多。该实验表明，在400℃到950℃温度范围内，如欲防止/减少炭的生成或存在，可采用BaZr0.3Ce0.7O3。
例7
用热重量分析仪在氦-水蒸汽混合物(氦与水蒸气体积比为50∶50)中测试样本3～13。样本3～5和样本7-13分别是炭黑分别和BaZr0.3Ce0.7O3、BaCeO3、BaCe0.5Zr0.5O3、BaZr0.7Ce0.3O3、BaZrO3、BaZr0.1Ce0.7Y0.2O3、BaCe0.85Y0.15O3、BaCO3、BaCe0.9Y0.1O3和BaCe0.8Y0.2O3的粉末混合物(质量比为1∶10，总质量分别为330mg)。样本6为炭黑粉末(30mg)。热重量分析仪的加热速率为5℃每分钟，并且温度范围为约400℃到约950℃。通过计算得出样本中炭黑重量减少的百分比，如图3所示。图3中的曲线3至13分别对应样本3至13。
如图3所示，样本3～5和样本7～13中所消耗炭黑的量比样本6中的多，尤其当温度在785℃左右或高于785℃时更是如此。本实验表明，在400℃到950℃温度范围内，如欲防止/减少炭的生成或存在，可采用BaZr0.3Ce0.7O3、BaCeO3、BaCe0.5Zr0.5O3、BaZr0.7Ce0.3O3、BaZrO3、BaZr0.1Ce0.7Y0.2O3、BaCe0.85Y0.15O3、BaCO3、BaCe0.9Y0.1O3和BaCe0.8Y0.2O3。
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 (11)

1.一种烃类裂解方法，包括：提供水蒸汽和烃类；将水蒸汽和烃类输入反应装置，所述反应装置接触烃类的表面含有化学式为AaBbCcDdO3-δ的钙钛矿材料，其中0＜a＜1.2，0≤b≤1.2，0.9＜a+b≤1.2，0＜c＜1.2，0≤d≤1.2，0.9＜c+d≤1.2，-0.5＜δ＜0.5；A从钙(Ca)、锶(Sr)、钡(Ba)及其组合中选取；B从锂(Li)、钠(Na)、钾(K)、铷(Rb)及其组合中选取；C从铈(Ce)、锆(Zr)、锑(Sb)、镨(Pr)、钛(Ti)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、镓(Ga)、锡(Sn)、铽(Tb)及其组合中选取；D从镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)、钪(Sc)、钛(Ti)、钒(V)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、锌(Zn)、钇(Y)、锆(Zr)、铌(Nb)、钼(Mo)、锝(Tc)、钌(Ru)、铑(Rh)、钯(Pd)、银(Ag)、镉(Cd)、铪(Hf)、钽(Ta)、钨(W)、铼(Re)、锇(Os)、铱(Ir)、铂(Pt)、金(Au)、镓(Ga)、铟(In)、锡(Sn)、锑(Sb)及其组合中选取。
2.如权利要求1所述的烃类裂解方法，其特征在于其在约480℃到约600℃温度范围内运行，烃类包含原油经过常压、减压分馏获得的底层物质，且水蒸汽占水蒸汽和烃类总重量的百分比在约1％到约2％之间。
3.如权利要求1所述的烃类裂解方法，其特征在于其在约700℃到约870℃温度范围内运行，水蒸汽和烃类的质量比在约3∶7到约7∶3的范围内，烃类包含乙烷、庚烷、液化石油气、石脑油、石油和天然气中的至少一种。
4.如权利要求1至3中任一权利要求所述的烃类裂解方法，其特征在于所述钙钛矿材料从SrCeO3、SrZr0.3Ce0.7O3、BaMnO3、BaCeO3、BaZr0.3Ce0.7O3、BaZr0.3Ce0.5Y0.2O3、BaZr0.1Ce0.7Y0.2O3、BaZrO3、BaZr0.7Ce0.3O3、BaCe0.5Zr0.5O3、BaCe0.9Y0.1O3、BaCe0.85Y0.15O3和BaCe0.8Y0.2O3中选取。
5.一种烃类裂解反应装置，其接触烃类的表面含有化学式为AaBbCcDdO3-δ的钙钛矿材料，其中0＜a＜1.2，0≤b≤1.2，0.9＜a+b≤1.2，0＜c＜1.2，0≤d≤1.2，0.9＜c+d≤1.2，-0.5＜δ＜0.5；A从钙(Ca)、锶(Sr)、钡(Ba)及其组合中选取；B从锂(Li)、钠(Na)、钾(K)、铷(Rb)及其组合中选取；C从铈(Ce)、锆(Zr)、锑(Sb)、镨(Pr)、钛(Ti)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、镓(Ga)、锡(Sn)、铽(Tb)及其组合中选取；D从镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)、钪(Sc)、钛(Ti)、钒(V)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、锌(Zn)、钇(Y)、锆(Zr)、铌(Nb)、钼(Mo)、锝(Tc)、钌(Ru)、铑(Rh)、钯(Pd)、银(Ag)、镉(Cd)、铪(Hf)、钽(Ta)、钨(W)、铼(Re)、锇(Os)、铱(Ir)、铂(Pt)、金(Au)、镓(Ga)、铟(In)、锡(Sn)、锑(Sb)及其组合中选取。
6.如权利要求5所述的烃类裂解反应装置，其特征在于所述钙钛矿材料为SrZr0.3Ce0.7O3。
7.如权利要求5所述的烃类裂解反应装置，其特征在于所述钙钛矿材料为BaZr0.3Ce0.7O3。
8.如权利要求5所述的烃类裂解反应装置，其特征在于所述钙钛矿材料为BaZr0.1Ce0.7Y0.2O3。
9.如权利要求5所述的烃类裂解反应装置，其特征在于所述钙钛矿材料为BaCe0.8Y0.2O3。
10.如权利要求5至9中任一权利要求所述的烃类裂解反应装置，其特征在于其包含裂解炉管、管路接头、反应容器和辐射管中至少一个。
11.如权利要求5至9中任一权利要求所述的烃类裂解反应装置，其特征在于所述钙钛矿材料存在于接触烃类的表面涂层中。
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US20110295051A1 (en) 2011-12-01
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