CN102355948B - 用于生产合成气的镍/氧化镧催化剂 - Google Patents
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 83
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 46
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 44
- 230000008569 process Effects 0.000 claims abstract description 32
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 28
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 62
- 239000007789 gas Substances 0.000 claims description 51
- 230000015572 biosynthetic process Effects 0.000 claims description 30
- 238000003786 synthesis reaction Methods 0.000 claims description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 238000009938 salting Methods 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 9
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- 238000005538 encapsulation Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 238000000151 deposition Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 33
- 229910002091 carbon monoxide Inorganic materials 0.000 description 33
- 239000000203 mixture Substances 0.000 description 22
- 238000002407 reforming Methods 0.000 description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000010321 Noronhia emarginata Nutrition 0.000 description 1
- 240000002903 Noronhia emarginata Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012120 mounting media Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
本发明涉及用于由烃进料流产生合成气的镍/氧化镧(Ni/La2O3)催化剂,该催化剂如下原位制成:通过使氧化镧(La2O3)载体与镍盐(Ni盐)水溶液在含氧气流存在下接触,在所述La2O3载体上沉积镍(Ni);之后将沉积的Ni还原。本发明催化剂的特征在于它能够在不表现出显著的催化剂活性损失的情况下,在由烃进料流产生合成气的工艺中连续操作大于14天。
Description
技术领域
本发明涉及含镍/氧化镧的催化剂的制备方法。所述催化剂适合于重整烃进料以产生合成气。
背景技术
重整烃类以产生包含合成气(也称作合成煤气)的重整气体组合物的工艺是本领域已知的而且包括蒸汽重整、催化干法重整、部分氧化或它们的组合。
烃类的蒸汽重整是公知的生产合成气的方法,其包括使烃与蒸汽接触。蒸汽重整高度吸热并且需要例如700-1100℃的高反应温度。因此,应当注意避免热力学限制。此外,烃类的蒸汽重整需要相对较长的接触时间。典型地,由诸如甲烷之类的烃的蒸汽重整产生的合成气混合物具有约4.5-5.2的非常高的H2/CO比率。由甲烷蒸汽重整所产生的合成气的H2/CO比率可以例如通过添加CO或通过脱除H2进行调节。作为选择,合成气组合物的H2/CO比率可以通过使它经历反向水煤气变换反应调节至期望的值。
可以通过甲烷用CO2的催化干法重整直接产生H2/CO比率大约为1的合成气组合物。甲烷的催化干法重整也是高度吸热的并且应当在高反应温度下执行。许多催化干法重整工艺已知包括导致催化剂失活的快速焦炭沉积。在这些催化干法重整工艺中,可以通过在高温下向催化剂供氧使反应器再生。
烃进料存在下的部分氧化是产生合成气混合物的另一种手段。部分氧化的缺点在于产生二氧化碳作为副产物,这限制了烃重整工艺的脂族和芳族C2-C6烃类选择性。
通过将包括上文所述那些在内的不同的重整反应组合,可以例如 通过规避热力学限制和/或通过降低用于加热或脱除工艺热量的成本来优化重整工艺。
特别有利的用于生产合成气的组合重整工艺为诸如甲烷之类的低级烃的催化自热干法重整。通过使甲烷(CH4)、氧气(O2)和二氧化碳(CO2)的混合物与催化剂接触,能够在单一体系中进行吸热的干法重整和放热的甲烷氧化,这代表了减少合成气合成过程中的能量消耗的有效手段;例如参见MORTOLA等,NORONHA等编辑,Elsevier,2007,第409-414页。自热干法重整的另一优势在于产生的合成气组合物的H2/CO比率约为1.4-1.8,这对于所产生的合成气在诸如费-托(F-T)合成之类的工艺中的进一步应用非常有利。
已经描述过镍基催化剂也可以用于轻质烃类部分氧化成合成气的工艺。特别地,包含在氧化镧上担载的镍的催化剂已知在由轻质烃类生产合成气的工艺中提供相对较高的转化率和选择性;例如参见EP741107 A;US 5447705和US 2004/0127351。
在例如甲烷的自热干法重整中使用常规Ni/La2O3重整催化剂时,缺点是至少部分归因于焦炭形成的催化剂失活。该催化剂失活导致降低的烃选择性和降低的工艺经济性。
构成本发明基础的技术问题是提供在将诸如甲烷之类的烃转化成合成气的工艺中有用的改进的催化剂。
发明内容
通过提供如下文所述以及如权利要求中表述的实施方案实现上述问题的解决方案。
因此,本发明提供制备镍/氧化镧(Ni/La2O3)催化剂的方法,其包括下述步骤:(a)通过使氧化镧(La2O3)载体与镍盐(Ni盐)水溶液在含氧气流存在下接触在所述La2O3载体上沉积镍(Ni);之后(b)将沉积的Ni还原,由此原位制成所述Ni/La2O3催化剂;或者-否则的话-其中工艺步骤(a)和(b)都原位进行。
按常规,通过Ni在La2O3上的化学气相沉积产生Ni/La2O3重整催化剂,之后将该产生的Ni/La2O3催化剂颗粒装入催化剂包封物中。然而,这些之前描述的Ni/La2O3催化剂在长时间的催化剂操作之后显示出降低的烃转化速率,因而逐渐变得失活。在本发明的上下文中,令人惊讶地发现原位制备的Ni/La2O3重整催化剂能够在不表现出显著的催化剂活性损失的情况下连续操作大于14天。这导致与常规制备的Ni/La2O3重整催化剂相比时,本发明的原位制备的Ni/La2O3催化剂在长时间的催化剂操作之后的优良活性。
术语“原位”在化学工程领域中是公知的而且是指原地进行的工业设备操作或过程。例如,工业反应器中的老化催化剂可以在不从反应器中取出的情况下原地(原位)再生;例如参见WO03/041860和WO03/076074。因此,在本发明的上下文中,原位制备的催化剂是指原地、即在后来存在于其中发生催化工艺的工艺装置内的同一包封物中制备的催化剂。
在一种实施方案中,以使得在置于其中有待采用Ni/La2O3催化剂的工艺装置、例如制造合成气的反应器内的催化剂包封物中制备Ni/La2O3催化剂的方式进行本发明的方法。在另一实施方案中,以使得在能够直接放入所述工艺装置内的催化剂包封物中制备Ni/La2O3催化剂的方式进行本发明的方法。
在本发明的方法中,在如上文所述的步骤(a)中优选使La2O3载体与Ni盐溶液接触直至在该La2O3载体上沉积至少约0.1质量%Ni、优选约1质量%Ni但是不超过约5质量%Ni、优选不超过4质量%Ni。最优选地,在La2O3载体上沉积约3质量%Ni。在本发明的上下文中,基于La2O3载体的重量计算催化剂的Ni负载质量%。
在本发明方法中优选用于在La2O3载体上沉积Ni的Ni盐水溶液为Ni(NO3)2的水溶液。然而,技术人员能够容易地选择其它合适的Ni盐制备可以用于本发明方法的Ni盐溶液。这些合适的Ni盐包括但不限于乙酸镍。
当选择La2O3载体颗粒的尺寸时,应当考虑到选择太小的La2O3粒度(高筛目大小数)可能伴随着反应器中不期望的压降,而选择太大的La2O3粒度(低筛目大小数)可能导致效率低的Ni盐溶液浸渍。在一种实施方案中,在使La2O3载体与Ni盐水溶液接触之前,La2O3载体为粒度约为14-60目的La2O3颗粒。更优选地,将25-40目的La2O3颗粒用于本发明的方法。目理解为是指如同由a.o.ASTM E 11-70限定的标准筛目大小。
氧化镧(La2O3)载体可以进一步包含合适的惰性粘结剂如氧化铝(Al2O3)、二氧化硅(SiO2)、二氧化钛(TiO2)、氧化锆(ZrO2)、氧化镁(MgO)以及它们的混合物。在这种情况下通过常规方法将La2O3载体与粘结剂合并,例如MgO-La2O3,然后用Ni原位浸渍。然而,优选的是本发明的催化剂不含这类粘结剂。
在包含分子氧的气流存在下使Ni盐溶液在La2O3载体上沉积。不希望受任何理论束缚的情况下,认为氧的存在容许产生Ni氧化物相并因此防止金属Ni相的分离,这在没有足够的分子氧存在下沉积时会在载体介质中形成。优选地,在使La2O3载体与Ni盐溶液接触之前,使该La2O3载体与温度约为450℃的含氧气流接触。优选地,在使La2O3载体与Ni盐溶液接触之前,使该La2O3载体与所述含氧气流接触至少30分钟和更优选至少45分钟,但是不超过24小时和更优选不超过8小时。最优选地,在使La2O3载体与Ni盐溶液接触之前,使该La2O3载体与所述含氧气流接触大约1-2小时。
当在La2O3上沉积Ni盐溶液时所述含氧气流中包含的其它气态组分可以选自甲烷(CH3)、二氧化碳(CO2)和一种或多种惰性气体。本文使用的术语“惰性气体”涉及在相应条件下处于气相中并且不参与和/或妨碍工艺或者相应工艺步骤过程中发生的化学反应的任何元素或化合物。因此,可以存在于各股气流中的“惰性气体”能够充当重整气体的其余气体组分的惰性稀释剂。本发明上下文中优选的惰性气体为氮气(N2)。在一种实施方案中,沉积Ni盐溶液时存在的含氧气流与在本发明方法生产的催化剂存在下经历自热干法重整以产生合成气的含烃进料流具有相同的组成。甚至更优选地,沉积Ni时存在的含氧气流由大约27-30摩尔%CH4+10-12摩尔%O2+17-18摩尔% CO2+41-44摩尔%N2(总计100%)组成,更优选由约28.4摩尔%CH4+11摩尔%O2+17.4摩尔%CO2+42.8摩尔%N2组成。
在La2O3载体上沉积Ni直至达到期望的Ni负载之后,将沉积的Ni原位还原成其金属态。优选通过使沉积的Ni与大约650-750℃的含甲烷气流接触30分钟-24小时将沉积的Ni还原。最优选地,在约660℃下还原该沉积的Ni。
在用于本发明方法还原步骤的含甲烷气流中包含的其它气态组分可以选自O2、CO2和如上文定义的惰性气体。在一种实施方案中,用于还原Ni盐溶液的含甲烷气流与在本发明方法生产的催化剂存在下经历自热干法重整以产生合成气的含烃进料流具有相同的组成。在这种情况下,生产的Ni/La2O3最初将甲烷完全氧化成二氧化碳。当达到稳态条件时,沉积的Ni被还原,原位制备的Ni/La2O3产生合成气。甚至更优选地,用于还原沉积的Ni的含甲烷气流由大约27-30摩尔%CH4+10-12摩尔%O2+17-18摩尔%CO2+41-44摩尔%N2(总计100%)组成,更优选由约28.4摩尔%CH4+11摩尔%O2+17.4摩尔%CO2+42.8摩尔%N2组成。
在另一实施方案中,本发明涉及生产合成气的工艺,其包括使适合于生产合成气的烃进料流与如上文所述和如权利要求表述的本发明方法所产生的催化剂接触。因此,本发明进一步涉及生产合成气的工艺,其包括制备Ni/La2O3催化剂,该制备包括下述步骤:(a)通过使La2O3载体与Ni盐水溶液在含氧气流存在下接触在所述La2O3载体上沉积镍(Ni);之后(b)将沉积的Ni还原,由此原位制成所述Ni/La2O3催化剂,随后使所述制成的催化剂与适合于产生合成气的烃进料流接触。
所述烃进料中包含的烃类可以包括气态烃类如甲烷、乙烷、天然气或液化石油气(LPG),但是还有更重质的烃类如C6+烃类。优选地,本发明工艺的烃进料中所含的主要烃成分是甲烷。在本发明的上下文中,术语“主要烃成分”是指给定的烃构成所有包含的烃类的大于50摩尔%,更优选所有包含的烃类的大于60摩尔%,甚至更优选所有包 含的烃类的大于70摩尔%,以及最优选所有包含的烃类的大于75摩尔%。因此,本发明特别优选地涉及用于甲烷的催化自热干法重整(ATDRM)的工艺,其包括使如上文所述原位产生的Ni/La2O3催化剂与含甲烷的烃进料流接触。
用于本发明重整工艺的烃进料中包含的其它气态组分可以选自O2、CO2和一种或多种如上文定义的惰性气体。在一种实施方案中,接触本发明方法中所产生的催化剂的含烃进料流与沉积Ni时存在的含氧气流和/或原位制备本发明的催化剂时用于还原Ni盐溶液的含甲烷气流具有相同的组成。甚至更优选地,本发明重整工艺的烃进料流由大约27-30摩尔%CH4+10-12摩尔%O2+17-18摩尔%CO2+41-44摩尔%N2(总计100%)组成,更优选由约28.4摩尔%CH4+11摩尔%O2+17.4摩尔%CO2+42.8摩尔%N2组成。显然的是在某些情况下可以改变或调整该组成。然而,应当避免大于约3的甲烷/O2比率,因为太低的含氧量导致归因于焦炭形成的催化剂失活。小于2.5的甲烷/O2比率由于催化剂过度氧化(催化剂中太多氧化物相)也是不那么有利的。
确定适合于进行包括使合适的烃进料流与本发明方法所产生的催化剂接触的合成气生产工艺的工艺条件完全是在技术人员能力范围内。优选地,本发明的(重整)工艺在650-750℃的反应温度和0.4-2秒的接触时间下进行。更优选680-710℃的反应温度和0.4-1秒的接触时间。低于680℃的反应温度下转化率可能开始不期望地降低。
本发明使用的术语“重整气体”涉及如本文所述的重整工艺的气态产物,其基本上由合成气(H2和CO)、氧气(O2)和任选地选自甲烷(CH4)、二氧化碳(CO2)和惰性气体的另外的组分组成。
因此,“重整气体”的主要成分是合成气(合成煤气;H2和CO的混合物)。本发明的重整气体包含至少50摩尔%和优选至少55摩尔%合成气。优选地,由本发明的重整工艺产生的重整气体中存在的合成气具有至少为1、更优选至少为1.2、甚至更优选至少为1.4和特别优选至少为1.6的氢气(H2)与一氧化碳(CO)比率,但是其优选不超过4、更优选不超过3、甚至更优选不超过2和特别优选不超过1.8。 最优选地,该“重整气体”具有至少1.6但不超过1.8的H2与CO比率(1.6-1.8的H2与CO比率)。
本发明的“重整气体”可以包含至少0.1摩尔%O2、更优选至少0.2摩尔%O2,甚至更优选至少0.3摩尔%O2和特别优选至少0.35摩尔%O2。此外,本发明的“重整气体”包含不超过5摩尔%O2,更优选不超过2.5摩尔%O2和甚至更优选不超过1摩尔%O2以及特别优选不超过0.5摩尔%O2。最优选地,本发明工艺中制成的重整气体包含0.4摩尔%氧气(O2)。
如下文所述,包含CH4、O2和CO2的进料流可以通过使所述进料流与原位制备的Ni/La2O3催化剂在710℃的反应温度下接触而经由催化自热干法重整得到转化,从而产生大约包含22摩尔%CO、35摩尔%H2和0.4摩尔%O2的重整气体。
通过重整烃类产生的“重整气体”可以直接用作另一工艺的进料,这些工艺包括但不限于F-T合成或羰基化反应如烯烃加氢甲酰化或生产芳醛的芳烃加氢甲酰化。
F-T合成是公知的受催化的化学反应,其中合成气、即一氧化碳和氢气的混合物通过使合成气与F-T催化剂在F-T合成条件下接触得以转化成烃化合物的复杂混合物;例如参见KANEKO TAKAO等,Ullmann’s Encyclopedia of Industrial Chemistry,第7版,John Wiley,1997,第17-31页。
最常见的可用于F-T合成的催化剂(“F-T催化剂”)基于Fe和/或Co,尽管还描述过Ni基和Ru基催化剂;例如参见US 4,177,203;COMMEREUC等,J.Chem.Soc.,Chem.Commun.,1980,第154-155页;OKUHARA等,J.Chem.Soc.,Chem.Commun.,1981,第1114-1115页。一般地,Ni基催化剂对于生产甲烷而言相对更有选择性,而Co、Fe和Ru基催化剂对于具有至少一个碳原子的烃类(C2+烃)更有选择性。此外,通过减小H2/CO比率、降低反应温度和降低反应器压力可以提高C2+烃类的选择性。
可以使用的合适的费-托催化剂是钴/铁双组分氧化物(Co/Fe-O) 催化剂。该钴/铁双组分氧化物可以担载于惰性载体上。适合于费-托催化剂的惰性载体是本领域已知的而且包括氧化铝(Al2O3)、二氧化硅(SiO2)、二氧化钛(TiO2)、氧化锆(ZrO2)和氧化镁(MgO),以及它们的混合物。优选地钴/铁双组分氧化物担载于二氧化硅(SiO2)上。上述Co/Fe-O-SiO2催化剂例如在以下得到描述:YONGHONG BI等,The Canadian Journal of Chemical Engineering,2003,第81卷,第230-242页。
在另一实施方案中,本发明涉及如上文所述和如权利要求中表征的由本发明方法所产生的Ni/La2O3催化剂。本发明所提供的Ni/La2O3催化剂的特征在于其提高的稳定性,该稳定性容许所述催化剂在不表现出显著的催化剂活性损失的情况下于上文所述和如权利要求中表述的重整工艺中连续操作大于14天。
实施发明的方式
现在将通过下列非限制性实施例更完整地描述本发明。
实施例1
如下制备用于甲烷自热干法重整的重整催化剂“原位3%Ni/La2O3”:在内径12mm、长45cm的石英反应器中装入粒度为25-40目的2ml La2O3颗粒。向装料的反应器供给450℃下由约28.4摩尔%CH4+11摩尔%O2+17.4摩尔%CO2+42.8摩尔%N2组成的气态混合物。在用反应混合物处理载体(少于24小时)以获得稳定相组合物之后,开始用0.1-0.3%Ni(NO3)2水溶液浸渍La2O3载体。为此通过注入气流将该0.1-0.3%Ni(NO3)2溶液供给La2O3载体,从而用Ni盐逐渐浸渍La2O3载体。持续La2O3载体的Ni(NO3)2浸渍直至达到3质量%Ni/La2O3基准的计算量为止。在Ni(NO3)2浸渍步骤过程中观察到NO2的形成,这显示在La2O3载体内形成Ni氧化物。
在完成Ni(NO3)2浸渍步骤之后,将反应温度升至660℃从而用含甲烷的气态混合物(如上)还原Ni氧化物。所得的原位制备的重整催化 剂“原位3%Ni/La2O3”最初将甲烷完全氧化成CO2。然而在达到稳态条件之后,该“原位3%Ni/La2O3”催化剂形成CO和H2。
使该含甲烷进料流与重整催化剂“原位3%Ni/La2O3”在680-710℃下以0.5秒的接触时间接触,从而产生由大约21.5摩尔%CO+35.5摩尔%H2+34.79摩尔%N2+6.17摩尔%CH4+1.55摩尔%CO2+0.4摩尔%O2组成的合成气组合物。使用设置在长45cm的电加热炉中的内径12mm石英反应器。如下表1所示,原位制备的Ni/La2O3催化剂显示出超过120小时的稳定活性。
试验2(对比)
通过在70-80℃下用Ni(NO3)2溶液浸渍La2O3粉末制备常规的Ni/La2O3催化剂,从而产生3质量%的Ni含量(如实施例1中)。随后,将Ni浸渍的La2O3保持在70-80℃直至所有的水蒸发为止。然后在120℃干燥该固体混合物并在700℃煅烧4小时。随后,将煅烧过的Ni/La2O3颗粒装入用作催化剂包封物的内径12mm的石英反应器。
由约28.4摩尔%CH4+11摩尔%O2+17.4摩尔%CO2+42.8摩尔%N2组成的进料流与0.5ml常规制备的Ni/La2O3重整催化剂在680-710℃下以0.5秒的接触时间接触以产生合成气组合物。
如下表1所示,通过用Ni盐浸渍La2O3制备的重整催化剂的活性在操作14天内逐渐下降。
表1
CH4转化率(%) | ||
催化剂筛选(screening)持续时间(天) | 原位制备的催化剂(实施例1) | 常规制备的催化剂(实施例2) |
5 | 73.7 | 72.5 |
14 | 73.0 | 65.8 |
如同可以从表1中得出的那样,原位制备的催化剂能够在不表现出显著的催化剂活性损失的情况下连续操作14天以上。这导致与通过Ni在La2O3上化学气相沉积所制备的常规催化剂相比时,如同可以从催化剂操作14天之后明显更高的甲烷转化速率中得出的那样,本发明催化剂在长时间的催化剂操作之后的优良活性。
Claims (12)
1.制备镍/氧化镧(Ni/La2O3)催化剂的方法,其包括下述步骤:
(a)通过使氧化镧(La2O3)载体与镍盐(Ni盐)水溶液在含氧气流存在下接触,在所述La2O3载体上沉积镍(Ni);之后
(b)将沉积的Ni还原,
其中工艺步骤(a)和(b)都在后来存在于其中发生催化工艺的工艺装置内的同一包封物中进行。
2.权利要求1的方法,其中在置于其中有待采用所述Ni/La2O3催化剂的工艺装置内的催化剂包封物中制备所述Ni/La2O3催化剂;或者其中在能够直接放入所述工艺装置内的催化剂包封物中制备所述Ni/La2O3催化剂。
3.权利要求1的方法,其中在步骤(a)中使所述La2O3载体与所述Ni盐溶液接触直至在该La2O3载体上沉积基于La2O3载体0.1-5质量%的Ni。
4.权利要求1的方法,其中所述Ni盐溶液为Ni(NO3)2溶液。
5.权利要求1的方法,其中在使La2O3载体与Ni盐水溶液接触之前,所述La2O3载体为粒度为14-60目的La2O3颗粒。
6.权利要求1的方法,其中在使La2O3载体与Ni盐溶液接触之前,使所述La2O3载体与为450°C下的含氧气流接触30分钟-24小时。
7.权利要求1的方法,其中通过使沉积的Ni与650-750°C的含甲烷气流接触30分钟-24小时将所述沉积的Ni还原。
8.权利要求1的方法,其中所述气流由总计100%的27-30摩尔%CH4+10-12摩尔%O2+17-18摩尔%CO2+41-44摩尔%N2组成。
9.生产合成气的方法,其包括使适合于产生合成气的烃进料流与权利要求1-8任一项的方法所产生的催化剂接触。
10.权利要求9的方法,其中所述烃进料流由总计100%的27-30摩尔%CH4+10-12摩尔%O2+17-18摩尔%CO2+41-44摩尔%N2组成。
11.权利要求9的方法,其中所述方法在650-750°C的反应温度和0.4-2秒的接触时间下进行。
12.权利要求1-8任一项的方法所产生的催化剂。
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JP (1) | JP5551234B2 (zh) |
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CN102356044B (zh) * | 2009-03-16 | 2014-10-15 | 沙特基础工业公司 | 制备脂族和芳族烃类混合物的方法 |
WO2013135662A1 (de) | 2012-03-13 | 2013-09-19 | Bayer Intellectual Property Gmbh | Verfahren zur reduktion von kohlendioxid bei hohen temperaturen an mischmetalloxidkatalysatoren |
WO2013135707A1 (de) | 2012-03-13 | 2013-09-19 | Bayer Intellectual Property Gmbh | Verfahren zur herstellung eines kohlenmonoxid enthaltenden gasgemisches bei hohen temperaturen an mischmetalloxidkatalysatoren umfassend edelmetalle |
WO2013135663A1 (de) | 2012-03-13 | 2013-09-19 | Bayer Intellectual Property Gmbh | Verfahren zur reduktion von kohlendioxid bei hohen temperaturen an mischmetalloxid-katalysatoren umfassend edelmetalle |
US9688593B2 (en) | 2013-10-29 | 2017-06-27 | Saudi Basic Industries Corporation | Method for carbon dioxide hydrogenation of syngas and the integration of the process with syngas conversion processes |
WO2016059569A1 (en) | 2014-10-15 | 2016-04-21 | Sabic Global Technologies B.V. | Integrated polycarbonate production process |
WO2016059566A1 (en) | 2014-10-15 | 2016-04-21 | Sabic Global Technologies B.V. | Integrated syngas-based production of dimethyl carbonate |
WO2016059568A1 (en) | 2014-10-15 | 2016-04-21 | Sabic Global Technologies B.V. | Integrated chemical production |
WO2016059565A2 (en) | 2014-10-15 | 2016-04-21 | Sabic Global Technologies B.V. | Integrated crude oil refining and cracking |
KR101725293B1 (ko) * | 2015-11-04 | 2017-04-10 | 한국과학기술연구원 | 혼합 개질 반응용 니켈 담지촉매 |
US20180362418A1 (en) * | 2015-12-14 | 2018-12-20 | Sabic Global Technologies B.V. | Conversion of methane to ethylene comprising integration with the in-situ ethane cracking and direct conversion of co2 byproduct to methanol |
SG11202012245WA (en) | 2018-06-29 | 2021-01-28 | Shell Int Research | Electrically heated reactor and a process for gas conversions using said reactor |
WO2020142594A1 (en) * | 2019-01-02 | 2020-07-09 | Sabic Global Technologies, B.V. | Oxidative conversion of methane to c2 hydrocarbons and synthesis gas |
CN113019383A (zh) * | 2021-03-10 | 2021-06-25 | 中国科学院兰州化学物理研究所 | 一种镍/氧化镧催化剂及其制备方法与应用 |
CN114749182A (zh) * | 2022-03-29 | 2022-07-15 | 中国科学院兰州化学物理研究所 | 一种用于甲烷干重整的镍-氧化镧催化剂及其制备方法 |
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EP0741107A2 (en) * | 1995-05-03 | 1996-11-06 | Foundation for Research and Technology Hellas, (Institute of Chemical Engineering and High Temperature Chemical Processes) | Catalysts for the partial oxidation of light hydrocarbons to synthesis gas |
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JPH01148343A (ja) * | 1987-12-02 | 1989-06-09 | Res Dev Corp Of Japan | 合成ガス製造用触媒 |
JPH05170404A (ja) * | 1991-12-25 | 1993-07-09 | Tosoh Corp | メタンによる二酸化炭素の変換方法 |
FR2696109B1 (fr) | 1992-09-28 | 1994-11-04 | Inst Francais Du Petrole | Catalyseur d'oxydation et procédé d'oxydation partielle du méthane. |
US6900151B2 (en) | 2001-11-13 | 2005-05-31 | Exxonmobil Research And Engineering Company | In situ catalyst regeneration/activation process |
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EP1419814A1 (en) | 2002-11-15 | 2004-05-19 | L'AIR LIQUIDE, Société Anonyme à Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des | Perovskite catalyst for the partial oxidation of natural gas |
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JP5551234B2 (ja) | 2014-07-16 |
WO2010105788A8 (en) | 2011-10-20 |
EA019045B1 (ru) | 2013-12-30 |
WO2010105788A2 (en) | 2010-09-23 |
EP2408559B1 (en) | 2016-09-28 |
US9227185B2 (en) | 2016-01-05 |
CN102355948A (zh) | 2012-02-15 |
JP2012520177A (ja) | 2012-09-06 |
WO2010105788A3 (en) | 2011-02-17 |
US20120007025A1 (en) | 2012-01-12 |
EP2408559A2 (en) | 2012-01-25 |
EA201101340A1 (ru) | 2012-04-30 |
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