CN102149463A - 制备羰基铁粉末和烃的一体化方法 - Google Patents
制备羰基铁粉末和烃的一体化方法 Download PDFInfo
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Abstract
本发明涉及一种一体化方法,其中纯羰基铁粉末通过在装置A中分解纯五羰基化铁制备,在五羰基化铁的分解中释放的一氧化碳(CO)在装置A中用于从铁制备其它羰基铁粉末,或加入用于制备合成气的相关装置B中,或加入用于从合成气制备烃的相关装置C中。将在装置A中制备的羰基铁粉末加入相关装置C中并且作为催化剂或催化剂组分用于从来自装置B的合成气制备烃。
Description
本发明涉及一种通过分解纯的五羰基化铁(IPC)制备纯羰基铁粉末(CIP)和从合成气制备烃的一体化方法。
通过分解纯的五羰基化铁(IPC)制备纯羰基铁粉末(CIP)的方法是已知的,例如参见Ullmann’s Encyclopedia f Industrial Chemistry,铁化合物,E.Wildermuth,H.Stark等,在线公布:2000年6月15日(Wiley-VCH-Verlag)。
为此,铁粒子在高压和高温下反应形成五羰基化铁(IPC,Fe(CO)5)。在铁中存在的杂质优选部分地通过在羰基阶段蒸馏除去,并且获得非常纯的IPC。此化合物是用于在随后步骤中将IPC分解成CIP的前体。在此步骤中,IPC在高温下被分解成CIP,例如在下流式分解器中。
在下游的工艺步骤中,这种初级的CIP可以加工得到用于Fischer-Tropsch合成的催化剂。在专利申请EP 07112853.2(2007年7月20日)和EP 08156965.9(2008年5月27日)(都来自BASF AG或SE)中描述了这种催化剂用于从合成气制备烃、尤其低级烯烃的进一步加工和合适性。
已经知道,烃可以从一氧化碳(CO)和氢气(H2)在金属催化剂上制备,例如铁或钴催化剂。
WO 2006/127261 A1的第2页[005]段(沉淀型催化剂)和[006]段(稠合催化剂)中描述了用于Fischer-Tropsch合成的其它铁催化剂。
在制备Fischer-Tropsch铁催化剂或沉淀型催化剂中的主要缺点一般是制备耗能高并且劳动强度高,获得了废料,它们通常属于对环境有害的材料。
本发明的目的是克服现有技术的缺点,并发现制备纯羰基铁粉末(CIP)和烃的改进的经济可行的方法。所述第一个工艺应当尤其能避免在常规催化剂生产中获得的大摩尔量的废产品。盐负荷和废水尤其代表需要复杂后处理的生产因素,并且必须以高成本处理。第二个工艺应当能从合成气获得短链烃。在一个具体实施方案中,此方法应当优选得到C2-C8烯烃(C2-C8烯烃),尤其是C2-C4烯烃(C2-C4烯烃),尤其是乙烯、丙烯和1-丁烯,同时获得非常少量的甲烷、二氧化碳、链烷(例如C2-C4链烷)和高级烃,即具有5或更多个碳原子的烃(C5+级分)。
根据本发明,尤其认识到:如果考虑到一氧化碳(CO)的物质循环,则IPC的制备和随后分解成CIP的操作可以考虑成循环工艺,其中CO发生循环。与其它制备方法相比,例如铁化合物的沉淀、煅烧和随后还原成金属铁的过程,经由羰基化合物的路线尤其是有利的,这是因为不会获得废料(例如盐)和废水。有利的是这样的一体化方法:其中能量和物质循环组合,使得用于化学反应、尤其用于Fischer-Tropsch合成的基于铁的催化剂是从作为原料的铁或氧化铁经由羰基铁粉末(CIP)的中间阶段制备的。
我们因此发现了一体化方法,其中纯羰基铁粉末(CIP)通过在装置A中分解纯五羰基化铁(IPC)制备;在IPC的分解中释放的一氧化碳(CO)在装置A中用于从铁制备其它CIP,或加入用于制备合成气的相关装置B中,或加入用于从合成气制备烃的相关装置C中;
并且在装置A中制备的CIP用做在相关装置C中的催化剂或催化剂组分以从来自装置B的合成气制备烃。
关于在装置A中制备纯CIP的工艺:
IPC的分解优选是气态IPC的热分解。
在IPC分解之后获得的CIP优选在进一步使用之前用氢气处理。
用氢气处理CIP的操作优选在300-600℃范围内的温度下进行。
此处理降低了在CIP中的碳、氮和氧的残余含量(DE 528 463 C1,1927)。
所用的氢气优选来自用于制备合成气的相关装置B。
用于制备CIP的铁优选预先用氢气处理。
用氢气处理铁的操作优选在300-1000℃范围内的温度下进行。
此处理尤其降低了铁的氧含量。
所用的氢气优选来自用于制备合成气的相关装置B。
用于制备纯CIP的IPC优选预先通过蒸馏提纯。
这种蒸馏以羰基化合物的形式除去了杂质,例如过渡金属,尤其是Ni和Cr。
用于制备其它IPC所需的额外CO优选来自用于制备合成气的相关装置B。
根据在装置A中的工艺所制备的纯羰基铁粉末(CIP)优选具有以下特征:
CIP含有球形初级粒子,其直径优选在≥1至50微米的范围内。初级粒子可以聚集。
关于在装置B和C中通过一氧化碳与氢气(即合成气)的反应制备烃的工艺:
所需的合成气优选在装置B中通过公知的方法制备(参见例如Weissermel等,Industrial Organic Chemistry,Wiley-VCH,Weinheim,2003,第15-24页),例如通过煤或甲烷与水蒸气反应,或通过甲烷的部分氧化反应。合适的用于制备合成气的主要能量载体是煤和天然气以及生物质。
合成气优选具有一氧化碳与氢气的摩尔比是在3∶1至1∶3的范围内。在装置C中,特别优选使用这样的合成气,其具有一氧化碳与氢气的摩尔混合比是在2∶1至1∶2的范围内。
在本发明一体化方法的一个具体实施方案中,合成气含有二氧化碳(CO2)。CO2含量优选在1-50重量%范围内。
在一个具体实施方案中,合成气优选通过煤在装置B中的气化制备。这些方法例如也参见Nexant Inc./Chem Systems PERP 03/04-S4-合成气技术的进展(Developments in Syngas Technology),2005,10/11和58-63页。可以通过煤的气化所制备的合成气具有一氧化碳与氢气的摩尔比是在2.36-0.4的范围内,特别优选在2-0.6的范围内,尤其是在1.5-0.8的范围内。
在装置C中制备烃的方法中获得的已用过的催化剂优选在如上所述用氢气处理之后,优选用做在装置A中用于制备羰基铁粉末(CIP)的额外铁源。
根据本发明,特别有利的是,在装置A中制备用做在制备烃的相关装置C中的催化剂或催化剂组分的CIP与CO循环工艺组合,并且与用于制备合成气的装置B整合,并与通过将已用过的催化剂从装置C循环到装置A进行的铁循环组合。
本发明的一体化方法的优选实施方案显示在图1中。
在图1中的各步骤可以如下作为优选实施方案描述,从“已消耗的催化剂(含铁)”开始:
1)氧化铁与铁(Fe)或氧化铁(后两种在每种情况下来自装置C的已用过的催化剂)混合并还原。用于还原的氢气是来自合成气装置B。未消耗的氢气可以送回合成气装置B或直接加入用于制备烃的Fischer-Tropsch装置C。
2)所获得的金属铁与来自合成气装置B的CO在装置A中反应,形成IPC。
3)IPC在装置A中被分解成CIP,并且将释放出的CO加入合成气装置B、Fischer-Tropsch装置C或返回在装置A中的EPC合成。最后一种选择对应于直接CO循环。
4)来自装置A的CIP在随后的步骤中加工得到铁Fischer-Tropsch催化剂,并用于合成烃的Fischer-Tropsch装置C中。另外,CIP可以在外部市场销售。
5)从装置C除去的催化剂经由合成金属铁的“催化剂回路”送回EPC生产工艺(步骤1)。
由于本发明各个工艺步骤的联合,优选对于所用的一氧化碳和铁两者获得基本上闭合的物质循环。因此,所得的一体化工艺是环境友好的,并且使得基于铁的催化剂的来源保护式生产成为可能。
在用于通过合成气的反应制备烃的装置C中的工艺的其它描述如下:
具有球形初级粒子的羰基铁粉末(CIP)优选用于制备烃、优选烯烃的装置C中的工艺中,其中通过一氧化碳和氢气在含CIP的多相催化剂的存在下反应。
球形初级粒子在羰基铁粉末中的比例优选是>90重量%,特别优选>95重量%,非常特别优选>98重量%。
球形初级粒子优选具有0.01-250微米的直径,尤其是0.1-200微米,非常尤其是0.5-150微米,更尤其是0.7-100微米,更特别是1-70微米,特别优选1.5-50微米。
球形初级粒子的铁含量优选>97重量%,特别优选≥99重量%,尤其优选≥99.5重量%,在每种情况下在不存在促进剂的情况下计算。
球形初级粒子优选不含孔。
尤其是,优选的羰基铁粉末不含任何线状的初级粒子,尤其是不含在DE 29 19 921A和“Fachberichate fur Oberflachentechnik”,1970年7/8月,145-150页中公开的铁须晶,除了球形初级粒子之外。
图2-4显示了优选使用的具有球形初级粒子的羰基铁粉末的扫描电子显微镜图。
可以用于本发明方法中的具有球形初级粒子的羰基铁粉末可以例如以“Carbonyleisenpulver CN”从BASF AG获得(现在的BASF SE,D-67056Ludwigshafen)。
羰基铁粉末、尤其是具有球形初级粒子的羰基铁粉末是通过气态五羰基化铁(IPC,Fe(CO)5)的热分解获得的,其尤其已经通过蒸馏预先提纯。
球形初级粒子可以部分地聚集,例如达到25-95重量%的程度。
以此方式获得的产物优选通过用氢气还原来后处理。
即使没有任何添加剂,羰基铁粉末也显示有利的催化活性。
羰基铁粉末可以用一种或多种促进剂掺杂,以提高催化活性。
在用于Fischer-Tropsch合成中的铁催化剂中的促进剂例如参见M.Janardanaro,Ind.Eng.Chem.Res,1990,29,1735-1753页,或C.D.Frohning等在“Chemierohstoffe aus Kohle”,1977,219-299页。作为合适的促进剂,催化剂可以含有例如一种或多种以下元素:钒、铜、镍、钴、锰、铬、锌、银、金、钾、钙、钠、锂、铯、铂、钯、钌、硫、氯,在每种情况下是元素形式或离子形式。
羰基铁粉末的总掺杂量(即,如果使用多种掺杂剂的话,促进剂的总和)优选是0.01-30重量%,特别优选0.01-20重量%,非常特别优选0.1-15重量%,例如0.2-10重量%,尤其是0.3-8重量%,在每种情况下基于铁计。在本发明方法的一个具体实施方案中,羰基铁粉末用作为掺杂剂的钾离子和/或钠离子掺杂。
在一个实施方案中,羰基铁粉末特别优选用总共0.01-10重量%、优选0.1-5重量%的钾离子和/或钠离子掺杂(在每种情况下基于铁)。
所述促进剂的施用可以例如通过用所述金属的含水盐溶液浸渍羰基铁粉末来进行,优选碳酸盐、氯化物、硝酸盐或氧化物。
此外,用做促进剂的元素也可以通过在制备羰基铁粉末期间相应气态羰基化合物的热分解施用,例如铜、钴或镍的羰基化物。
在催化剂的另一个实施方案中,羰基铁粉末可以施用到载体材料上。优选的载体材料是TiO2、SiO2、Al2O3、沸石、碳(C)。
在制备烃、尤其烯烃的方法中,任选掺杂和任选负载的羰基铁粉末可以以粒料的形式使用。
粒料是通过本领域技术人员已知的方法获得的。优选的粒料形状是片和环。
粒料也可以在用于工艺中之前再次粉碎,例如通过研磨。
催化剂可以通过在用于工艺中之前用氢气和/或一氧化碳在高温下处理而被转化成对于合成更活泼的状态,尤其在高于300℃的温度下。但是,这种额外的活化不是绝对必要的。
制备烃、尤其烯烃的方法优选在200-500℃范围内的温度下进行,特别优选300-400℃。
绝对压力优选在1-100巴范围内,特别优选5-50巴。
GHSV(气体小时空速)优选在100-10,000、特别优选300-5000体积份的进料流/每体积份催化剂和小时(l/l.h)的范围内。
优选用于进行本发明方法的反应器是:流化床反应器,固定床反应器,悬浮反应器。
在流化床或悬浮反应器中,催化剂优选以粉末形式使用。粉末可以是羰基铁粉末的初级粒子,或是其聚集体。
粉末也可以通过研磨预先制备的粒料而获得。
在固定床反应器中,催化剂用做成型体,优选是粒料的形式。
这些反应器用于Fischer-Tropsch合成的应用例如参见C.D.Frohning等,“Chemierohstoffe aus Kohle”,1977,219-299页,或B.H.Davis,Topics in Catalysts,2005,32(3-4),143-168页。
C2-C8烯烃、尤其是C2-C4烯烃,尤其是乙烯、丙烯和1-丁烯,优选作为在装置C中的烃制备。
用于制备尤其烯烃的工艺得到了产物混合物,其含有具有烯烃碳选择性的烯烃,尤其是α-烯烃碳选择性,此选择性对于C2-C4范围是优选至少30%,例如在30-45%的范围内。在选择性的计算中不考虑所形成的二氧化碳(即,排除CO2)。
在一个特别优选的实施方案中,含有烯烃的产物混合物是以对于C2-C4范围的烯烃碳选择性为至少30%获得的,其中所述至少30%选择性中的至少90%进而由乙烯、丙烯、1-丁烯构成。在选择性的计算中不考虑所形成的二氧化碳(即,排除CO2)。
在一个特别优选的实施方案中,含有烯烃的产物混合物是以对于C2-C4范围的烯烃碳选择性为至少40%获得的,例如在40-45%范围内,其中所述至少40%选择性中的至少90%进而由乙烯、丙烯、1-丁烯构成。在选择性的计算中不考虑所形成的二氧化碳(即,排除CO2)。
所获得的烯烃例如用于制备聚烯烃、环氧化物、羰基合成产物、丙烯腈、丙烯醛、苯乙烯的工艺中。参见:Weissermel等,Industrial OrganicChemistry,Wiley-VCH,Weinheim,2003,145-192页和267-312页。
图1:
本发明一体化方法的优选实施方案的示意流程图[一体化装置包括合成气装置(B)、Fischer-Tropsch装置(C)、CIP装置(A)]。
图2-4:在装置C中用于制备烃、尤其烯烃的工艺中优选使用的具有球形初级粒子的羰基铁粉末(CIP)。
Claims (12)
1.一种一体化方法,其中纯羰基铁粉末(CIP)通过在装置A中分解纯五羰基化铁(IPC)制备;在IPC的分解中释放的一氧化碳(CO)在装置A中用于从铁制备其它CIP,或加入用于制备合成气的相关装置B中,或加入用于从合成气制备烃的相关装置C中,
并且在装置A中制备的CIP用做在相关装置C中的催化剂或催化剂组分以从来自装置B的合成气制备烃。
2.前述权利要求的方法,其中在装置C中获得的已用过的催化剂用做用于在装置A中制备CIP的额外铁源。
3.前述权利要求中任一项的方法,其中在IPC分解之后在装置A中获得的CIP在进一步应用之前用氢气处理。
4.前述权利要求的方法,其中用氢气处理CIP的操作在300-600℃范围内的温度下进行。
5.前述权利要求中任一项的方法,其中在用于制备CIP的装置A中使用的铁预先用氢气处理。
6.前述权利要求的方法,其中用氢气处理铁的操作在300-1000℃范围内的温度下进行。
7.前述权利要求3-4和/或5-6中任一项的方法,其中所用的氢气来自用于制备合成气的相关装置B。
8.前述权利要求中任一项的方法,其中在用于制备其它IPC的装置A中所需的额外CO是来自用于制备合成气的相关装置B。
9.前述权利要求中任一项的方法,其中C2-C4烯烃是在装置C中作为烃制备的。
10.前述权利要求中任一项的方法,其中合成气是通过煤在装置B中的气化制备的。
11.前述权利要求中任一项的方法,其中在用于制备纯CIP的装置A中使用的IPC预先通过蒸馏提纯。
12.前述权利要求中任一项的方法,其中在装置A中的IPC分解是气态IPC的热分解。
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CN104551013A (zh) * | 2014-12-07 | 2015-04-29 | 金川集团股份有限公司 | 一种在分解过程中控制羰基铁粉中粒度的方法 |
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WO2011061183A1 (de) | 2009-11-19 | 2011-05-26 | Basf Se | Verfahren zur selektiven herstellung von leichten olefinen |
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