CN1252021C - 通过煅烧含金属的碱性离子交换树脂来回收金属的方法 - Google Patents
通过煅烧含金属的碱性离子交换树脂来回收金属的方法 Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 62
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- 238000000034 method Methods 0.000 title claims abstract description 52
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000003456 ion exchange resin Substances 0.000 title claims abstract description 29
- 229920003303 ion-exchange polymer Polymers 0.000 title claims abstract description 29
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- 150000002739 metals Chemical class 0.000 title description 4
- 239000010948 rhodium Substances 0.000 claims abstract description 98
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 96
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- 229920005989 resin Polymers 0.000 claims abstract description 54
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 33
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- 239000007795 chemical reaction product Substances 0.000 claims abstract description 16
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 6
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
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- -1 carboxylate salt Chemical class 0.000 description 8
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- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
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- UMBLTRVSJFEFLD-UHFFFAOYSA-N octadecanoic acid;rhodium Chemical compound [Rh].CCCCCCCCCCCCCCCCCC(O)=O UMBLTRVSJFEFLD-UHFFFAOYSA-N 0.000 description 2
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- 150000003284 rhodium compounds Chemical class 0.000 description 2
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- 150000003839 salts Chemical group 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 150000001869 cobalt compounds Chemical class 0.000 description 1
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- 238000003795 desorption Methods 0.000 description 1
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- 229910001873 dinitrogen Inorganic materials 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 1
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- 238000011069 regeneration method Methods 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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Abstract
一种从键合有金属成分的离子交换树脂中回收金属的方法,包括将反应产物流与碱性离子交换树脂相接触,使得至少一部分的金属作为金属成分键合到该树脂上,并且煅烧该树脂生成含有该金属和/或金属氧化物的灰分,从灰分的残余物中分离该金属和/或其氧化物。该方法用于从烯烃与一氧化碳的均相催化加氢甲酰化反应中回收铑催化剂的有效成分。
Description
本发明涉及金属有效成分的回收,特别涉及铑或钴催化剂有效成分的回收,尤其是从烯烃加氢甲酰化反应催化剂中回收金属有效成分。
醇类,特别是较长链的醇,在工业上是以烯烃与一氧化碳和氢在升高的温度和压力下发生催化加氢甲酰化反应制得的。该反应一般以两阶段进行,如下所述,首先是烯烃的加氢甲酰化,产生C(n+1)醛,接着将醛氢化为醇:
(i)
(ii)
一般,所用的催化剂为过渡金属,特别是钴或铑。该催化剂可以简单金属盐的形式加入到反应中,例如:作为溶解于一些原料烯烃中的羧酸盐。对铑而言,活性催化剂的种类是未知的,虽然其很可能是该金属的羰基配合物。两种催化剂金属的每一种都具有优于另一种的特别优点,且在任何特定情况下的选择都将基于对所需催化剂性质的综合考虑,这些性质包括催化剂的活性、将金属加入到该系统的成本及对目标产物的选择性。铑的优点是与钴相比,是活性更好的催化剂,并更具有选择性,得到更纯的产物。特别是,对中间产物醛而言,铑是一种活性很差的氢化催化剂,这使得醛可从起始反应,以相当纯的形式被回收。醇可在第二阶段中通过氢化醛来形成。当用钴作催化剂时,部分醛一般被氢化成醇。然而,这种氢化是不完全的,因此仍然需要一个单独的氢化步骤。用铑催化剂的一个缺点是铑比钴昂贵的多,而且这使得从产物中回收该金属对于这一方法的经济性很重要。即使铑催化剂的高活性意味着催化剂在产物中的水平一般仅为几个ppm w/w(百万分之一重量份数),这种情况也仍然存在。由于缺乏能从这样低浓度的产物流中回收几乎所有铑有效成分的实用方法,铑的使用受到了抑制。
GB-A-1321275中描述了一种从该反应产物流中回收的方法,其中,通过在一种碱性离子交换树脂上特定的金属羰基氢化物的吸附分离铑。该分离方法需要将压力良好地保持在大气压之上,以确保铑羰基氢化配合物的存在。
在高压下操作的要求,在工业规模的操作中需要复杂且昂贵的容器、阀门和管线,这会限制该方法的应用。没有描述过从树脂中回收铑的方法。
铑的有效成分意味着:经济地运行该方法必须从废树脂中回收铑。因此,需要一种经济的方法从离子交换树脂回收诸如铑的金属,其中该树脂上吸附了该金属化合物。这不像大多数离子交换树脂的再生方法那样简单。我们发现:很难通过简单的离子交换从废树脂中来转移铑有效成分。虽然不希望被该理论所局限,我们认为:起初萃取到树脂中的铑成分可能是不溶的,或者在萃取之后转化为不溶性的成分。不管原因如何,重要的实际结果是需要不同于那些一般用于从离子交换树脂中回收的技术。
GB-A-1355209描述了一种从离子交换树脂中回收铑的方法,通过用低级烷醇、水、水溶性脂肪族胺和氧气来处理键合有铑的树脂。
GB-A-1576514描述了这样一种方法,其中用含氧无机酸和过氧化物处理来自铑催化加氢甲酰化过程中的产物流的蒸馏残余物,然后将得到的铑盐用离子交换剂处理。之后该离子交换树脂进一步用盐酸处理以脱附铑离子,其然后例如在烷基膦和水溶性有机溶剂的存在下与一氧化碳反应,再形成用于加氢甲酰化反应的铑催化剂。
DE2045415描述了一种回收钴的方法,钴是在碱性离子交换树脂上的羰基钴的形式,该方法用低级烷醇和碱水溶液的混合物处理负载有羰基钴的离子交换树脂。
US-A-4388279描述了转移在有机反应所得产物中存在的微量催化剂的方法,例如在加氢甲酰化反应所得醇产物中存在的铑,该方法在温度范围从约室温到约100℃和压力范围为约大气压至约100个大气压的条件下,用固体吸附剂处理前述产物,该固体吸附剂例如为周期表中的IA或IIA族金属化合物、分子筛或离子交换树脂。
含有醇产物的反应混合物必须首先与诸如氢氧化铵水溶液、无水氨或胺化合物的反萃取剂接触。在完成萃取或处理阶段之后,包含几乎所有铑配合物催化剂的反萃取剂溶液从包含醇产物的有机相中分离,并且仅将含微量残余铑的反萃取后的醇物流与固体吸附剂接触。没有建议从离子交换树脂中回收铑金属的方法。
US-A-5208194描述了一种从有机溶剂中回收配位的铑烃基配合物的方法,该方法通过与具有磺酸活性基团的酸性离子交换树脂接触来实现。
本发明的一个目的是提供另一种方法来回收金属有效成分,特别是从铑催化加氢甲酰化反应中回收铑有效成分。
本发明的另一个目的是提供另一种从键合有所述金属有效成分的离子交换树脂中回收该金属有效成分的方法。
因此,本发明提供了一种从反应产物流中回收金属有效成分的方法,包括步骤:
a)将反应产物流与碱性离子交换树脂接触,使得至少一部分金属作为金属成分键合到该树脂上,
b)煅烧含该金属成分的所述碱性离子交换树脂,生成一种包含该金属和/或金属氧化物的灰分,和
c)从灰分残余物中分离所述的金属和/或氧化物。
本发明的第二方面,我们提供了一种从键合有金属成分的离子交换树脂中回收金属有效成分的方法,该方法包括煅烧所述树脂,生成一种含有该金属和/或金属氧化物的灰分,并且从该灰分的残余物中分离上述的金属和/或氧化物。
本发明的方法特别用于在从加氢甲酰化反应产物流中回收钴或铑有效成分。因此优选的金属包括钴和铑。
在本发明的另一方面,我们提供了一种加氢甲酰化的方法,包括:
a)在超室温和超大气压下,将烯烃与一氧化碳及氢在均相铑催化剂的存在下反应,形成含所述铑催化剂的反应产物流,和
b)将至少一部分反应产物流与碱性离子交换树脂接触,使其中至少一部分铑键合到该树脂上。
均相铑催化剂优选是未配位的铑化合物。优选,反应产物流不进行在加氢甲酰化步骤和与树脂接触之间作为中间步骤的用氨或胺化合物的处理。我们发现:在先有技术中用于从产物流中转移大部分金属有效成分的这个步骤是不必要的。
该方法优选包括附加步骤,即,煅烧键合有铑成分的上述碱性离子交换树脂,生成含铑金属和/或金属氧化物的灰分;从灰分的残余物中分离铑和/或氧化物,然后任选将分离的铑或氧化物转化为可在加氢甲酰化反应中用作均相催化剂的形式。
反应产物流任选通过氢化反应步骤和/或被分离成单独的产物流,通常在与离子交换树脂接触之后。这是因为液体产物流的任何进一步处理都需要蒸发,例如:实现汽相氢化或分离的过程,这会在工艺设备上残留一些金属,并且因此会减少易于从产物流中回收的金属的量。本发明当然可以用来处理这样的产物流,该产物流经过上述步骤(a)和(b)之间的进一步处理,而这些进一步的处理不被排除在本发明范围之外。
键合铑或钴成分的离子交换树脂可从已知技术的任何方法得到,其包括用离子交换树脂处理含有铑或钴的物流。已知技术的方法需要来自加氢甲酰化反应的产物流在与离子交换树脂接触之前进行预处理,或者此物流用离子交换树脂的处理是在大大升高的压力下进行的,以使金属成分以羰基氢化物存在。我们发现:与GB1321275所教导的相反,可从加氢甲酰化反应产物流中、不存在GB1321275所述配合物的条件下萃取铑。适当的条件是接近大气压及接近室温或中度超室温,并且铑的萃取是非常接近定量。我们已经成功地通过使用新鲜的离子交换树脂,将反应产物流中的铑浓度从约5ppm减少到约0.1ppm。这代表98%的回收率,但回收率可能会随着离子交换树脂剩余容量的减少而减少。
因此,在本发明的另一方面,我们提供了一种从反应产物流中转移铑有效成分的方法,该方法包括:在压力不超过5巴表压(bargauge),温度不超过120℃的条件下,将反应产物流与碱性离子交换树脂接触,使得至少一部分铑键合到该树脂上,随后煅烧含有铑成分的碱性离子交换树脂,生成含有金属铑和/或铑氧化物的灰分,并且从灰分的残余物中分离所述铑和/或氧化物。
离子交换树脂可以是强或弱碱性树脂。我们发现,由于使用酸性树脂回收效果差,所以酸性树脂是不合适的。这些树脂一般含有氨基作为活性吸附位点,通常为叔胺或季铵盐。在后者的情况下,优选避免使用含例如氯离子的树脂,这些离子可能会影响设备材料。在这种情况下,阴离子可以交换成例如氢氧根离子。特别有用的树脂实例包括来自Rohm and Haas的AmberlystTMA21、A26和A27。
上述温度和压力条件为接近环境的条件。压力小于5巴表压,通常小于4巴表压,更典型的是压力小于2巴表压。在液体产物流与树脂接触之前进行的增加操作压力以加速液体脱气之前,压力可减少至如:<1巴表压。提高压力有助于避免任何已溶解的气体从溶液中溢出从而导致树脂床层的沟流,同时提高压力还有利于反应产物流在树脂床层的流动。通过本发明所用树脂柱的压力降一般为从0.2至0.5巴(bar)。通过新鲜柱的压力降通常要比通过接近废弃的树脂柱的压力降要低,这可能是由于树脂柱中沉积和/或捕集的微粒造成的。
离子交换树脂在较高的温度下吸附铑更迅速,因此吸附过程通常在高于室温的温度下进行。然而,在大气压下,加氢甲酰化反应的醛产物流中的铑成分在温度高于约120℃时是不稳定的。实际上,在从20至100℃的温度下,吸附速度和稳定性之间达到平衡,特别是70至80℃。当处理不同的反应产物流时,最佳温度可能会与此不同,用于吸附的条件应依据要处理的产物流的性质选择。
经离子交换树脂萃取的铑的形式与GB1321257中描述的氢化羰基成分不同,因为该配合物需要更高的氢和/或一氧化碳分压,以便以相当大的浓度存在(相对于存在的铑的总量),这正如J.L Vidal&W.E.Walker,Inorg Chem,1981
20第249-254页所述。上述吸附速度随温度的升高而升高表明,在树脂上形成这些成分的活化能是一个定值。不限于理论,我们由此推测:该吸附过程不是一个简单的离子交换过程。
显然,铑作为一种成分存在与产物流中,在暴露于空气中时大概是经过了氧化反应而改变得到的被氧化形式不能被离子交换树脂有效萃取。因此,在从反应产物流中萃取铑之前,特别优选避免将该反应产物流暴露于空气或具有氧化作用的其他来源。实际上,来自加氢甲酰化的反应产物流在直到生成醇产物的任何后续氢化反应之后都没有故意暴露于空气中。
在一般工业操作上,许多离子交换柱是连结在一起的,这样产物流可被导入到这些管柱的一个或多个当中,废柱可从使用中移除出来,并且填充新鲜树脂以再次使用。虽然这样做不可避免地会使得所需的管线和阀门相当复杂,但是本发明优于GB1321275的一个主要优点是不在高压下进行操作。
我们发现,特别方便的安排是具有三个管柱和相应的管线和阀门,使得任何两个管柱可以流动串联连结,与余下的另一个管柱隔离。在此类操作中,第一和第二个管柱可以串联连结并使用,同时第三个管柱被隔离并移除废树脂并用新鲜树脂置换。正常选择的各管柱尺寸和能力使得一个管柱从反应产物流中萃取铑,在数天优选不超过两周的时间内,排除的铑的浓度接近零,例如:低于0.5ppm,并且通常是约0.1ppm。因此,实际上,各管柱的尺寸和能力及所选管柱的数目取决于要被处理的含铑产物流的量。优选的管柱的不同数目和安排取决于对回收铑的过程的经济评估。
在本发明方法的操作实例中,运行第一及第二管柱直到上游管柱被废弃,使得相当浓度的铑有效成分通过第二管柱。此时,第三个管柱被连结到第二个管柱的下游,隔离并移除第一个管柱、置换树脂,并且重复该方法,以使得能够基本上连续地进行铑萃取。使用串联的两个管柱意味着上游管柱使用至接近全容量时下游管柱仍较新鲜。在第一个管柱吸附铑接近全容量时,第二个管柱保持较为新鲜,并且能够吸附从第一个管柱流出的产物流中的几乎所有铑。从经隔离的管柱中移除并置换废树脂所需要时间一般比一个管柱的实际使用寿命短许多,因此安排基本上为连续的操作并不困难。
树脂容易燃烧而优选以这样的方式控制燃烧,该方式能避免该过程中颗粒的非控制性脱除。因此优选干燥树脂,通常在流动的空气中和100-500℃的温度下。干燥过程必须小心地完成,避免溅出而造成树脂的损失。然后该树脂可在约500至600℃下被引燃,随后含金属树脂的煅烧在约600至约850℃的温度下进行,例如:可达到约800℃。该树脂一般盛在浅盘中,以最大限度地暴露在空气中促进燃烧。当煅烧完成时,将设备冷却,收集灰分准备用于所需金属的分离,并且需要的话,接着转化为催化剂的形式。
当一般碱性离子交换树脂基于含芳香环的聚合物时,例如聚苯乙烯,适当的商业规模的燃烧炉优选包括第二燃烧段,以确保来自起始燃烧的烟雾被燃烧。因此适当的燃烧炉包括燃烧树脂的主燃烧室。将空气吹经过此室,并且用油或气体火焰的加热器引发燃烧,将温度升高到燃烧的温度。然后,来自主燃烧室的排出气体可以通过第二燃烧室,该燃烧室用油或气体火焰加热器保持在800℃。合适设备的实例为Evans Universal的“Maximaster”II。
残余的灰分含有回收的金属有效成分,例如铑或钴;以及其他无机物,如来自反应器设备本身的金属成分或来自交换树脂的其他残余物。回收的金属成分通常以金属或氧化物的形式,或更有可能是以包含两者的混合物的形式存在于灰分中。对金属加工领域的技术人员来说,从灰分中分离回收的金属化合物的方法是公知的,并且取决于金属的性质及需要回收的形式。
存在于灰分中的金属,例如铑或钴,可被提纯并再转化为催化剂,该催化剂在最初形成了这种金属,或转化为该金属的另一种形式。在一种优选的方法中:铑或钴氧化物被转化为能在烯烃的加氢甲酰化中作活性催化剂的铑或钴化合物。例如:当金属为铑且需要再用于加氢甲酰化时,用HCl水溶液或氯处理灰分将其分离,任选在一个转化Rh氧化物为Rh金属的还原步骤之后,得到RhCl3,如果需要,在纯化之后,其与金属羧酸盐-如钠盐-反应,转化为烯烃可溶性羧酸盐,如硬脂酸铑。然后,沉淀的铑羧酸盐可溶于烯烃原料中,再用作催化剂。通过使用该回收技术,我们已经成功地将大于90%的铑原料作为催化剂再用于加氢甲酰化反应。
实际上,可以很方便地由专业的金属加工人员使用贵金属工业专用技术从灰分中回收金属。
作为一个实例:自煅烧离子交换树脂回收得到的铑氧化物,在进一步加工成所需的铑化合物或金属之前,可以通过公知的方法转化为一种铑“海绵”,即:一种高度多孔形式的铑。
下列的实施例具体说明本发明。除非另有说明,所有的份数和百分比均以重量计。
实施例1
铑萃取柱安装如下。将碱性离子交换树脂AmberlystA 21用干燥的甲醇洗涤以移去水分,并在氮气流中干燥。在一个垂直的干燥玻璃管柱中放置22.5ml的干燥树脂(约6g),该管柱配有由恒温控制水浴供水的外层水夹套,内径6mm,并保持在2英寸水压表压(water gauge)(约5mbar)的干燥的氮气气氛中压力。
在铑作为均相催化剂存在的情况下,由混合庚烯原料的加氢甲酰化反应制备的醛反应产物中包含约80%的C8醛,其余的主要是未反应的烯烃和石蜡副产物,该醛反应产物用作萃取管柱的原料。这些醛反应产物在萃取管柱的进口被预热到80℃。由80℃的水通过水夹套将管柱的温度保持在80℃。为启动该管柱,将反应产物流以向上的流动方向加入到管柱中,以此来扩展床层约50%的体积并移除气泡。然后萃取以向下的流动方向进行,保持管柱中的液面在树脂顶部之上,以此将树脂保持在淹没状态。醛产物流的流速为约每小时450ml。萃取连续进行了27天,并对进入和输出流的铑浓度进行了间隔性的检测。检测结果列于如下表1。
表1
在线的时间(天) | 铑浓度(ppm w/w) | |
进料流 | 出料流 | |
1 | 5.3 | 0.1 |
5 | 5.3 | 0.2 |
10 | 5 | 0.4 |
15 | 5.3 | 0.4 |
20 | 4.8 | 0.9 |
25 | 4.8 | 1.2 |
27 | 4.8 | 1.2 |
表1的数据表明:铑的有效萃取保持了至少15天。在操作27天之后,从管柱中移除的树脂中铑的含量为1012mg,相当于每100毫升干树脂4.5克的铑(约每公斤树脂160g)。由于树脂的寿命较长,能使多管柱、特别是三管柱在如上所述的操作下相对简单地运行。
实施例2
在用铑作为均相催化剂进行C12至C14烯烃的加氢甲酰化反应,从得到的醛反应流萃取铑有效成分。所用的萃取管柱如实施例1所述,但尺寸更大:内径为13mm,使用的树脂填充为87ml(约24g)。萃取管柱的来自连续合成器进料含有约95%的C13-15醛。进料在脱气容器中被减至大气压,并且在排除空气的情况下被泵入萃取管柱。管柱的温度控制在70℃,且流速为808ml.hr-1。萃取连续进行11天,该期间管柱进料流中铑的浓度在2.9和4.7ppm之间变化,并且出口流的铑浓度被恒定在0.1ppm。
实施例3
在存在铑和钴作为混合的均相催化剂的情况下,由混合庚烯原料的加氢甲酰化反应制备醛反应产物其含有约80%的C8醛,其余的主要是未反应的烯烃和石蜡副产物,该醛反应产物用作萃取管柱的进料,萃取管柱的构造如实施例1所描述。萃取温度为80℃。铑的浓度从5ppm减少至0.15ppm。钴的浓度从15ppm减少至4ppm。
实施例4
存在于废弃碱性离子交换树脂中的铑,在类似于实施例1和2所述的条件下产生,在两室燃油燃烧器(埃文斯通用(EvansUniversal)“Maximaster”II)中燃烧进行回收。该树脂用甲醇洗涤以除去残余的醛,然后用水洗涤以除去甲醇。将湿树脂(10kg)铺在一个尺寸为300mm×850mm×75mm的钢盘上,并置于燃烧器的主燃烧室内。开始,在空气流(90m3/小时)中加热树脂到500℃35分钟干燥。在干燥期间,近距离观察显示:盘中没有由于“飞溅”或热冲击而损失树脂。然后将温度用15分钟升高到580℃,并引燃该树脂。再经15分钟后,主燃烧室的温度达到800℃,并且在700~800℃再保持45分钟,以使煅烧完成。煅烧期间,第二燃烧室的空气流在70m3/小时温度保持在约800℃,以燃烧来自主燃烧室的分解产物。煅烧完成后,将灰分冷却。该灰分含有65%的金属及金属氧化物形式的铑,以及微量的其他金属(如:铁)和其氧化物。然后用HCl和氯处理该灰分以生成三氯化铑溶液。通过与硬脂酸钠溶液反应得到催化用的铑。硬脂酸铑从溶液中沉淀出来,分离,并溶解于烯烃原料中,形成可在另外的加氢甲酰化反应中用做催化剂的原料溶液。
Claims (8)
1.一种加氢甲酰化的方法,包括的步骤为:
a)将烯烃与一氧化碳及氢在超室温和超大气压的压力下、在包括铑或钴、或铑和钴的混合物的均相催化剂的存在下反应,形成含有所述铑和/或钴催化剂的加氢甲酰化反应产物流;并且
b)将至少一部分的加氢甲酰化反应产物流与碱性离子交换树脂在不超过5巴表压的压力和不超过120℃的温度下接触,使得其中至少一部分铑和/或钴键合到该树脂上。
2.如权利要求1所述的加氢甲酰化方法,进一步包括的步骤为:
c)煅烧键合有铑和/或钴成分的所述碱性离子交换树脂,生成含铑和/或钴作为金属和/或金属氧化物的灰分;
d)从灰分残余物中分离该金属和/或氧化物;和
e)任选将分离后的金属和/或氧化物转化为一种能在步骤(a)中用作均相催化剂的形式。
3.如权利要求1或2所述的加氢甲酰化方法,进一步包括:在加氢甲酰化反应产物流与离子交换树脂接触之后,将其经过一个加氢甲酰化反应步骤和/或一个分离步骤。
4.如权利要求1或2所述的方法,其中加氢甲酰化反应产物流与碱性离子交换树脂在小于2巴表压的压力下接触。
5.如权利要求1或2所述的方法,其中加氢甲酰化反应产物流在与离子交换树脂接触之前被脱气。
6.如权利要求1或2所述的方法,其中至少两个离子交换柱连接在一起,使得加氢甲酰化反应产物流被导到一个或多个所述管柱中,并且至少一个管柱可从加氢甲酰化反应产物流中被隔离。
7.如权利要求1或2所述的方法,其中至少两个离子交换柱被连接在一起,使其串联操作。
8.如权利要求1或2所述的方法,其中在煅烧之前,该树脂在100至500℃之间的温度下干燥。
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WO2004071456A2 (en) | 2003-02-11 | 2004-08-26 | Plus Chemicals, B.V. | Process for preparing simvastatin having controlled ranges of simvastatin dimer content |
DE10357718A1 (de) | 2003-12-09 | 2005-07-21 | Basf Ag | Verfahren zur Herstellung von Tricyclodecandialdehyd |
AR054096A1 (es) * | 2004-11-12 | 2007-06-06 | Monsanto Technology Llc | Recuperacion de metales nobles de corrientes de proceso acuosas y proceso de preparacion de n-(fosfonometil)-glicina |
US7902398B2 (en) | 2007-04-25 | 2011-03-08 | Celanese International Corporation | Method and apparatus for carbonylation with reduced catalyst loss |
DE102008057857B4 (de) * | 2008-11-18 | 2014-09-11 | Oxea Gmbh | Verfahren zur Rückgewinnung von Rhodium aus Rhodiumkomplexverbindungen enthaltenden wässrigen Lösungen |
DE102009001230A1 (de) | 2009-02-27 | 2010-09-02 | Evonik Oxeno Gmbh | Verfahren zur Abtrennung und teilweiser Rückführung von Übergangsmetallen bzw. deren katalytisch wirksamen Komplexverbindungen aus Prozessströmen |
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TWI709566B (zh) | 2015-09-30 | 2020-11-11 | 美商陶氏科技投資公司 | 用於製造有機磷化合物的方法 |
KR101668727B1 (ko) * | 2015-11-25 | 2016-10-25 | 한국원자력연구원 | 방사성 핵종을 포함하는 폐이온 교환수지 처리방법 및 장치 |
CN111439875B (zh) * | 2020-03-31 | 2022-05-31 | 东莞市逸轩环保科技有限公司 | 一种电镀铑钌清洗废水的铑钌资源化回收及水回用工艺 |
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JPS5845411B2 (ja) * | 1978-05-10 | 1983-10-08 | 東亜燃料工業株式会社 | ヒドロホルミル化方法 |
US4388279A (en) * | 1981-06-03 | 1983-06-14 | Uop Inc. | Recovery of metal values from organic reaction products |
US4599206A (en) * | 1984-02-17 | 1986-07-08 | Union Carbide Corporation | Transition metal complex catalyzed reactions |
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US5208194A (en) * | 1992-02-25 | 1993-05-04 | Arco Chemical Technology, L.P. | Recovery of group VIII transition metals from organic solutions using acidic ion-exchange resins |
US5312996A (en) * | 1992-06-29 | 1994-05-17 | Union Carbide Chemicals & Plastics Technology Corporation | Hydroformylation process for producing 1,6-hexanedials |
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TWI229069B (en) | 2005-03-11 |
NO20031007D0 (no) | 2003-03-04 |
BR0113685A (pt) | 2003-07-15 |
CZ303102B6 (cs) | 2012-04-04 |
NO20031007L (no) | 2003-05-02 |
BR0113685B1 (pt) | 2012-07-24 |
ZA200301323B (en) | 2004-02-05 |
WO2002020451A1 (en) | 2002-03-14 |
DE60114647T2 (de) | 2006-07-27 |
KR100741261B1 (ko) | 2007-07-19 |
KR20030036749A (ko) | 2003-05-09 |
CA2422477A1 (en) | 2002-03-14 |
NO328970B1 (no) | 2010-07-05 |
ATE308498T1 (de) | 2005-11-15 |
GB0021715D0 (en) | 2000-10-18 |
JP5534631B2 (ja) | 2014-07-02 |
EP1315693B1 (en) | 2005-11-02 |
PL360580A1 (en) | 2004-09-06 |
AU2001282315A1 (en) | 2002-03-22 |
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