CN1144621C - 再生涂布有金粒的用于氧化不饱和烃的载体上的催化剂的方法 - Google Patents
再生涂布有金粒的用于氧化不饱和烃的载体上的催化剂的方法 Download PDFInfo
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- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
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- C—CHEMISTRY; METALLURGY
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- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明涉及一种再生涂布金粒的、基于二氧化钛或水合二氧化钛的并且用于在气相中氧化不饱和烃的载体上的催化剂的方法。本发明的特征在于,通过将所述催化剂与水、稀酸或稀过氧化氢溶液接触将其再生并恢复其催化活性。本发明也涉及再生催化剂在气相中将乙烯、丙烯、1-丁烯或2-丁烯氧化的应用。
Description
发明的领域
本发明涉及一种再生催化剂的方法,其中所述催化剂是用于通过在分子氢存在下在气相中用分子氧氧化从不饱和烃催化生产环氧化物。本发明还涉及这些再生后的催化剂用于氧化不饱和烃的应用。
发明的背景
通常在低于200℃下,即使存在催化剂,也不能在气相中用分子氧直接氧化不饱和烃,并且因此很难选择性地生产易被氧化的氧化产物如环氧化物、醇或醛,因为通常这些氧化产物接下来的反应比所使用的烯烃本身的氧化更容易进行。
作为不饱和烃,氧化丙烯构成化学工业中最重要的基本化学品之一。60%以上该物质用于塑料领域,特别是用于生产用来合成聚氨酯的聚醚多元醇。此外,氧化丙烯衍生物在二元醇领域中占有较大的市场,特别是用作润滑剂和防冻剂组合物。
现在,全世界大约有50%的氧化丙烯是通过“氯醇方法”合成的。其余50%是通过“环氧乙烷方法”合成的,并且该趋势正在增加。
在氯醇方法(F.Andreas等人.;Propylenchemie,Berlin 1969)中,首先,通过将丙烯与HOCl(水和氯)反应得到氯醇,接下来通过用石灰分离出HCl,从氯醇得到氧化丙烯。该方法费用大,但当恰如其分地充分利用时,该方法在高转化率下具有高度的选择性(>90%)。在氯醇方法中,氯以无价值的氯化钙或或氯化钠水溶液形式遗失,导致了今天对不含氯的氧化系统的研究。
代替无机氧化剂HOCl,现已选择有机化合物来将氧转移到丙烯中(环氧乙烷方法)。该间接环氧化作用基于下列事实,即有机过氧化物如在液相中的氢过氧化物或过氧羧酸能够选择性地将它们过氧化物中的氧转移到烯烃上,形成环氧化物。在该过程中,氢过氧化物转化为醇并且过氧羧酸转化为酸。氢过氧化物和过氧羧酸分别是由相应的烃或醛通过与空气或分子氧进行自动氧化产生的。间接氧化的一个重要不利之处是氧化丙烯价格对其偶联产品市场价格的经济依赖。
当利用硅酸钛(TS1)作催化剂(Notari等人,US 44 10 501(1983)和US 47 01 428)时,第一次证明,可在非常温和的反应条件下,在液相中用过氧化氢将丙烯环氧化,其选择性>90%(Clerici等人,EP-A230 949)。
在液相中在含铂金属的硅酸钛上用分子氧和分子氢的气体混合物氧化丙烯,其产率低(JP-A 92/352771)。
在EP-A 0 709 360 A1(Haruta等人)中,第一次描述了丙烯直接气相氧化形成氧化丙烯,选择性为100%。这是在还原剂氢存在下,用分子氧的催化气相氧化作用。一种特定的用纳米-数值范围金粒涂布的、包含锐钛矿改进的二氧化钛用作催化剂。丙烯的最大转化率和产率为1%。所描述的Au/TiO2催化剂仅在非常短的时间内获得大约为1%的丙烯转化率。例如,在适中温度(40-50℃)下的典型半衰期仅为100-200分钟。
迄今,通过稀过氧化氢溶液将涂布金粒并且基于硅酸钛的催化剂再生是已知的(Thiele等人,J.Mol.Cat.117,pages 351-356,1997)。
对于开发经济利益型丙烯氧化方法来说,有效地再生催化剂的可能性具有决定的重要性。
发明内容
现已令人惊奇地发现,当用水、稀酸或稀过氧化氢溶液处理已经失活的催化剂时,可再次获得原活性最多80%的催化活性。优选地,用pH4-7.5、优选5.5-6的稀酸(例如稀H2SO4或HF)洗涤已失活的所述催化剂。
因此,本发明涉及一种再生涂布有金粒的并且基于二氧化钛或水合二氧化钛的、用于在气相中氧化不饱和烃的载体上的催化剂的方法,其中通过将所述催化剂与水或与稀酸或与稀过氧化氢溶液接触再生其催化活性。
本发明意义上的处理可在室温或升高的温度下进行。在本发明变体中,升高的压力和/或使用蒸汽可有利地发挥作用。
可在从反应器中除去催化剂后分开进行处理,或者如果在氢存在下催化氧化丙烯,并且用水或氢再生催化剂连续不断地进行则也可以在反应器中进行处理。在本发明该变体的一个实施方案中,在多个彼此连接的空间分离的反应器中同时进行催化和再生操作是有利的。可将这些阶段连接起来使得它们可交替进行。
搅拌再生混合物可能是有利的,但这不是对本发明的应用的要求。
按照本发明,可再生涂布纳米-数值范围金粒的并且基于二氧化钛或水合二氧化钛的载体上的催化剂。优选地,通过“沉积-沉淀”方法来制备这些催化剂。
稀过氧化氢水溶液的浓度通常在1-10wt%,优选在1-4wt%范围。
当本发明再生的催化剂用于氧化不饱和烃时,对所使用催化剂的量和所使用气体的量没有限制。通过催化剂床的气流的“空间速度”通常大约为每小时0.5-20升/g催化剂。
本发明的再生催化剂的应用在气体氧和氢存在下进行。当这些气体在150℃下存在时,除了含水、丙烷和CO2的主要产物外,也形成氧化产品氧化丙烯和丙酮。如果反应温度降到<100℃,优选30-60℃,那么大大地抑制了水的形成并且完全抑制了CO2的形成。已发现,在30-60℃的温度下,除了主要产品氧化丙烯(产率大约为4-5%)外,只有痕量的其它组分(就氧化丙烯而言大约为1%)。水的比例是氧化丙烯比例的2倍(摩尔比)。
包含丙烯、氧、氢和可能存在的惰性气体的气相组成不仅就空-时收率而言是重要的,而且在安全性方面也是重要的。在理论上,可使用所有摩尔组成的气体丙烯/氧/氢/氮气/惰性气体(例如氮气)。用于丙烯氧化的优选的气体比如下:H2/烃/氧/氮:20-80%/10-50%/1-10%/0-50%;优选的H2/烃/氧/氮比是30-75%/15-40%/3-8%/0-10%。反应所使用的分子氧可来源于不同的氧源,例如纯氧、空气和其它氧/惰性气体混合物。
实施例
直接将丙烯氧化为氧化丙烯
标准反应条件:反应器是一个由双壁玻璃构成的固定床管状反应器(直径1cm,长20cm),该反应器通过一个水恒温器在46℃控制温度下加热。将静态混合和温度控制区域排列在反应器的上流。预先将金粒-载体上的催化剂放置在玻璃料上。催化剂填充量为1.8升/克催化剂/小时。通过固体粒子密相输送控制器将气体起始物质自上而下计量加到反应器中。气体起始物质比为O2/H2/C3H6=0.1/1.3/0.4升/小时。将反应气体混合物通过气相色谱法分析,用FID检测器(除CO2以外,适用于所有含氧有机化合物)和热导检测器(适用于固定的气体CO、CO2和H2O)检测。该仪器通过中央数据记录系统控制。
通过TEM(透射式电子显微镜)来监测所有催化剂金粒的大小。
催化剂制备1
在室温和搅拌下,用60分钟的时间,将溶解在100ml去离子水中的100mg H(AuCl4)滴加到10g水合二氧化钛(BET比表面380m2/g,硫酸盐含量0.6%,12%的水)在0.3升去离子水中的悬浮液中。用0.5摩尔碳酸钠溶液调至pH8以便沉淀氢氧化金。将淡黄色悬浮液脱色。将悬浮液在室温下搅拌3小时,并将固体分离出来,洗涤4次,每次用25ml去离子水。将固体在150℃下干燥2小时并在200℃下干燥1小时,接着在空气中,将干燥的接触催化剂在250℃下煅烧2小时并在400℃下煅烧5小时。
得到含0.5wt%金的催化剂。其特征在于:TEM显示所含纳米-数值范围金粒的平均粒径大约为1-6nm。表1列出在标准反应条件(实施例A)下进行催化反应的结果。
催化剂制备2:
将0.104g HAuCl4×4H2O在400ml蒸馏水中的溶液加热到70℃并用0.1N氢氧化钠水溶液调至pH7.5。在充分搅拌下一次加入5g二氧化钛(锐钛矿-金红石混合氧化物;由Degussa提供的P25),并将该批量混合物再搅拌1小时。将该固体洗涤五次,每次用3升蒸馏水,在室温下真空干燥12小时,并在400℃下煅烧4小时。得到含1wt%金的金-二氧化钛催化剂。
表1列出在标准反应条件(实施例B)下进行催化反应的结果。
实施例1-10
已失活并且根据本发明用水、稀酸或稀过氧化氢溶液处理的金载体催化剂的再生和催化活性:
实施例1
将由于反应而失活的并且按照催化剂制备1方法制备的催化剂(2g;氧化丙烯产率为0.6%)悬浮在100ml H2O中,在室温下搅拌1小时,分离并在150℃下干燥1小时。按照标准方法,将因此得到的接触催化剂用于丙烯氧化中。
表1列出催化反应的结果。
实施例2
将由于反应而失活的并且按照催化剂制备1方法制备的催化剂(2g;氧化丙烯产率为0.6%)悬浮在100ml H2O中,在80℃下搅拌1小时,分离并在150℃下干燥1小时。按照标准方法,将因此得到的接触催化剂用于丙烯氧化中。
实施例3
将由于反应而失活的并且按照催化剂制备1方法制备的催化剂(2g;氧化丙烯产率为0.6%)悬浮在100ml H2O中,在室温下搅拌3小时,分离并在150℃下干燥1小时。按照标准方法,将因此得到的接触催化剂用于丙烯氧化中。
表1列出催化反应的结果。
实施例4
将由于反应而失活的并且按照催化剂制备1方法制备的催化剂(2g;氧化丙烯产率为0.6%)悬浮在100ml 3%H2O2溶液中,在室温下搅拌1小时,分离并在150℃下干燥1小时。按照标准方法,将因此得到的接触催化剂用于丙烯氧化中。
表1列出催化反应的结果。
实施例5
将由于反应而失活的并且按照催化剂制备1方法制备的催化剂(2g;氧化丙烯产率为0.6%)悬浮在100ml 6%H2O2溶液中,在室温下搅拌1小时,分离并在150℃下干燥1小时。按照标准方法,将因此得到的接触催化剂用于丙烯氧化中。
表1列出催化反应的结果。
实施例6
将由于反应而失活的并且按照催化剂制备1方法制备的催化剂(2g;氧化丙烯产率为0.6%)悬浮在100ml 3%H2O2溶液中,在50℃下搅拌1小时,分离并在150℃下干燥1小时。按照标准方法,将因此得到的接触催化剂用于丙烯氧化中。
表1列出催化反应的结果。
实施例7
将由于反应而失活的并且按照催化剂制备1方法制备的催化剂(2g;氧化丙烯产率为0.6%)悬浮在100ml用0.05摩尔H2SO4调至pH6的H2O中,在室温下搅拌3小时,分离,在150℃下干燥1小时并在400℃下煅烧2小时。按照标准方法,将因此得到的接触催化剂用于丙烯氧化中。
实施例8
将由于反应而失活的并且按照催化剂制备1方法制备的催化剂(2g;氧化丙烯产率为0.6%)悬浮在100ml用0.05摩尔H2SO4调至pH6.5的H2O中,在室温下搅拌3小时,分离,在150℃下干燥1小时并在400℃下煅烧2小时。按照标准方法,将因此得到的接触催化剂用于丙烯氧化中。
实施例9
将由于反应而失活的并且按照催化剂制备2方法制备的催化剂(2g;氧化丙烯产率为0.2%)悬浮在500ml水中,在室温下搅拌1小时,分离并在150℃下干燥1小时。按照标准方法,将因此得到的接触催化剂用于丙烯氧化中。
表1列出催化反应的结果。
实施例10
将由于反应而失活的并且按照催化剂制备2方法制备的催化剂(2g;氧化丙烯产率为0.2%)悬浮在100ml 3%H2O2溶液中,在室温下搅拌1小时,分离并在150℃下干燥1小时。按照标准方法,将因此得到的接触催化剂用于丙烯氧化中。
表1列出催化反应的结果。
表1
催化剂制备1 | 时间(分钟) | 氧化丙烯产率(%) | 氧化丙烯选择性(%) |
实施例A(活性) | 30 | 5.3 | >97 |
实施例A(失活) | 0.6 | >97 | |
实施例1 | 30 | 3.7 | >97 |
实施例2 | 30 | 3.8 | >97 |
实施例3 | 30 | 3.8 | >97 |
实施例4 | 30 | 3.9 | >97 |
实施例5 | 30 | 3.6 | >97 |
实施例6 | 30 | 3.8 | >97 |
实施例7 | 30 | 4.2 | >97 |
实施例8 | 30 | 4.0 | >97 |
催化剂制备2 | 时间(分钟) | 氧化丙烯产率(%) | 氧化丙烯选择性(%) |
实施例B(活性) | 30 | 1.4 | >97 |
实施例B(失活) | 0.2 | >97 | |
实施例9 | 30 | 0.9 | >97 |
实施例10 | 30 | 1.0 | >97 |
Claims (2)
1.一种再生涂布金粒的并且基于二氧化钛或水合二氧化钛的、用于在气相中氧化不饱和烃的载体上的催化剂的方法,其特征在于通过将所述催化剂与pH为4-6.5的稀酸或与浓度为1-10重量%的稀过氧化氢溶液接触再生其催化活性。
2.如权利要求1所述的方法,其特征在于将通过“沉积-沉淀”方法产生的催化剂再生。
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JP4917549B2 (ja) | 2005-01-14 | 2012-04-18 | ダウ グローバル テクノロジーズ エルエルシー | チタノシリケートの再生、及び活性な酸化触媒の再構成 |
US8742147B2 (en) * | 2010-12-08 | 2014-06-03 | Shell Oil Company | Process for improving the selectivity of an EO catalyst |
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