CN1739851A - 载体金属催化剂、其制备方法和其在直接制备过氧化氢中的用途 - Google Patents

载体金属催化剂、其制备方法和其在直接制备过氧化氢中的用途 Download PDF

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CN1739851A
CN1739851A CNA2005100739688A CN200510073968A CN1739851A CN 1739851 A CN1739851 A CN 1739851A CN A2005100739688 A CNA2005100739688 A CN A2005100739688A CN 200510073968 A CN200510073968 A CN 200510073968A CN 1739851 A CN1739851 A CN 1739851A
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米歇尔·德维克
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Abstract

本发明涉及一种适宜于从氢和氧直接制备过氧化氢的载体金属催化剂，该催化剂基于选自由钯、铂、钌、铑、铱、锇、钬和金组成的M组的至少一种金属。本发明还涉及所述载体催化剂的制备方法，该方法顺序包括：把基于选自M组的至少一种金属的一种或多种盐的溶液浸渍在载体上的步骤，和还原步骤，其特征在于：还原步骤后，用含有溴和溴离子的酸水溶液A处理该催化剂。催化剂的特征在于金属或结晶的聚集体的粒径为0.1－20μm，优选0.1－10μm。优选载体双金属催化剂，例如Pd－Pt，Au－Pt，Pd－Ho和Pd－Au。

Description

载体金属催化剂、其制备方法和 其在直接制备过氧化氢中的用途
本申请是中国发明申请(发明名称：载体金属催化剂、其制备方法和其在直接制备过氧化氢中的用途，申请日：2000年6月7日；申请号00813884.2)的分案申请。
                           技术领域
本发明涉及适宜于从氢和氧直接制备过氧化氢的载体金属催化剂。本发明的目的还在于所述催化剂的制备方法和用所述的催化剂制备过氧化氢的方法。
                           发明背景
从氢和氧直接催化制备过氧化氢的方法的低生产率妨碍了其的开发。进行过许多努力来提高其产率。例如，可提到：US 3 336 112、US 3 361 533、US 4 007 526、US 4 009 252、US 4 279 883和US 4 335 092。这些研究主要是基于基本概念，即用螯合剂(sequestrate)或分解抑制剂来稳定过氧化氢。
还开发了提高直接法过氧化氢的产率的其它方法。因此，US 4 379 778公开了在含有分解抑制剂的含水介质中、在用醛或酮预处理、并还优选也用稀的氢氯酸溶液预处理的铂-碳催化剂的存在下，由氢和氧直接生产过氧化氢的方法。
在US 4 772 458中介绍了在直接过氧化氢制备法的含水反应混合物中使用溴。
最后，US 5 128 114和US 5 352 645介绍了一种制备载于非附聚的均匀多孔氧化硅微球上的基于钯或铂-钯的催化剂，由于使用了柠檬酸铵或脲作为添加剂其是抗磨损的且适宜于直接制备过氧化氢。
US 5 128 114中的实施例12介绍了两步法制备含有约0.05％重量铂和1％重量多孔氧化硅微球上的钯的承载催化剂的方法。通过喷淋干燥Ludox AS40和脲的混合物、然后在650℃的氮气中烧结，来首先制备载体。然后把载体加入到把H2PtCl6和PdCl2溶于水中而预先制备的Pt和Pd的溶液中，加热至60-70℃的温度，用浓HCl酸化直到pH达到约1.2。搅拌生成的混合物，然后喷淋干燥并把最终得到的粉末在300℃的氢气流下还原。
US 5 352 645的实施例15中载体催化剂的制备类似于US 5 128 114中的实施例12，但是有一个不同。这是因为代之以喷淋干燥，把生成的混合物在100℃下真空干燥过夜，然后把干燥的固体物在100℃的氢气流下还原。由此得到顺序为30-50埃的金属晶体。
                           发明详述
本发明人开发了一种制备基于选自由钯、铂、钌、铑、铱、锇、钬和金组成的M组的至少一种金属载体催化剂、特别是载体双金属催化剂的方法。通常，该载体催化剂由选自M组的多数的金属和选自M组的少量金属组成。多数的金属表示占催化剂的0.1-10％重量，优选为0.5-1％重量。少量金属表示为催化剂的约0.001-0.1％重量，优选为0.01-0.05％。
钯和金选作多数金属是有利的。
铂和钬选作少量金属是有利的.
载体双金属催化剂特别优选由钯作为多数金属和铂作为少数金属组成。
本发明的目的还在于由选自M组的多数金属和选自组M的几种少量金属组成的载体多金属催化剂。优选的载体多金属催化剂包括钯作为多数金属，铂和至少一种选自M组的金属作为少量金属。
载体多金属催化剂中的大多数金属的含量实质上同于双金属催化剂中的含量，每种少量金属在催化剂中的存在量为催化剂的约0.001～0.1％重量，优选为0.01-0.05％。
本发明还提供了一种载体单金属催化剂，优选铂或金作为M组的金属组分。金属组分的含量为催化剂的0.1-10％重量，优选为0.5-1％重量。
优选，本发明的载体催化剂的特征在于结晶的金属或几种金属的簇的粒径为0.1-20μm，优选1-10μm。
氧化硅、氧化铝、碳和硅铝酸盐可适宜作为载体。然而，优选使用硅酸盐，且平均粒径为1-50μm的氧化硅颗粒是有利的。还优选使用BET比表面积大于200m2/g、并通常为300-600m2/g的氧化硅。已证明称为28，851-9的Aldrich’s微孔氧化硅是特别有用的。
在所选择的催化剂中铁的量优选小于0.001％重量。
本发明的第二个目的在于一种制备基于选自上述M组的至少一种金属载体催化剂的方法，该方法顺序包括：把基于选自M组的至少一种金属的一种或多种盐的溶液浸渍在载体上的步骤，和还原步骤，其特征在于：还原步骤后，用含有溴和溴离子的酸水溶液A处理该催化剂。
根椐本发明，水溶液A中溴离子的浓度可为20-200mg/l，并优选为20-100mg/l。溴(Br2)的浓度为2-20mg/l，并优选为2-10mg/l。
水溶液A中优选pH为1-3。
例如，可如下制备水溶液A，即把碱或碱土金属溴化物溶于水中，然后把溴加入溴水中以形成浓度优选接近于1％重量，最后可用酸调节pH。当先待制备的催化剂含有Pd时，溶液A由硫酸或磷酸呈酸性。然而优选正磷酸(H3PO4)。
溶液A特别优选含有约100mg/l的NaBr，10mg/l的Br2和10g/l的正磷酸。
通常，用每升溶液A有5-50g的少量载体催化剂来进行该方法。催化剂的量接近于每升溶液10g是优选的。
处理温度为10-80℃并优选为40-60℃。
处理时间可在很宽的限度内变化。该时间可为1-12小时并优选为4-8个小时。
处理后，用任何已知的方法从水溶液A中分离催化剂固体物，然后在100-140℃、并优选接近120℃的温度下干燥。通常在大气压下例如通过通风炉进行干燥。
可任何已知的方法进行载体的浸渍。优选，浸渍步骤包括把所选的载体与选自M组的至少一种金属的一种或多种盐的可能最浓的水溶液接触，以形成浆料。该接触步骤可通过在室温下将金属盐的浓水溶液加入到含有载体的混合器中来进行。混合时间通常取决于所用的载体的量，但为了产率的原因，优选在加入金属溶液后混合约0.5-3小时。
混合之后和还原步骤前，优选对生成的浆料进行过滤，然后排水并最终干燥。为了确保最大程度地排水，推荐仔细压缩过滤后的浆料。排水后，优选在20-50℃的温度下干燥浸渍的载体。优选在有助于慢速结晶并优选在无搅拌的条件下进行干燥。干燥时间通常取决于温度和压力。通常为1-7天，例如在加热到40℃的真空烘箱中，加热48小时足以干燥浸渍和排水后的固体物。干燥也可在室温下进行一周。
一种制备基于选自M组的至少一种金属的载体催化剂的具体方法顺序包括下列步骤：
(a)把选自氧化硅、氧化铝、碳和硅铝酸盐的载体与选自M组的至少一种金属的一种或多种盐的浓水溶液接触，以形成浆料；
(b)过滤、排水、然后在有助于慢速结晶的条件下进行干燥；
(c)还原在步骤(b)中干燥的固体物；
(d)用含有溴和溴离子的酸水溶液A处理步骤(c)中还原的固体物；和
(e)过滤步骤(d)中处理的固体物并在100-140℃的温度下进行干燥。
制备过程的每个步骤中的优选操作条件如上所述。关于还原步骤，可使用现有技术如US5 128 114和US 5 352 645中已用的实验条件。
可使用有助于金属盐溶解以得到浸渍步骤(a)所需的浓水溶液的任何已知方法。特别可提到使用几滴酸、稍稍加热和超声搅拌。
优选在进行还原步骤前研磨步骤(b)中的干燥固体物。实际中，还原中所用的烘箱首先用氮气冲洗足够时间，通常15-60分钟，然后在加热到250-350℃的温度前用氢冲洗(flush)。在选定的温度下固体物的还原时间可为1至3小时。还原后，烘箱回到室温，然后用氮气冲洗。
本发明的第三个目的是从氢和氧直接制备过氧化氢的方法。该方法的特征在于使用上面所述并制备的催化剂。
该催化剂可用于在管式反应器和搅拌反应器中直接制备过氧化氢的方法中。最特别适宜于其中把氢和氧喷入搅拌反应器的含水反应混合物中并把氧引入到搅拌反应器的连续气相中的方法中。
优选该催化剂可用于下述的直接制备过氧化氢的方法中，其中把氢和氧喷入含水反应混合物的下部中并把氧引入到搅拌反应器的连续气相中，氧的加入量使得连续气相的组成在可燃性范围之外。
已证明当搅拌反应器装有沿着单一垂直轴排列的几个涡轮机时，该催化剂是非常有益的。当氢和氧呈小气泡喷入含有反应混合物的下部，其量使得氢的摩尔流速与氧的摩尔流速之比大于0.0416时，得到高于现有技术产率的过氧化氢。
该催化剂已证明特别有利于连续直接制备过氧化氢法，并回收反应剂如氢。
                          实施例
制备催化剂
实施例1
在室温下把下列组分加入到50cm3的去离子水中：
-0.33g PdCl2(Aldrich reference：20，588-5)；
-0.021g H2PtCl6(Aldrich reference：25，402-9)；
和几滴30％重量的HCl以有助于溶解；
-20g微孔氧化硅Aldrich(reference：28，851-9)，其具有下列性能：
平均粒径：25μm
BET表面积：500m2/g
平均孔径：60埃
置于玻璃杯中，用棒磁铁搅拌。然后快速加入述制备的50cm3的金属盐溶液。
在25℃下搅拌1小时30分钟后，制得稠的原料，其在3号玻璃质的陶器上过滤并真空脱水30分钟。把滤饼置于玻璃布上的结晶器中并在40℃的真空烘箱中干燥48小时。接着，在300℃下在60Nl/h的氢气流中还原干燥的固体物1小时30分钟，然后在6小时冷却到室温。
然后在40℃下用2000cm3的含有100mg/l NaBr、10mg/l Br2和10g/l的H3PO4的溶液处理还原的固体物5小时。
接着，把生成的混合物过滤并把该催化剂在120℃的通风烘箱中干燥24小时。
分析后，催化剂含有0.7％Pd和0.03％铂，以重量计。
实施例2
方法同实施例1，唯一区别在于把-还原的固体物直接用作催化剂，而不用溴化的水溶液处理。
实施例3
把氧化硅如实施例1浸渍后，不过滤原料和对过滤后的浆料脱水，而把原料在实验室旋转蒸发器中(带有500cm3有凹槽的圆底烧瓶的Heidolph)进行干燥。烧瓶在120℃的油浴中在40mmHg真空中旋转。蒸发后，还原固体物，然后如实施例1还原和处理固体物。
实施例4
方法如同实施例3，不同的是把还原后的固体物不用溴化的水溶液进行处理外。
实施例5
方法如同实施例3，不同的是浸渍后把原料在大气中放置1周，而不是在旋转蒸发器中干燥。
实施例6
方法如同实施例1，不同的是用Au代替Pd外。
实施例7
方法如同实施例1，不同的是用Ho代替Pt外。
实施例8
方法如同实施例1，不同的是用Au代替Pt外。
制备过氧化氢溶液
通常的操作方法
把选定量的含水反应混合物和催化剂加入到圆柱形反应器中，该反应器的总容量为1500cm3，装有两个或三个直径为45mm的凸缘涡轮机、具有4个垂直的挡板和一束冷却管。
把12g H3PO4、58mg NaBr、5mg Br2加入到1000cm3的去离子水中制备含水反应混合物。
通过把氧气以选择的流速喷入到连续的气相中来对反应器进行加压。用压力调节器来保持压力恒定。通过冷却管组循环恒温水来把液体介质升到所选择的温度。
把搅拌设到1900rpm，并把氧和氢以所选择的流速喷入到底部涡轮机的中部的液相中。
测量离开压力调节器的气体混合物的流速和氢的含量。预期的反应时间后，中断向含水反应混合物中加入氢和氧，并继续喷入氧气到连续气相中直到氢后来消失。然后中断加入氧并把反应器减压。
把过氧化氢水溶液称重并在Millipore过滤器上与催化剂分离。
然后用碘量法评估该溶液以测定H2O2的浓度。H2O2的选择率定义为形成的摩尔数与消耗掉的H2的摩尔数之比的百分数。
转化率定义为消耗掉的H2的体积与喷入的H2的体积之比的百分数。
每次实验的催化剂结果概述于表1中。
                                                                                     表1
实验号 催化剂实验例       反应混合物                                           反应条件                结果
催化剂重 工作溶液重 P(巴)   反应温度(℃)   H2喷入到液相中的(Nl/h) O2喷入到液相中的(Nl/h) O2喷入到气相中的(Nl/h)   涡轮机数 时间(h) H2O2(％)   H2O2选择率   H2转化率(％)
(g) (g)
1 1 6 700 50 20 80 188 1760 2 3   17.5   97   42.0
2 1 6 700 50 20 80 188 1760 2 3   17.4   96   42.0
3 2 6 700 50 20 80 188 1760 2 3   16.2   85   45.0
4 3 6 700 50 20 80 160 1760 2 3   16.3   84   45.8
5 4 6 700 50 20 80 160 1760 2 3   15.4   82   44.0
6 1 6 700 50 41.2 120 240 2640 2 1   12.2   90   60.2
7 5 6 700 50 41.5 120 240 2640 3 1   12.4   86   64.3
8 1 8.5 1000 50 39.0 120 240 2640 3 1   10.6   90   72.5
9 6 8.5 1000 50 40.5 120 240 2640 3 1   6.4   54   71.6
10 7 8.5 1000 50 39.5 120 240 2640 3 1   7.8   76   61.6
11 8 8.5 1000 50 40 120 240 2640 3 1   7.9   73   65.6

Claims (13)

1、一种基于选自由钯、铂、钌、铑、铱、锇、钬和金组成的M组的至少一种金属的载体催化剂，选择的金属的含量为催化剂重量的0.1-10％，其中结晶的金属或几种金属的簇的粒径为0.1-20μm。
2、根椐权利要求1的载体催化剂，其特征在于结晶的金属或几种金属的簇的粒径为1-10μm。
3、根椐权利要求1或2的催化剂，其特征在于选择铂和金。
4、根椐权利要求1或2的催化剂，其特征在于该催化剂是承载的双金属催化剂，其中少量金属的存在量为催化剂的0.001-0.1％。
5、根椐权利要求4的催化剂，其特征在于少量金属是铂。
6、根椐权利要求1-5中任一项的催化剂，其特征在于载体是BET比表面积大于200m2/g的氧化硅。
7、一种基于选自由钯、铂、钌、铑、铱、锇、钬和金组成的M组的至少一种金属的载体催化剂，选择的金属的含量为催化剂重量的0.1-10％，其中结晶的金属或几种金属的簇的粒径为0.1-20μm，其中该催化剂是采用如下方法制备，该方法顺序包括：把基于选自M组的至少一种金属的一种或多种盐的溶液浸渍在载体上的步骤，和还原步骤，其特征在于：还原步骤后，用含有溴和溴离子的酸水溶液A处理该催化剂。
8、根椐权利要求7的载体催化剂，其特征在于结晶的金属或几种金属的簇的粒径为1-10μm。
9、根椐权利要求7或8的催化剂，其特征在于选择铂和金。
10、根椐权利要求7或8的催化剂，其特征在于该催化剂是承载的双金属催化剂，其中少量金属的存在量为催化剂的0.001-0.1％。
11、根椐权利要求10的催化剂，其特征在于少量金属是铂。
12、根椐权利要求7-11中任一项的催化剂，其特征在于载体是BET比表面积大于200m2/g的氧化硅。
13、从氢和氧直接制备过氧化氢的方法，其特征在于使用根椐权利要求1-12中任一项的催化剂。
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AU4931100A (en) 2001-02-05
CN100490969C (zh) 2009-05-27
FR2796311B1 (fr) 2001-09-14
NO325226B1 (no) 2008-02-25

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