CN114805449A - 一种水溶性Pd(II)配合物及其合成方法和作为催化前驱体的用途 - Google Patents
一种水溶性Pd(II)配合物及其合成方法和作为催化前驱体的用途 Download PDFInfo
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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Abstract
本发明公开了一种水溶性Pd(II)配合物及其合成方法和作为催化前驱体的用途。该水溶性Pd(II)配合物的化学名为二(亚硝基)草酸合钯酸铵,分子式为(NH4)2[Pd(NO2)2(C2O4)]·nH2O(n为结晶水的数目)。本发明的Pd(II)配合物的合成是以PdCl2或钯湿法精炼得到的中间产物[Pd(NH3)2Cl2]为起始原料,先与氨水反应,转化为[Pd(NH3)4]Cl2,然后与过量的NaNO2反应,得到trans‑[Pd(NH3)2(NO2)2],最后与草酸反应,得到目标产物(NH4)2[Pd(NO2)2(C2O4)]·2H2O。该配合物不含氯和其他对催化剂有害的元素(如K、Na、S、P),水溶性高,热分解温度低,用作催化前驱体制备出的负载型钯基催化剂具有很高的催化活性,是一个很好钯催化前驱体。
Description
技术领域
本发明涉及一种水溶性Pd(II)配合物及其合成方法和作为催化前驱体的用途,该水溶性Pd(II)配合物不含Cl、P、S、Na、K等元素,属于化学化工领域。
背景技术
钯(Pd)属于铂族的一种金属,其独特的d电子结构赋予负载型钯基催化剂具有卓越的催化性能,广泛应用于石油化工、医药和精细化工、工业有害废气和汽车尾气的净化处理等各个领域。
目前,制备负载型钯基催化剂的主流方法为化学浸渍法[1-3],主要工序包括载体的选择和预处理、液相负载、干燥还原(或煅烧)。载体主要有活性炭、氧化铝、二氧化硅、二氧化钛,液相负载是其关键步骤。液相负载涉及到催化前驱体的选择和使用。催化前驱体为可溶性的钯化合物,系负载型钯基催化剂的活性成分来源,已有大量的研究表明:前驱体的组成、结构和理化性质对最终催化剂的性能有着重要的影响,不同用途的催化剂对前驱体的组成和结构有着不同的要求。
目前,工业上常用的钯催化前驱体主要是氯化钯PdCl2、硝酸铂Pd(NO3)2溶液(含10%硝酸)、醋酸钯Pd(OAc)2、乙酰丙酮钯Pd(acac)2。其中,氯化钯、乙酰丙酮钯主要用于Pd/C催化剂的生产;汽车尾气净化催化剂(Pd-Rh-稀土氧化物/Al2O3)和有机废气(VOCs)净化催化剂(Pd-Pt/Al2O3、Pd-Pt/TiO2)的生产主要采用硝酸铂溶液作催化前驱体,环已烷行业苯脱硫催化剂(也称吸附剂)Pd/Al2O3的生产则以醋酸钯为前驱体,这是因为含氯的前驱体会引起这三类催化剂中有氯离子的残留而氯离子将显著降低催化剂的耐高温性能和使用寿命[4-6]。
硝酸钯在水中不稳定、很快分解成固态的氧化钯,但在较高浓度的硝酸介质中可稳定存在,因此,市场上硝酸钯均以10%硝酸的溶液形式销售。氯化钯不溶于水,需要采用较高浓度的盐酸作溶媒。盐酸和硝酸皆为强酸,在较高浓度时会腐蚀载体(氧化铝和二氧化钛)、破坏载体表面的结构,影响负载效果和催化活性。同时,使用硝酸钯溶液和氯化钯作为前驱体,在催化剂的干燥、还原或者煅烧过程中会分解出酸雾气(如氮化化物和盐酸),不利于清洁生产。
醋酸钯和乙酰丙酮钯不溶于水,负载工序前需要采用有机溶剂(如丙酮、氯仿)溶解,而工业上大量使用易燃和易挥发性有机溶剂,会带来安全和环保隐患。
另外,多年的铂族金属催化剂的研究和应用还表明[7,8]:P和S元素与钯有很强的键合作用,将导致催化剂中毒。Na+、K+在高温下会发生迁移,引起活性金属的团聚和烧结现象,一般认为:P、S、Na、K为对负载型钯基催化剂有害的元素。工业上要求选用不含Cl、P、S、Na、K元素的钯化合物作催化前驱体,以使生产出了的最终催化剂产品中无Cl、P、S、Na、K的残留。
因此,研制一种既有较高的水溶性又不含Cl、P、S、Na、K元素的钯化合物作催化前驱体,具有重要的应用前景。我们团队曾经合成出包括硝酸四氨合钯[Pd(NH3)4](NO3)2、二(草酸)合钯酸铵(NH4)2[Pd(C2O4)2]·2H2O在内多种这样的钯化合物,但它们作为钯催化前驱体制备的钯基催化剂的性能并不优越。同时,硝酸四氨合钯合成过程涉及到使用硝酸银沉淀氯离子、制造成本较高;(NH4)2[Pd(C2O4)2]·2H2O不稳定,即使室温放置也会发生自身氧化还原反应,析出金属钯。这些缺点导致它们不能满足工业应用的要求。
上述文献[1-8]为:
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[3]孙锦宜编著,《工业催化剂的失活和再生工程》.化学工业出版社,2006。
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发明内容
本发明的目的是解决工业上使用的PdCl2、硝酸铂Pd(NO3)2溶液(含10%硝酸)、醋酸钯Pd(OAc)2、乙酰丙酮钯Pd(acac)2作催化前驱体的不足和缺点,提供一种不含Cl、P、S、Na、K等元素的高水溶性Pd(II)配合物,同时还具有优越的应用性能、制备成本可控的优点,以替代现有的钯催化前驱体。
本发明的水溶性Pd(II)配合物是二(亚硝基)草酸合钯酸铵,分子式为(NH4)2[Pd(NO2)2(C2O4)]·nH2O,其中,n为结晶水的数目(n通常为2),具有如下的化学结构:
与现有的钯催化前驱体相比较,本发明的Pd(II)配合物具有如下特点:
(1)不含对催化剂有害的氯、硫、磷、钠、钾元素;
(2)具有很高的水溶性,室温在纯水中溶解度大于400g/L(相当于120gPd/L),且在水中很稳定,室温放置2天或在60℃下保持5小时溶液颜色不会变化,也不会出现沉淀的现象,在100g/L浓度下溶液的pH约4-5之间。
(3)固态室温放置很稳定。在模拟空气气氛和氮气中,能在较低的温度下(<190℃)发生热分解反应,生成金属钯(见图2、图3),这有利于催化剂制备的热还原或煅烧工序节省能源。且分解产物为Pd、CO2、N2和H2O,有利于工业上的清洁生产。
其对应的热分解反应为:
(5)以本发明的Pd(II)配合物作催化前驱体、采用水相负载制备的苯脱硫催化剂(又称吸附剂)Pd/γ-Al2O3的脱硫效果明显优于工业上以醋酸钯为前驱体、采用有机相负载制备得到的商业催化剂,也明显优于以硝酸四氨合钯或二(草酸)合钯酸铵为前驱体同等条件下制得的催化剂。(见实施例3)
(6)以本发明的Pd(II)配合物作催化前驱体,采用化学水相浸渍法制备出了的工业有机废气净化处理催化剂Pd-Pt/γ-Al2O3,对挥发性有机物的催化氧化效率明显高于以硝酸钯溶液作催化前驱体制备的商业催化剂(见实施例4)。
本发明的Pd(II)配合物的合成采用以下路线和三个步骤来完成:
第一步:以市售的PdCl2或钯湿法精炼得到的中间产物[Pd(NH3)2Cl2]为起始原料,在50-70℃温度下,滴加氨水至PdCl2或[Pd(NH3)2Cl2]全部溶解,控制最终溶液的pH=9-10,溶液在50-70℃下减压浓缩至近干、以除去可能过量的氨。再加水溶解,膜滤,得到黄色的[Pd(NH3)4]Cl2溶液。
第二步:取含一定量[Pd(NH3)4]Cl2的溶液。称取化学计量150%-250%的NaNO2,用水溶解,配制成近饱和的溶液,滴加入[Pd(NH3)4]Cl2溶液,在50-70℃下搅拌反应,析出难溶于水的trans-[Pd(NH3)2(NO2)2]浅黄色沉淀,继续反应1-2小时,冷却到室温,过滤收集、分别用水洗涤和乙醇洗涤,以除去氯离子和过量的NaNO2。在65℃烘干,得到trans-[Pd(NH3)2(NO2)2],产率大于95%。
第三步:制备出一定量的草酸溶液,加热至50-60℃,在搅拌状态下,加入化学计量102%trans-[Pd(NH3)2(NO2)2]固体,搅拌反应1小时,trans-[Pd(NH3)2(NO2)2]几乎全部溶解,冷却至室温,过滤除去少量的不溶碴,得到红色溶液,冷冻干燥或在50℃下减压浓缩至干,得到橙黄色的目标产物(NH4)2[Pd(NO2)2(C2O4)]·2H2O,产率大于97%。
涉及的主要反应为:
第一步反应:
第二步反应:
[Pd(NH3)4]Cl2+2NaNO2→trans-[Pd(NH3)2(NO2)2]↓+2NaCl+2NH3
第三步反应:
trans-[Pd(NH3)2(NO2)2]+H2C2O4→(NH4)2[Pd(NO2)2(C2O4)]
本发明的所提供的(NH4)2[Pd(NO2)2(C2O4)]·2H2O合成方法具有反应条件温和、操作简单、产率高、成本可控的特点,适合于批量生产。
附图说明
图1:本发明的水溶性Pd(II)配合物二(亚硝基)草酸合钯酸铵的化学结构。
图2:本发明的(NH4)2[Pd(NO2)2(C2O4)]·2H2O在模拟空气中的热重曲线图(TG-DTA)。
图3:本发明的(NH4)2[Pd(NO2)2(C2O4)]·2H2O在氮气中的热重曲线图(TG-DTA)。
图4:实施例4的催化剂样件的制备流程图。
具体实施方式
实施例1:(NH4)2[Pd(NO2)2(C2O4)]·2H2O的合成
称取100克(564mmol)PdCl2,加入200mL,加热至60℃,在搅拌下滴加30%氨水至PdCl2全部溶解,所消耗的氨水约165mL,此时pH=10,溶液在60℃下减压浓缩至近干后,加200mL水溶解,得到浅黄色的[Pd(NH3)4]Cl2溶液,再加热至60℃,在搅拌下,慢慢加入200mL、含156克(2256mmol)NaNO2的水溶液,析出难溶于水的trans-[Pd(NH3)2(NO2)2]淡黄色沉淀,继续反应1小时,冷却到室温,过滤收集、用60mL水洗涤3次后再用60mL乙醇洗涤1次,在65℃下烘干4小时,得trans-[Pd(NH3)2(NO2)2]127克,产率约97%。
称取65克(516mmol)H2C2O4·2H2O,加入400mL的水,加热至55℃直至全部溶解。在搅拌状态下,加入122克(526mmol)trans-[Pd(NH3)2(NO2)2]固体,搅拌反应1小时,trans-[Pd(NH3)2(NO2)2]几乎全部溶解,形成红色溶液,冷却至室温,过滤除去少量的不溶碴,母液冷冻干燥,得到橙黄色的(NH4)2[Pd(NO2)2(C2O4)]·2H2O 184克,产率约98%。
实施例2:(NH4)2[Pd(NO2)2(C2O4)]·2H2O的合成
称取50克(237mmol)[Pd(NH3)2Cl2],加入100mL,加热至60℃,在搅拌下滴加30%氨水至[Pd(NH3)2Cl2]全部溶解,所消耗的氨水约37mL,此时pH=9,溶液在60℃减压浓缩至近干,加100mL水溶解,得到浅黄色的[Pd(NH3)4]Cl2溶液,再加热至60℃,在搅拌下,慢慢加入100mL、含65克(948mmol)NaNO2水溶液,析出难溶于水的trans-[Pd(NH3)2(NO2)2]淡黄色沉淀,继续反应1小时,冷却到室温,过滤收集、用30mL水洗涤3次后再用30mL乙醇洗涤1次,然后在65℃下烘干4小时,得trans-[Pd(NH3)2(NO2)2]53克,产率约96%。
称取26.5克(211mmol)H2C2O4·2H2O,加入150mL的水,加热至55℃直至全部溶解。在搅拌状态下,加入50克(215mmol)trans-[Pd(NH3)2(NO2)2]固体,搅拌反应1小时,trans-[Pd(NH3)2(NO2)2]几乎全部溶解,形成红色溶液,冷却至室温,过滤除去少量的不溶碴,母液用旋转蒸发器在55℃下浓缩至干,得到橙黄色的(NH4)2[Pd(NO2)2(C2O4)]·2H2O 76克,产率约99%。
将(NH4)2[Pd(NO2)2(C2O4)]·2H2O样品送组成和结构测试,结果如下:
<1>元素分析:测定值Pd 29.4%、C 6.62%、H 3.38%、N 15.4%(计算值Pd29.7%、C6.70%、H 3.34%、N 15.6%);
<2>IR(cm-1,KBr):3435(s,ν(H2O)、3232,3177(s,ν(NH4 +))、1612(s,νas(COO-))、1401(s,νs(COO-))、1137,1311(s,νs(NO2 -))、558(w,ν(Pd-O)、527(w,ν(Pd-NO2);
<3>13C NMR(D2O,ppm):167(COO-);
<4>MS-ESI-:m/e 140[(M-2NH4-2H2O)/2,104Pd]
测定结果符合本发明的(NH4)2[Pd(NO2)2(C2O4)]·2H2O化学结构。
实施例3:以本发明Pd(II)配合物作为前驱体制备苯脱硫催化剂(又称吸附剂)及性能评价1.催化剂Pd/Al2O3的制备
(1)工业参比催化剂
称取Pd含量为1g的醋酸钯Pd(OAc)2于60g丙酮中,在40°下加热溶解。将质量为100g直径约2.3mm的γ-Al2O3小球浸渍于上述溶液中2h,然后过滤出其中的固体并在120℃下干燥2h,置于马弗炉中中在400℃下焙烧4小时,再在150℃下H2(20ml/min)氛围中还原4h,冷却到室温,得到工业参比催化剂,Pd含量1%,样品编号Pd/Al2O3-OAc。
(2)测试催化剂
称取Pd含量为1g的硝酸四氨合钯(简称Pd-S5)或二(草酸)合钯酸铵((简称Pd-X5)或本发明的Pd(II)配合物(简称Pd-X6)溶于60g水中,将质量为100g直径约2.3mm的γ-Al2O3小球浸渍于上述溶液中2h,然后过滤出其中的固体并在120℃下干燥2h,,置于马弗炉中在400℃下焙烧4小时,再在150℃下H2(20ml/min)氛围中还原4h,冷却到室温,得到测试催化剂,Pd含量1%,样品编号分别为Pd/Al2O3-S5,Pd/Al2O3-X5,Pd/Al2O3-X6。
2.脱硫活性评价方法
吸附实验在固定床反应器上进行。实验过程如下:将70g吸附剂置于管内恒温区,用氮气除去管内空气。噻吩苯(噻吩浓度为50ppm)在进入反应管前,先通过流动泵进入预热器预热至170℃。在150℃下,苯以4mL/min的流速通过吸附床。收集流出的苯在配备火焰光度检测器(FPD)的Shimadzu GC-2010Plus气相色谱上分析。吸附硫容计算公式如下:
其中q是吸附剂的吸附硫容量(mg/g),v是任何时间t(h)的进料体积流量(mL/min),m是吸附剂的重量(g),C0和Ct分别是苯中噻吩的初始浓度和瞬时浓度。
3.测试结果
对采用不同钯催化前驱体制备的4种Pd/Al2O3催化剂进行了12小时的固定床吸附脱硫活性测试,测试结果见表1,12小时后4种催化剂累计吸附硫容分别为1.479、1.518、1.419、1.747mg/g。即以本发明的Pd(II)配合物为前驱体制备的苯脱硫催化剂Pd/Al2O3-X6,吸附硫的效果最好,优于工业苯脱硫催化剂,也好于以硝酸四氨合钯或二(草酸)合钯酸铵为前驱体制备的催化剂。
表1.采用不同钯前驱体制备的Pd/Al2O3吸附硫的量(mgSulfur/g Catal)
样品编号 | 2h | 4h | 6h | 8h | 10h | 12h |
Pd/Al<sub>2</sub>O<sub>3</sub>-OAc | 0.351 | 0.711 | 1.061 | 1.344 | 1.428 | 1.479 |
Pd/Al<sub>2</sub>O<sub>3</sub>-S5 | 0.332 | 0.665 | 1.046 | 1.394 | 1.494 | 1.518 |
Pd/Al<sub>2</sub>O<sub>3</sub>-X5 | 0.315 | 0.674 | 0.923 | 1.116 | 1.301 | 1.419 |
Pd/Al<sub>2</sub>O<sub>3</sub>-X6 | 0.373 | 0.658 | 1.045 | 1.271 | 1.576 | 1.747 |
将催化剂样品进行XRD、XPS、TEM测试和分析,结果表明:以Pd-X6作催化前驱体,可以加强Pd/Al2O3催化剂中Pd与Al的相互作用,阻止Pd纳米颗粒的迁移和团聚,增加分散度,从而提高脱硫活性。
实施例4:以本发明Pd(II)配合物作为前驱体制备VOCs催化剂及性能评价
1.主要原材料和仪器、设备
陶瓷载体(300目),La改性氧化铝,稀土复合氧化物,乙醇胺羟基铂,硝酸钯溶液,本发明Pd(II)配合物(简称Pd-X6),醋酸,氢氧化钡,羟乙基纤维素,拟薄水铝石,硝酸,去离子水。天平,搅拌器,烘箱,马弗炉,催化剂小样评价装置SGB-2#,MKS红外分析仪,打孔器等。
2.催化剂样件的制备及催化性能测试方法
1.样件制备
如图4所示,催化剂样件制备包括将基础涂层料与贵金属溶液混合、搅拌,经调节pH后进行焙烧烘干生成贵金属涂层料,然后制浆并涂覆于催化剂载体孔面,经烘焙得到催化剂样件。该样件中贵金属负载量1.8g/L,Pt:Pd=5:1。
2.催化活性测试方法
截取直径1in、高2in催化剂样品,四周用石棉布包裹后装入样品管内,设备升温,温度达到反应所需数值时通入反应气,测试温度为350~500℃,温度梯度为50℃;反应气流量根据空速20000/h、一氧化碳浓度4000ppm、甲烷浓度1000ppm、丙烷浓度1000ppm、氧气浓度5%、水蒸气浓度0~20%计算确定;尾气浓度由气体红外分析仪实时检测。
3、测试结果
两种钯前驱体制备的催化剂在相同条件下对一氧化碳、甲烷和丙烷氧化转化率的测试数据见表2-表4。
(1)从表2的测试数据可知,二种不同的钯化合物Pd-X6、硝酸钯溶液制备的催化剂在不同温度、水含量下对CO氧化转化率大于99.5%,达到使用技术要求。
表2.采用两种钯前驱体制备的催化剂对CO的氧化转化效果
(2)从表3测试数据可知,二种不同的钯化合物Pd-X6、硝酸钯溶液制备的催化剂对甲烷氧化转化率与温度呈正相关性,与水含量大小呈负相关性。在相同的反应条件下,特别是较低的温度下,二种不同的钯化合物制备的催化剂对甲烷的氧化转化率为Pd-X6>>硝酸钯溶液。
(3)表4为2种不同的钯化合物制备的催化剂在相同条件下对丙烷氧化转化率的测试数据。丙烷氧化转化率与温度呈正相关性,与水含量大小呈负相关性;随着温度升高,水对丙烷转化率影响变小,反应温度450℃及以上时,丙烷转化率大于99.5%;在相同的反应条件下,两种钯化合物制备的催化剂对丙烷的转化率为Pd-X6>硝酸钯。
表3.采用两种不同钯前驱体制备的催化剂对甲烷的氧化转化效果
表4.采用两种不同钯前驱体制备的催化剂对丙烷的氧化转化效果
因此,以本发明的Pd(II)配合物作催化前驱体制备的催化剂,对有机废气的净化处理效果明显优于以硝酸钯溶液为前驱体制备出来的工业催化剂。
Claims (6)
2.根据权利要求1所述的水溶性Pd(II)配合物,其特征在于:所述结晶水的数目n为2。
4.根据权利要求3所述的合成方法,其特征在于,包括以下步骤:
第一步:以市售的PdCl2或钯湿法精炼得到的中间产物[Pd(NH3)2Cl2]为起始原料,在一定温度下,滴加氨水至PdCl2或[Pd(NH3)2Cl2]全部溶解,控制溶液最终的pH=9-11,溶液在一定温度下减压浓缩至近干后,再加水溶解,得到淡黄色的[Pd(NH3)4]Cl2溶液;
第二步:取以上含一定量[Pd(NH3)4]Cl2的溶液,称取化学计量150%-250%的NaNO2,用水溶解,配制成近饱和的溶液,滴加入[Pd(NH3)4]Cl2溶液中,在50-70℃下搅拌反应,析出难溶于水的trans-[Pd(NH3)2(NO2)2]浅黄色沉淀,继续反应1-2小时,冷却到室温,过滤收集、分别用水洗涤和乙醇洗涤,在65℃下烘干,得到trans-[Pd(NH3)2(NO2)2];
第三步:取一定量的草酸,溶于40-60℃的热水中,配制成近饱和的溶液,在搅拌状态下加入化学计量102%的trans-[Pd(NH3)2(NO2)2]固体,在50-60℃下搅拌反应直至trans-[Pd(NH3)2(NO2)2]全部溶解,得到红色溶液,冷冻干燥或在50℃下减压浓缩至干,得到目标产物(NH4)2[Pd(NO2)2(C2O4)]·2H2O。
5.如权利要求1或2所述的一种水溶性Pd(II)配合物作为催化前驱体的用途。
6.根据权利要求5所述的用途,其特征在于,用于制备负载型钯基催化剂。
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CN117138775A (zh) * | 2023-07-24 | 2023-12-01 | 昆明贵金属研究所 | 一种无碱条件下催化二氧化碳加氢制甲酸的催化体系 |
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