CN113120916B - 一种多价贵金属改性分子筛的方法 - Google Patents
一种多价贵金属改性分子筛的方法 Download PDFInfo
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 55
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 32
- 150000002500 ions Chemical class 0.000 claims abstract description 25
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- 238000005342 ion exchange Methods 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 7
- 238000000909 electrodialysis Methods 0.000 claims description 5
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- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
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Abstract
一种多价贵金属改性分子筛的方法，含待交换多价贵金属离子的溶液通过至少两个待交换氢型分子筛的交换柱，含待交换多价贵金属离子的溶液每经过一次所述待交换氢型分子筛的交换柱，将从交换柱中分离出的交换液引入电渗析器，利用电渗析器将其中的H+分离，分离出的溶液进入下一个交换柱继续进行多价贵金属离子交换，改性分子筛。本发明利用电渗析器分离交换液中的H+，实现交换液的可利用性，操作方便简单，提高了贵金属的利用率，节约了贵金属资源。
Description
技术领域
本发明涉及一种贵金属改性分子筛的方法，特别是在相同贵金属离子交换度下提高贵金属离子利用率的方法。
背景技术
离子交换法是分子筛贵金属离子改性的常用技术手段之一，其操作过程为将分子筛与贵金属离子溶液混合，经过搅拌与多次补充或更换待交换离子达到所需交换度。因为待交换离子与分子筛上已交换离子间的浓度梯度是离子交换过程的控制步骤之一，所以达到目的交换度通常需要长时间搅拌与多次补充或更换交换液达到所需交换度。离子交换过程耗时且产生大量废水，废水中含有大量待交换离子，一定程度上造成资源浪费。
CN1350887A公开了同时含贵金属和非贵金属的改性Y沸石及其制备方法，在对NaY沸石原料进行贵金属离子交换时，更换了1-2次交换液，每次交换10h，离子交换过程耗时同时产生了含大量贵金属离子的废水，造成了一定的资源浪费。
CN201210414883.1公开了一种分子筛离子交换方法，该方法将含有离子的水溶液在双极膜电渗析器中进行双极膜电渗析，得到酸液，使含有模板剂的分子筛与酸液接触，进行离子交换。此方法的双极膜电膜电渗析装置的用途仅是解离水以提供酸液和碱液，阴、阳离子膜对不同价态的正、负离子没有选择性。
CN201510725653.0公开了一种分子筛制备过程中的含硅废水的处理方法，该方法将含硅废水经过一系统预处理操作，将干净的液相放入双极膜电渗析器，得到酸液和/或碱液，此方法能获得较高的硅回收率和更高的废水利用率，基本不产生或仅产生极少量的外排废水，同时外排的固体物料的量也很低，但是操作流程长，过程操作繁琐。
现有的分子筛贵金属离子交换的技术方案，存在着交换时间长且交换离子利用率低的不足。
发明内容
为解决现有技术中分子筛进行贵金属改性时存在交换时间长且贵金属交换度低造成贵金属浪费的问题，本发明提供了一种贵金属改性分子筛的方法，提高贵金属交换度，并提高贵金属利用率。
本发明通过以下技术方案实现上述技术目的：
一种多价贵金属改性分子筛的方法，将含待交换多价贵金属离子的溶液通过至少两个待交换氢型分子筛的交换柱，含待交换多价贵金属离子的溶液每经过一次所述待交换氢型分子筛的交换柱，将从交换柱中分离出的交换液引入电渗析器，利用电渗析器将其中的H+分离，分离出的溶液进入下一个交换柱继续进行多价贵金属离子交换，改性分子筛。
进一步的，所述含待交换多价贵金属离子的溶液中的阴离子为负一价阴离子。
进一步的，所述电渗析器的正极到负极之间，按顺序依次排列至少一对一价阴离子交换膜和一价阳离子交换膜，按从正极到负极的顺序，每对一价阴离子交换膜和一价阳离子交换膜之间为淡室，相邻的一价阳离子交换膜和一价阴离子交换膜之间为浓室，与两极相邻的膜与两电极之间形成极室；向所述淡室中通入从交换柱中分离出的交换液，开启电渗析装置，H+和交换液中的负一价阴离子在电极和膜的作用下定向迁移，从而分离出H+。
进一步的，所述一价阴离子交换膜和一价阳离子交换膜附着在有流道的隔板上，所述隔板对膜起到支撑作用，并不妨碍液体的流动。
进一步的，所述电渗析器的操作电压为0.6～1.5V/膜对，进入所述电渗析器淡室的交换液的流量为1~5L/h，浓室和极室中通入选自NaCl、KCl、NaNO3和KNO3溶液中的至少一种作为冲洗液，所述电渗析器的淡室和浓室/极室溶液流量比为1：1~1：3。
进一步的，将含待交换多价贵金属离子的溶液通过交换柱为固定床形式或流化床形式，优选填装成型分子筛的固定床。
进一步的，所述的待交换分子筛优选为硅铝基分子筛，如Y型分子筛、X型分子筛、A型分子筛、ZSM-5分子筛、丝光分子筛、β分子筛或镁碱分子筛，将以上分子筛先进行铵交换、干燥、焙烧，得到氢型分子筛后，再利用上述方法进行贵金属改性。
进一步的，所述多价贵金属选自Ru、Rh、Pd、Os、Ir、Pt中的一种或几种。
与现有技术相比，本发明利用电渗析器分离交换液中的H+，实现交换液的可利用性，操作方便简单，提高了贵金属的利用率，节约了贵金属资源。
本发明的其它特征和优点将在随后的具体实施方式部分予以详细说明。
附图说明
图1. 实施例所使用的电渗析装置示意图；
图2. 四级交换柱、电渗析器工艺流程示意图；
其中：1.电渗析器的正极，2.电渗析器的负极，3.一价阴离子交换膜，4是一价阳离子交换膜，11.淡室，12.极室，21.交换柱，22.电渗析器，A.冲洗液，B.从交换柱中分离出的交换液，。
具体实施方式
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明，但不以任何方式限制本发明。
以下实施例中所使用的的电渗析器装置如图1所示，电渗析器的正极1到电渗析器的负极2之间，依次设置有一价阴离子交换膜3和一价阳离子交换膜4。膜之间为淡室11，膜与两极之间为极室12。上述电渗析器由浙江千秋环保水处理有限公司提供，所述一价阴离子交换膜3一价阴离子选择透过率为95%，所述一价阳离子交换膜4的选择透过率为94%。
利用图2所示的工艺流程示意图进行多价贵金属改性分子筛：4个交换柱21与电渗析器22交替排列，将待改性分子筛装填至4个交换柱21中，向其中通入含待交换多价贵金属离子的溶液，离子交换后从交换柱中分离出的交换液B引入第一个电渗析器22的淡室11中，其中的H+被分离，分离出H+的交换液引入第二个交换柱21中，如此反复，电渗析器22的浓室和极室中通入冲洗液A。
下述实施例中所用的NaK-FER分子筛由东曹达（上海）贸易有限公司提供，按重量百分比计，Na2O含量为0.9%，K2O含量为6.32%，SiO2/Al2O3摩尔比为16.7。分子筛成型所用的粘结剂为SW-17型氢氧化铝粉，孔容为0.47-0.53 ml/g，比表大于250 m2/g，平均孔径为7.5-8.5 nm，由淄博泰光化工有限公司提供。
下列实施例中的贵金属Mn+和Al含量由ICP-AES方法测定。假定Mn+平衡铝氧四面体的负电荷，因此M/Al摩尔比为1/n时，其Mn+交换度为100%。下列实施例中Mn+交换度计算方法如下：
其中M M和M Al分别表示样品中贵金属M和Al的质量摩尔浓度，mol/g。
实施例1
将800g的NaK-FER沸石、856 g的NH4Cl和1600g去离子水混合均匀打浆，于室温下（25℃）搅拌2小时，过滤，再于室温下（25℃）重复上述交换过程，交换后经过滤，所得滤饼用30倍于NaK-FER沸石干基重量的去离子水彻底冲洗，经110℃干燥和600℃焙烧，得到氢型镁碱沸石，标记为HFER，其中Na2O和K2O总重量含量低于0.01%，SiO2/Al2O3摩尔比为17.1。
将HFER分子筛，同SW-17氢氧化铝粉、田菁粉、硝酸和去离子水（质量比为40：5：1.5：1：50）在CD4X1TS型多功能催化剂成型机捏合形成浓稠膏体，采用1.5mm孔的不锈钢模压板挤压成型，所得挤出物先于室温下干燥24小时，再于110℃烘干8小时，最后于600℃焙烧4小时，得到条状成型分子筛，相应标记为A。
实施例2
取实施例1中A样品100g，装填在四个交换柱21中，用去离子水配制0.5mol/L的RuCl3溶液，在室温下以2L/h依次通过4个交换柱21和电渗析器的淡室11，流量为2L/h，以0.5mol/L的NaCl溶液通入极室，极室溶液流量为2L/h，即淡室、浓室流量比为1：1，电渗析器操作电压设为0.7V/膜对。由第4个电渗析器22排出的溶液进入RuCl3溶液储罐，循环利用。实验进行4小时后，将固定床中的分子筛过滤，110℃干燥8小时，并于600℃焙烧4小时，所得样品分别标记为A-11、A-12、A-13、A-14。经ICP-AES方法测定，A-11样品Ru3+交换度为6.4%，A-12样品Ru3+交换度为6.2%，A-13样品Ru3+交换度为5.9%，A-14样品Ru3+交换度为5.4%。
实施例3
取实施例1中A样品100g，装填在四个交换柱21中，用去离子水配制0.5mol/L的PdCl2溶液，在室温下以2L/h依次通过4个交换柱21和电渗析器的淡室11，控制淡室溶液流量2L/h，以0.1mol/L的NaCl溶液通入极室，极室溶液流量为4L/h，即淡室、浓室流量比为1：2，电渗析器操作电压设为1.2V/膜对，由第4个电渗析器22排出的溶液进入PdCl2溶液储罐，循环利用。实验进行4小时后，将固定床中的分子筛过滤，110℃干燥8小时，并于600℃焙烧4小时，所得样品分别标记为A-21、A-22、A-23、A-24。经ICP-AES方法测定，A-21样品Pd2+交换度为6.4%，A-22样品Pd2+交换度为6.4%，A-23样品Pd2+交换度为6.2%，A-24样品Pd2+交换度为5.9%。
实施例4
取实施例1中A样品100g，装填在四个交换柱21中，用去离子水配制0.5mol/L的氯铂酸溶液，在室温下以2L/h依次通过4个交换柱21和电渗析器的淡室11，流量为2L/h，以1.0mol/L的NaCl溶液通入极室，极室溶液流量为3L/h，即淡室、浓室流量比为2：3，电渗析器操作电压设为0.8V/膜对，由第4个电渗析器22排出的溶液进入氯铂酸溶液储罐，循环利用。实验进行4小时后，将固定床中的分子筛过滤，110℃干燥8小时，并于600℃焙烧4小时，所得样品分别标记为A-31、A-32、A-33、A-34。经ICP-AES方法测定，A-31样品Pt4+交换度为6.4%，A-32样品Pt4+交换度为6.3%，A-33样品Pt4+交换度为6.0%，A-34样品Pt4+交换度为5.7%。
对比例1
取实施例1中A样品100 g，装填在交换柱中，制作4个交换柱。用去离子水配制0.5mol/L的PdCl2溶液，在室温下以2L/h依次通过4个交换柱，交换液通过第4个交换柱后排掉。交换4小时后，将分子筛110℃干燥8小时，600℃焙烧4小时，所得样品分别标记为A-41、A-42、A-43和A-44。经ICP-AES方法测定，A-41样品Pd2+交换度为6.4%，A-42样品Pd2+交换度为5.3%，A-43样品Pd2+交换度为3.9%，A-44样品Pd2+交换度为2.4%。
Claims (10)
1.一种多价贵金属改性分子筛的方法，其特征在于，将含待交换多价贵金属离子的溶液通过至少两个待交换氢型分子筛的交换柱，含待交换多价贵金属离子的溶液每经过一次所述待交换氢型分子筛的交换柱，将从交换柱中分离出的交换液引入电渗析器，利用电渗析器将其中的H+分离，分离出的溶液进入下一个交换柱继续进行多价贵金属离子交换，改性分子筛；所述电渗析器的正极到负极之间，按顺序依次排列至少一对一价阴离子交换膜和一价阳离子交换膜，按从正极到负极的顺序，每对一价阴离子交换膜和一价阳离子交换膜之间为淡室，相邻的一价阳离子交换膜和一价阴离子交换膜之间为浓室，与两极相邻的膜与两电极之间形成极室；向所述淡室中通入从交换柱中分离出的交换液，开启电渗析装置，H+和交换液中的负一价阴离子在电极和膜的作用下定向迁移，从而分离出H+。
2.根据权利要求1所述的方法，其特征在于，所述含待交换多价贵金属离子的溶液中的阴离子为负一价阴离子。
3.根据权利要求2所述的方法，其特征在于，所述一价阴离子交换膜和一价阳离子交换膜附着在有流道的隔板上。
4.根据权利要求1所述的方法，其特征在于，所述电渗析器的操作电压为0.6～1.5V/膜对，进入所述电渗析器淡室的交换液的流量为1～5L/h。
5.根据权利要求1所述的方法，其特征在于，浓室和极室中通入选自NaCl、KCl、NaNO3和KNO3溶液中的至少一种作为冲洗液。
6.根据权利要求1所述的方法，其特征在于，所述电渗析器的淡室和浓室/极室溶液流量比为1：1～1：3。
7.根据权利要求1所述的方法，其特征在于，将含待交换多价贵金属离子的溶液通过交换柱为固定床形式或流化床形式。
8.根据权利要求7所述的方法，其特征在于，将含待交换多价贵金属离子的溶液通过交换柱为填装成型分子筛的固定床形式。
9.根据权利要求1所述的方法，其特征在于，所述的待交换分子筛为硅铝基分子筛，选自Y型分子筛、X型分子筛、A型分子筛、ZSM-5分子筛、丝光分子筛、β分子筛或镁碱分子筛，将以上分子筛先进行铵交换、干燥、焙烧，得到氢型分子筛后，再利用上述方法进行贵金属改性。
10.根据权利要求1所述的方法，其特征在于，所述多价贵金属选自Ru、Rh、Pd、Os、Ir、Pt中的一种或几种。
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