CN115335352A - 低级烯烃的纯化 - Google Patents

低级烯烃的纯化 Download PDF

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CN115335352A
CN115335352A CN202180025240.5A CN202180025240A CN115335352A CN 115335352 A CN115335352 A CN 115335352A CN 202180025240 A CN202180025240 A CN 202180025240A CN 115335352 A CN115335352 A CN 115335352A
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copper
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C·M·S·奎罗斯
V·佩尔菲托维森蒂尼
M·塞维兰斯
D·亚当斯
P·曼尼坎丹
U·迪尔
A·巴克梅耶
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Abstract

本文公开了材料床和及其用于从不限于乙烯的低级烯烃去除不限于一氧化碳、氧气、二氧化碳、乙炔、氢气、水、羰基硫化物和硫化氢的污染物的用途。

Description

低级烯烃的纯化
发明领域
本文公开的实施方案涉及材料床的制备和用途以及纯化包括但不限于乙烯的低级烯烃的方法，其可与使用烯烃纯化用单一填充床中的材料的进料流纯化一起使用。
背景
许多产品由聚合物材料制成。一个实例是聚乙烯(PE)。PE以各种形式生产，包括作为高密度聚乙烯(HDPE)。然而，必须纯化以其各种形式形成PE的乙烯单体单元从而去除污染物。事实上，聚合物行业关于单体纯度的要求趋向于更加严格。这个趋势与在聚合前从单体料流去除痕量甚至超痕量水平的污染物的更高需要有关。考虑到对某些污染物的高敏感性，在一些聚合方法中可接受的杂质水平已经从ppm/ppb水平降低至低ppb水平。例如，茂金属催化剂表现出高敏感性，并且通常存在许多杂质，这些杂质即使在低和变化的浓度下也有可能负面影响各种产物例如聚乙烯的收率和有效生产。
特别对于PE行业而言，茂金属催化剂类型的常见乙烯毒物包括：CO、CO2、O2、乙炔、H2、H2O、硫化合物例如羰基硫化物(COS)、硫化氢(H2S)、CH2SH、含氧化合物和含氮化合物等。以ppm水平存在这些元素倾向于阻碍催化剂活性位点并降低PE制造的生产率和总体收率。为了增强PE聚合装置的催化生产率，常规地在聚合反应前纯化乙烯原料(乙烯单体)。
常规地，具有特定催化剂或吸收剂的多个床用于顺序方式在不同工艺条件下去除各个污染物。这个途径需要显著更高的资本和操作成本以及加工时间。然而，有利的是，将本发明的材料布置在单个床上，能够在一种工艺条件下除去所有污染物，从而克服以上限制。
因此，按照本发明实施方案可以以各种形式和替代形式提供的材料床和纯化方法减少了烯烃纯化所需的步骤数。根据需要，这些有可能用作使用单个大反应器的纯化系统的一部分。
实施方案概述
根据多种实施方案和替代方案，将理解本文公开的材料和它们的生产方法适合于去除大范围的污染物，包括本文提到的污染化合物的类型，使其降低至ppb水平。这种材料床可在多个循环内周期性地再生并再次使用。通过说明而不是限制的方式，与本公开内容有关的示例性实施方案包括材料组合物的床，包含铜催化剂与任选的一种或多种促进剂和载体，以及多孔无机氧化物载体。在一些实施方案中，这些材料置于单个床中。除了其它用途之外，如此形成的根据多种实施方案和替代方案的材料床可用于乙烯纯化。可以使用这些材料在环境(例如大反应器)中去除乙烯单体单元或作为气态料流中的进料移动的其它产物中的杂质，所述环境在约40℃至120℃的温度范围下，在约1,000至约10,000h-1气时空速(GHSV)的示例性进料流速范围，和在使用期间在可以为约1-1,000磅/平方英寸表压(psig)的示例性压力下操作。根据需要，当进料通过材料床时操作条件可以为约10-70℃、更特别地20-50℃的温度下，和约5-50巴的压力下。
如本文公开的，根据本发明实施方案和替代方案的这样的材料(例如材料床)适用于从进料流去除杂质。这样的进料的实例是行进通过反应器的乙烯单体，或丙烯或丁烯单体的料流(作为非限制性实例)。一氧化碳(CO)是一种这样的杂质。CO可以单独去除，或它可以与其它化合物的去除同时去除，其它化合物包括但不限于氧气(O2)、二氧化碳(CO2)、炔/乙炔、氢气(H2)、水、羰基硫化物、硫化氢和含氧化合物。因此，本发明实施方案的材料(例如材料床)可比常规多床体系更有效。此外，它们降低了PE生产需要的时间和成本(作为一个实例)，降低了其它可能的资本成本并提供了要求气态料流纯化的其它用途。
多种实施方案和替代方案
在一些实施方案中，本公开内容的材料(例如布置为材料床)包含铜催化剂与任选的一种或多种促进剂和载体，以及多孔无机氧化物。在其它实施方案中，促进剂选自Fe、Ni、Zn、La、Ce、Zr、Mg、Mn、Pd、Pt(以包括含有这些元素的化合物)和它们的组合。在又其它实施方案中，载体选自活性炭、碳纳米管、氧化铝、改性氧化铝、二氧化硅、沸石、氧化锆、二氧化铈。在一些实施方案中，材料中包括了包含氧化铝、沸石、粘土和它们的组合中的一种或多种的多孔无机材料。根据本公开内容的实施方案包括但不限于选自天然存在的或合成制造的材料的包含沸石的材料，和选自含钠膨润土或层状双氢氧化物粘土的粘土。
在一些实施方案中，床中材料的形成包括机械混合不同组分，之后挤出和干燥。任选地，在干燥后将材料造粒。在一些实施方案中，这些材料经受使用包含H2与任选的额外气体例如甲烷、N2的料流的还原。
实施例
实施例1-CuOZnO的生产
CuOZnO复合材料由共沉淀合成。根据一种这样的已知方法，制备混合金属硝酸盐溶液，使得该溶液的Cu硝酸盐浓度为40g/L和Zn硝酸盐浓度为80g/L。然后使用170g/L的碳酸钠溶液与该溶液共沉淀，保持pH在6至8个单位之间，并且然后在搅拌下老化该前体材料2小时直至形成饼。然后将饼在压滤机中过滤并洗涤直至测量的电导率小于50微西门子(micros iemen)。喷雾干燥洗涤的饼以产生CuOZnO粉末，然后在回转煅烧炉中在450℃下煅烧4小时。
实施例2-材料床的生产
通过混合以重量计75g的活性氧化铝、5g的含钠膨润土粘土和20g的CuOZnO(催化剂，Cu/Zn重量比为1至2)的粉末来生产材料。粉末的粒度测定小于100目。通过使用捏合混合器完成混合。在通过添加150ml的水实现原材料的完全均化之后，将材料挤出为6mm×3mm的大小并在85℃下干燥12h。
实施例3-6
表1中的以下实施例(实施例3-6)列出一组示例性材料的重量百分比，其由实施例2中列出的方法步骤形成，除了一个实施例。然而，实施例6由未煅烧的CuOZnO粉末形成，将其挤出并在85℃下干燥，之后在600℃下煅烧一个小时：
表1
Figure BDA0003868267520000041
实施例7-9
表2中的以下实施例(实施例7-9)列出不同组分材料的重量百分比，其通常由实施例2中列出的方法步骤制成：
表2
Figure BDA0003868267520000042
实施例10-CuFeCe共沉淀的实施方案
通过按照实施例1中关于CuOZnO描述的工序共沉淀来制备CuOZnOx，除了硝酸盐溶液对于Cu浓度为55g/L，对于Fe浓度为300g/L和对于Ce浓度为15g/L。使用以这种方式形成的CuOZnOx，然后按照实施例2的工序形成产物，和该产物含有以上关于实施例10在表2中列出重量百分比。
实施例11-材料床用于乙烯纯化的用途
在这些测试中，将各床材料粉碎为1.2至1.4mm的大小。在一方面，使用在N2中10％H2在200℃下原位还原实施例1-10的床材料12小时，然后使用99.99％H2原位还原2小时，之后使材料进行杂质去除实验。测试实施例2-10的CO去除和氧气、乙炔和氢气的同时去除(统称为同时污染物去除)。向固定床反应器装载15mL的根据本发明实施方案的粉碎床材料，从而维持D/Dp比(颗粒直径/反应器直径)大于10。根据需要进一步准备床，在使进料通过床之前，可以使床材料在100-400℃的温度下通过包含氢气、氮气和甲烷的还原气体蒸气，其中铜处于基本上还原的形式。在1,000-10,000h-1的GSHV范围，如以下讨论从40℃至100℃变化温度进行每次运行，并且在每个温度条件下测试运行至少十小时。任选地，GSHV可以1000-5000h-1运行。包含10ppm的CO(示例性污染物或杂质之一)的乙烯气体(即之后待转化成聚乙烯的单体)以25巴(g)加入反应器。对于涉及同时污染物去除的实验，使用用10ppm CO、20ppm O2、10ppm乙炔和80ppm H2污染的商购乙烯气体混合物。
关于实施例2-6，在40℃的温度和3,000h-1的GHSV，测试结果显示运行至少30小时之后>99％去除CO以及同时去除>99％的污染物。在80℃-100℃温度范围下，测试结果显示运行至少30小时之后>99％去除CO以及同时去除>99％的污染物。
关于实施例7-10，在40℃的温度和1,000h-1的GHSV，测试结果显示运行至少30小时之后>99％去除CO以及同时去除>99％的污染物。在80℃-100℃温度范围下，测试结果显示运行至少24小时之后>99％去除CO以及同时去除>99％的污染物。
如之前描述，实施例1提供使用通过之前已知的共沉淀技术合成的CuOZnO的对比例。在40℃的温度和1,000h-1的GHSV，测试结果显示运行至少30小时之后>99％去除CO以及同时去除>99％的污染物。在80℃-100℃温度范围和1,000h-1-3,000h-1的GHSV范围，测试结果显示运行至少24小时之后>99％去除CO以及同时去除>99％的污染物。另外，实施例1导致当在40℃的温度下以3,000h-1的GHSV加料通过反应器时CO2处于大于>10ppmv(以体积计份/百万)水平，其中经常需要具有额外的床以去除CO2和H2O(如果存在的话)。
因此，实施例2-10说明形成方法和通过实践这样的方法获得的一组床材料，全部按照本发明实施方案。对于这些实施例，发现床材料从气态料流去除全部CO的>99％。同样，发现它们将所有主要污染物从ppm范围内的浓度同时去除至ppb水平(远小于0.1ppm)。
实施例2-10中的结果与实施例1(对比例)的实践的结果相当，但是前者与更少的制造步骤并因此减少的时间有关，并且与常规实践例如实施例1相比成本减少，常规实践例如实施例1还需要通常具有分子筛以去除CO和H2O的额外床(一个或多个)。虽然提供了实施例2-10，但是本文提供和涵盖的多种实施方案和替代方案的范围内包括许多其它变体和替代方案。
将理解本文描述的实施方案不限于将它们应用于所列出教导和描述的细节。相反，将理解能够以各种方式实践或进行如本文描述和要求保护的本发明实施方案和替代方案。此外，应理解本文使用的措辞和短语出于描述的目的并且不应视为限制性的。本文使用这样的措辞和短语如“包括”、“例如”、“包含”、“如”、“含有”或“具有”和这些措辞的变体意为包括其之后列出的术语，和这些术语的等同物，以及额外的术语。
因此，实施方案和替代方案的前述描述意为说明而不是充当对本文公开了哪些范围的限制。本文的描述不意为将实施方案的理解限制为公开的精确形式。本领域普通技术人员将理解鉴于以上教导和描述这些实施方案的修改和变化是合理可能的。
以下权利要求是代表性的并且不意在限制在未来要求本申请的权益的申请中要求保护的主题的范围。

Claims (14)

1.用于纯化低级烯烃的杂质或污染物的方法，包括使进料通过材料床，该材料包含铜、一种或多种促进剂和载体，以及多孔无机氧化物。
2.根据权利要求1所述的方法，其中促进剂选自Fe、Ni、Zn、La、Ce、Zr、Mg、Mn、Pd、Pt、Ru和Rh。
3.根据权利要求1所述的方法，其中载体选自活性炭、碳纳米管、氧化铝、改性氧化铝、二氧化硅、沸石、氧化锆、二氧化铈。
4.根据权利要求1所述的方法，其中多孔无机氧化物包含氧化铝、沸石和粘土中至少一者。
5.根据权利要求1所述的方法，其中污染物包含CO、H2、C2或C3炔、H2O、CO2、H2S、甲醇、砷和膦中至少一者。
6.根据权利要求1所述的方法，导致每种污染物去除达到低于0.1ppm的水平。
7.根据权利要求1所述的方法，其中在使进料通过床之前，将床材料在100-400℃的温度下使用包含氢气、氮气和甲烷的还原气体蒸气还原。
8.根据权利要求1所述的方法，其中在约10-70℃的温度下，和在约5-50巴的压力下使进料通过床。
9.根据权利要求8所述的方法，其中温度为20-50℃。
10.根据权利要求1所述的方法，其中在包含氮气和甲烷的惰性气体料流下将床加热至100-400℃的温度持续1-24小时。
11.根据权利要求10所述的方法，其中在使进料通过床之前，使床材料在100-400℃的温度下通过包含氢气、氮气和甲烷的还原气体蒸气，其中铜基本上处于还原的形式。
12.根据权利要求1所述的方法，其中低级烯烃选自乙烯和丙烯以及丁烯。
13.根据权利要求1所述的方法，其中铜的浓度不大于50重量％。
14.根据权利要求12所述的方法，其中铜的浓度不大于20重量％。
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