CN110975934A - 一种合成气制低碳混合醇阳离子交换树脂基催化剂及制法和应用 - Google Patents
一种合成气制低碳混合醇阳离子交换树脂基催化剂及制法和应用 Download PDFInfo
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000003729 cation exchange resin Substances 0.000 title claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 32
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- 125000002091 cationic group Chemical group 0.000 description 1
- DQIPXGFHRRCVHY-UHFFFAOYSA-N chromium zinc Chemical compound [Cr].[Zn] DQIPXGFHRRCVHY-UHFFFAOYSA-N 0.000 description 1
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种由合成气制低碳混合的阳离子交换树脂基催化剂领域。一种合成气制低碳混合醇阳离子交换树脂基催化剂，重量百分比组成为：Cu:20‑34%，Fe:18‑30%，Mn:8‑26%，Zn:15‑30%，Zr:1‑9%，Co:1‑15%。本发明还涉及该催化剂的制备方法和应用。本发明由于借助高吸水分子（阳离子交换树脂）的稳定的孔道结构，催化剂各组分分布比较均匀，并各组分间存在强相互作用，沉淀效果好，抗烧结性能比较好，成本低，稳定性好，寿命长。
Description
技术领域
本发明属于一种由合成气制低碳混合的阳离子交换树脂基催化剂及其制备方法和应用。
背景技术
随着石油资源的日益枯竭和人类环保意识的不断提高，寻求新型洁净的替代燃料成为一项重要的能源开发利用议题。鉴于我国“富煤，贫油，少气”的资源禀赋特征，把煤转化为洁净液体燃料和化学品将在取代石油，生产高效替代燃料方面有着有益的应用前景。
由煤基合成气出发制备的低碳混合醇（C1～C5混合醇）可以作为燃料添加剂和某些化工产品的原料，甚至直接作为洁净燃料来使用。低碳混合醇与汽油之间具有良好的互溶性，能够有效改善汽油的防爆、防震性能和辛烷值。因此，开发新型催化剂，在合成气制低碳混合醇的同时联产汽油不仅可以大大降低对石油资源的依赖，而且对煤/天然气资源的洁净高效利用具有重要的现实意义。
由合成气直接合成低碳醇的研究较为广泛，所形成的催化剂体系主要有以下四种：
（1）改性甲醇合成催化剂（Cu/ZnO/Al2O3, ZnO/Cr2O3）：此催化剂由甲醇合成催化剂加入适量的碱金属或碱土金属化合物改性而得，较典型的专利有 EP-0034338-A2 （C.E.Hofstadt等人）及美国专利4513100（Snam公司资助,发明人为Fattore等人）。此类催化剂虽然活性较高，产物中异丁醇含量高，但缺点是反应条件苛刻（压力为14-20MPa，温度为350-450℃），高级醇选择性低(一般小于35％)，产物中含水量高（一般为30－50％）；（2）Rh基催化剂（如US 4014913及4096164 ）：负载型Rh催化剂中加入一到两种过渡金属或金属氧化物助剂后，对低碳醇合成有较高的活性和选择性，特别是对C2 +醇的选择性较高，产物以乙醇为主。但Rh化合物价格昂贵，催化剂易被CO2毒化，其活性和选择性一般达不到工业生产的要求。（3）抗硫MoS2催化剂：最值得一提是美国DOW公司开发的钼系硫化物催化剂（主要专利见Stevens等人的US patent 4882360），该催化体系不仅具有抗硫性，产物含水少，而且高级醇含量较高，达30-70%，其中主要是乙醇和正丙醇。此催化剂存在的主要问题是其中的助剂元素极易与一氧化碳之间形成羰基化合物，造成助剂元素的流失，影响催化剂的活性及选择性，致使催化剂稳定性和寿命受到限制。（4）Cu-Co催化剂：法国石油研究所(IFP)首先开发了Cu-Co共沉淀低碳醇催化剂，仅1985年就获得了四个催化剂专利(US Patent 4122110,4291126及GB Patent 2118061, 2158730)，此催化剂合成的产物主要为C1-C6直链正构醇，副产物主要为C1-C6脂肪烃，反应条件温和（与低压甲醇合成催化剂相似）。该催化剂的缺点是稳定性较差。
目前，国内外对于由合成气制低碳混合醇联产汽油馏分的催化剂研究还相对较少。中国专利CN 1736594A 报道了一种钴和钯负载锌铬尖晶石的催化剂及其制备方法，该催化剂可以选择地使合成气转化为低碳混合醇和液态烷烃混合物。该催化剂采用简单的浸渍法制备，但催化剂活性组分为钴和钯，价格昂贵，致使催化剂的广泛应用受到限制。
发明内容
本发明的目的是提供一种成本低，稳定性好，寿命长，在温和反应条件下高选择性的由合成气制低碳混合醇的催化剂制备方法和应用。
离子交换树脂是带有官能团（有交换离子的活性基团）、具有网状结构、不溶性的高分子化合物。主要分为孔隙结构分凝胶型和大孔型两种，分类属酸性的应在名称前加“阳”，分类属碱性的，强酸型阳离子交换树脂：主要含有强酸性的反应基如磺酸基（－SO3H），此离子交换树脂可以交换所有的阳离子。弱酸型阳离子交换树脂：具有较弱的反应基如羧基（－COOH基），此离子交换树脂仅可交换弱碱中的阳离子如Ca2+、Mg2+、Cu2+，对于强碱中的离子如Na+、K+等无法进行交换。
阳离子树脂是以苯乙烯和二乙烯苯聚合， 经硫酸磺化而制得的聚合物。 生产过程中不含有明 胶及其它任何动物提取物。阳离子交换树脂遇水可将其本身的某一种具有活性的离子和水中某电离子相互交换，即发生置换反应，去除水中可溶解的离子。是一种新型的功能高分子材料。
本发明的目的是这样实现的，以阳离子交换树脂作为骨架，将Fe，Cu基无机盐溶液浸渍到阳离子交换树脂骨架材料中，然后沉淀、煅烧成型。并且催化剂助剂中引入具有较强碳链增长能力的VIII族元素，以及过渡金属、碱金属、碱土金属或稀土金属，从而提高CO加氢反应的活性，改善C2 +醇和C4 +烃的选择性，并同时抑制CO2和甲烷等副产物的生成。
本发明催化剂重量百分比组成为：Cu:20-34%, Fe:18-30%, Mn:8-26%, Zn:15-30%, Zr:1-9%, Co:1-15%。
本发明提供的催化剂的制备方法包括以下步骤：
在温度为20-90℃条件下，现将阳离子交换树脂加入蒸馏水中，配成0.1wt%～10wt%基体溶液，在15-30r/min搅拌速率下，将催化剂组成的金属硝酸盐溶于基体溶液中混合均匀形成硝酸盐浓度为30wt%～60wt %的混合溶液（重量百分比组成，Cu:20-34%, Fe:18-30%,Mn:8-26%, Zn:15-30%, Zr:1-9%, Co:1-15%），并与浓度为30wt％的氨水溶液或可溶性碳酸盐并流进行沉淀，沉淀时的搅拌速率控制在30-45r/min，沉淀温度为40-80℃，保持溶液pH=6-10，沉淀后老化3-5h，沉淀经蒸馏水洗涤至中性为止。湿滤饼经80-120℃干燥后在350-500℃空气气氛下焙烧6h，破碎至40-60目。
阳离子交换树脂，离子交换树脂交换能力依其交换能力特征可分：
1. 强酸型阳离子交换树脂：这类树脂含有大量的强酸性基团，如磺酸基－SO3H，容易在溶液中离解出H+，故呈强酸性。树脂离解后，本体所含的负电基团，如SO3－，能吸附结合溶液中的其他阳离子。这两个反应使树脂中的H+与溶液中的阳离子互相交换。强酸性树脂的离解能力很强，在酸性或碱性溶液中均能离解和产生离子交换作用，强碱型阳离子交换树脂可以和所有的阳离子进行交换去除。这种树脂的离解性很强，在不同pH下都能正常工作。如上述的阳离子树脂是用强酸进行再生处理，此时树脂放出被吸附的阳离子，再与H+结合而恢复原来的组成。
2. 弱酸型阳离子交换树脂：这这类树脂含弱酸性基团，如羧基－COOH，能在水中离解出H+ 而呈酸性。树脂离解后余下的负电基团，如R-COO－（R为碳氢基团），能与溶液中的其他阳离子吸附结合，从而产生阳离子交换作用。这种树脂的酸性即离解性较弱，在低pH下难以离解和进行离子交换，只能在碱性、中性或微酸性溶液中（如pH5～14）起作用。这类树脂亦是用酸进行再生。
阳离子交换树脂为强碱型阳离子交换树脂，弱碱型阳离子交换树脂的一种或几种。
如上所述的可溶性碳酸盐更具体地说为碳酸钠或碳酸钾等。
本发明催化剂的应用条件为：
还原温度为210-300℃, 压力为4.0-12.0MPa, 空速为1000-10000h-1, H2/CO（摩尔）=0.5-3.0。
反应温度为210-280℃, 压力为4.0-12.0MPa, 空速为1000-10000h-1, H2/CO（摩尔）=0.5-3.0。
用本发明催化剂进行低碳醇的合成，CO转化率15-45%，总醇选择性为35-75%，总烃选择性20-35%，CO2选择性9-20%。总醇时空产率为0.20-0.45g/h.mL.cat；产物中水含量为20-30%；C2 +醇含量为50-80%，C4 +烃在总烃中所占百分含量40-50%。
本发明具有如下优点：
1、制备方法简单，易于操作，并且催化剂反应性能重复性比好。
2、本发明由于借助高吸水分子（阳离子交换树脂）的稳定的孔道结构，催化剂各组分分布比较均匀，并各组分间存在强相互作用，沉淀效果好，抗烧结性能比较好，成本低，稳定性好，寿命长。
3、本发明的催化剂在还原和反应过程中，不需要添加CO2气体，大大降低了操作费用。
具体实施方式
实施例1
首先将磺酸基（－SO3H）阳离子聚苯乙烯交换树脂，用蒸馏水配成wt0.1%高分子溶液，后将下列金属原子以硝酸盐的形式按摩尔比Cu: Fe: Mn: Zn: Zr: Co =1.0:1.0:0.5:1.0:0.1:0.2溶于该溶液当中形成wt30%的硝酸盐混合溶液。在70℃下与30wt%碳酸钠溶液并流沉淀，沉淀过程需充分搅拌，并保持pH=8-9。沉淀经蒸馏水洗涤至中性为止。湿滤饼经120℃干燥后在400℃空气气氛下焙烧6h，破碎至40-60目，得到催化剂。催化剂中各元素组成为Cu:27.5%, Fe:23.9%, Mn:11.8%, Zn:27.6%, Zr:4.0%, Co:5.2%。还原温度为210-300℃, 压力为4.0-12.0MPa, 空速为1000-10000h-1, H2/CO（摩尔）=0.5-3.0。反应条件如下：T=260℃, P=6.0MPa, GHSV=8000h-1, H2/CO（摩尔）=2.0。反应结果见表1。
实施例2
首先将磺酸基（－SO3H）苯乙烯阳离子交换树脂，用蒸馏水配成wt0.15%高分子溶液，将下列金属原子以硝酸盐的形式按摩尔比Cu:Fe:Mn:Zn:Zr:Co =0.5:1.0:0.5:1.0:0.1:0.2溶于蒸馏水当中形成wt45%的硝酸盐混合溶液。在70℃下与30wt%碳酸钠溶液并流沉淀，沉淀过程需充分搅拌，并保持pH=8-9。沉淀经蒸馏水洗涤至中性为止。湿滤饼经120℃干燥后在400℃空气气氛下焙烧6h，破碎至40-60目，得到催化剂。催化剂中各元素组成为Cu:15.9%, Fe:27.8%, Mn:13.7%, Zn:32.3%, Zr:4.5%, Co:5.8%。还原温度为210-300℃,压力为4.0-12.0MPa,空速为1000-10000h-1, H2/CO（摩尔）=0.5-3.0。反应条件如下：T=260℃, P=6.0MPa, GHSV=8000h-1, H2/CO（摩尔）=2.0。反应结果见表1。
实施例3
首先将丙烯酸（-COOH）阳离子交换树脂，用蒸馏水配成wt0.2%高分子溶液，后将下列金属原子以硝酸盐的形式按摩尔比Cu: Fe: Mn: Zn：Zr:Co =1.5: 1.0: 0.5: 1:0.1:0.2溶于高分子溶液中当中形成wt50%的硝酸盐混合溶液。在70℃下与30wt%碳酸钠溶液并流沉淀，沉淀过程需充分搅拌，并保持pH=8-9。沉淀经蒸馏水洗涤至中性为止。湿滤饼经120℃干燥后在400℃空气气氛下焙烧6h，破碎至40-60目，得到催化剂。催化剂中各元素组成为。Cu:36.0%, Fe:21.2%, Mn:10.5%, Zn:24.5%, Zr:3.4%, Co:4.4%。还原温度为210-300℃, 压力为4.0-12.0MPa, 空速为1000-10000h-1, H2/CO（摩尔）=0.5-3.0。反应条件如下：T=260℃, P=6.0MPa, GHSV=8000h-1, H2/CO（摩尔）=2.0。反应结果见表1。
实施例4
首先将丙烯酸（-COOH）阳离子交换树脂和丙烯酸（-COOH）苯乙烯阳离子交换树脂按1:1混合，用蒸馏水配成wt0.25%高分子溶液，后将下列金属原子以硝酸盐的形式按摩尔比Cu:Fe:Mn:Zn:Zr:Co =1.0:1.0:1.0:1:0.2:0.2溶于高分子溶液当中形成wt30%的硝酸盐混合溶液。在70℃下与20wt%碳酸钾溶液并流沉淀，沉淀过程需充分搅拌，并保持pH=8-9。沉淀经蒸馏水洗涤至中性为止。湿滤饼经120℃干燥后在400℃空气气氛下焙烧6h，破碎至40-60目，得到催化剂。催化剂中各元素组成为Cu:23.7%, Fe:20.7%, Mn:20.0%, Zn:24.1%, Zr:6.7%, Co:4.4%。还原温度为210-300℃, 压力为4.0-12.0MPa, 空速为1000-10000h-1,H2/CO（摩尔）=0.5-3.0。反应条件如下：T=260℃, P=4.0MPa, GHSV=6000h-1, H2/CO（摩尔）=2.0，反应结果见表1。
实施例5
首先将丙烯酸（-COOH）阳离子交换树脂，用蒸馏水配成wt0.3%高分子溶液，后将下列金属原子以硝酸盐的形式按摩尔比Cu:Fe:Mn:Zn:Zr:Co =1.0:1.0:1.0:1:0.3:0.2溶于高分子溶液当中形成wt60%浓度的硝酸盐混合溶液。在70℃下与20wt%碳酸钾溶液并流沉淀，沉淀过程需充分搅拌，并保持pH=8-9。沉淀经蒸馏水洗涤至中性为止。湿滤饼经120℃干燥后在400℃空气气氛下焙烧6h，破碎至40-60目，得到催化剂。催化剂中各元素组成为Cu:22.9%, Fe:20.1%, Mn:20.0%, Zn:23.3%, Zr:9.8%, Co:4.2%。还原温度为210-300℃, 压力为4.0-12.0MPa, 空速为1000-10000h-1, H2/CO（摩尔）=0.5-3.0。反应条件如下：T=260℃, P=4.0MPa, GHSV=6000h-1, H2/CO（摩尔）=2.0，反应结果见表1。
Claims (7)
1.一种合成气制低碳混合醇阳离子交换树脂基催化剂，其特征在于：该催化剂重量百分比组成为：Cu:20-34%, Fe:18-30%, Mn:8-26%, Zn:15-30%, Zr:1-9%, Co:1-15%。
2.如权利要求1所述的一种合成气制低碳混合醇阳离子交换树脂基催化剂的制备方法，其特征在于：将阳离子型交换树脂加入蒸馏水中，配成0.1wt%～10wt%基体溶液，将Cu、Fe、Mn、Zn、Zr、Co的硝酸盐溶于基体溶液中混合均匀形成硝酸盐浓度为30wt%～60wt %的混合溶液，加入浓度为30wt％的氨水溶液或可溶性碳酸盐进行反应并生成沉淀，沉淀后老化3-5h，将沉淀用蒸馏水洗涤至中性为止，然后将沉淀干燥，并在350-500℃空气气氛下焙烧6h，破碎至40-60目，其中，重量百分比组成，Cu:20-34%, Fe:18-30%, Mn:8-26%, Zn:15-30%, Zr:1-9%, Co:1-15%。
3.根据权利要求2所述的一种合成气制低碳混合醇阳离子交换树脂基催化剂的制备方法，其特征在于：在温度为20-90℃条件下，将阳离子型交换树脂加入蒸馏水中，配成0.1wt%～10wt%基体溶液，在15-30r/min搅拌速率下，将Cu、Fe、Mn、Zn、Zr、Co的硝酸盐溶于基体溶液中混合均匀形成硝酸盐浓度为30wt%～60wt %的混合溶液。
4.根据权利要求2所述的一种合成气制低碳混合醇阳离子交换树脂基催化剂的制备方法，其特征在于：沉淀反应时的搅拌速率控制在30-45r/min，反应温度为40-80℃，保持溶液pH=6-10。
5.如权利要求2所述的一种合成气制低碳混合醇阳离子交换树脂基催化剂的制备方法，其特征在于：阳离子型交换树脂为强碱型阳离子交换树脂或弱碱型阳离子交换树脂的一种或几种。
6.如权利要求2所述的一种合成气制低碳混合醇阳离子交换树脂基催化剂的制备方法，其特征在于：所述的可溶性碳酸盐为碳酸钠或碳酸钾。
7.一种合成气制低碳混合醇阳离子交换树脂基催化剂的应用，其特征在于：反应条件如下：
还原温度为210-300℃, 压力为4.0-12.0MPa, 空速为1000-10000h-1, H2/CO摩尔为0.5-3.0；
反应温度为210-280℃, 压力为4.0-12.0MPa, 空速为1000-10000h-1, H2/CO摩尔为0.5-3.0。
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| CN101185895A (zh) * | 2006-11-17 | 2008-05-28 | 南化集团研究院 | 用于合成气合成低碳醇的催化剂及其制备方法 |
| CN101269334A (zh) * | 2008-05-19 | 2008-09-24 | 中国科学院山西煤炭化学研究所 | 同时生产低碳混合醇和烯烃的催化剂及制法和应用 |
| CN101327434A (zh) * | 2008-07-30 | 2008-12-24 | 中国科学院山西煤炭化学研究所 | 合成气制低碳混合醇联产汽油馏分的催化剂及制法和应用 |
| CN102247852A (zh) * | 2011-05-18 | 2011-11-23 | 中国科学院广州能源研究所 | 一种合成气合成低碳醇的Cu-Fe-Co基催化剂及制备方法及其在合成气合成低碳醇工艺中的应用 |
| CN104437534A (zh) * | 2014-11-13 | 2015-03-25 | 中国科学院山西煤炭化学研究所 | 一种合成气制低碳混合醇联产汽油馏分的催化剂及制法和应用 |
| CN107486234A (zh) * | 2017-07-23 | 2017-12-19 | 复旦大学 | 用于合成气直接转化制备轻质芳烃的催化剂及其制备方法 |
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