CN108927133B - 一种二甲醚水蒸气重整催化剂及其制氢方法 - Google Patents
一种二甲醚水蒸气重整催化剂及其制氢方法 Download PDFInfo
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Abstract
本发明公开了一种二甲醚水蒸气重整催化剂及其制氢方法。该催化剂是以γ‑Al2O3为二甲醚水解活性组分、ZnO‑ZrO2固溶体为甲醇重整活性组分所构成的双功能催化剂(ZnO‑ZrO2/γ‑Al2O3)。该ZnO‑ZrO2/γ‑Al2O3催化剂中,ZnO‑ZrO2固溶体与γ‑Al2O3质量比为0.5~5。制氢方法为:将催化剂ZnO‑ZrO2/γ‑Al2O3装填在固定床反应器中,以N2为稀释气,水蒸气和二甲醚混合,在反应温区与催化剂接触进行重整反应制得氢气。该催化剂在380℃时可达到最优活性,活性达95.83%。本发明的催化剂活性高,产氢率高,CO选择性低,重整反应温度较传统锌基催化剂低,稳定性优良。
Description
技术领域
本发明属于化工与能源领域,具体涉及一种二甲醚水蒸气重整催化剂及其制氢方法。
背景技术
近年来,化石燃料急剧增大的消耗不可避免地导致能源短缺和各种环境污染问题。因此,人们对以氢能为代表的清洁能源的开发与利用给予了越来越密切的关注。以高品质氢气为燃料的质子交换膜燃料电池(PEMFC)以其高能量转换效率、高能量密度、低污染物排放或零排放等优点而受到人们的广泛关注,被普遍认为是替代日益稀缺的化石燃料的清洁可持续能源转换技术。然而,由于氢气运输和储存困难等问题极大限制了燃料电池的发展。二甲醚的物化性质与液化石油气类似,其储存运输等基础设施与现有液化石油气兼容,且具有能量密度高,H/C比高,清洁无毒,制氢条件温和等优点,因而以二甲醚为原料,利用水蒸气重整制氢技术的技术路线有望安全、高效、稳定地解决PEMFC供氢的问题。
二甲醚水蒸气重整制氢(DME SR)反应分两步进行,第一步是二甲醚在固体酸催化剂上水解生成中间产物甲醇,第二步是甲醇在金属或金属氧化物催化剂催化下与水蒸气发生重整反应生成H2和CO2。因此,二甲醚水蒸气重整制氢催化剂须同时提供水解和重整活性,通常使用的是由固体酸和金属或金属氧化物催化剂两种活性组份构成的双功能催化剂,固体酸以氧化铝及分子筛为主,金属催化剂主要是Cu、Ni、Pd、Pt等,金属氧化物催化剂有ZnO、Ga2O3等。Cu基催化剂因其价格低廉且低温活性好的优点,是使用最为广泛的甲醇重整催化剂,但存在选择性和热稳定性差,高温下容易烧结失活的问题;Ni基催化剂反应出口CO含量过高;贵金属性能虽然优良,但成本较高;金属氧化物催化剂稳定性好,副产物CO浓度低,但需要较高的反应重整温度,在450℃左右才可获得较高的二甲醚转化率。
专利CN103204472A报道了一种碱金属改性铜基催化剂X/CuZnAl/γ-Al2O3(X为Li、Na、K和Rb中的一种)用于二甲醚水蒸气重整制氢反应,该催化剂在高温下容易烧结失活,氢气收率较低,且稳定性不高。专利CN101822993A报道了由负载型磷钨酸催化剂与Cu/ZnO/Al2O3甲醇水蒸气重整催化剂复合而成的双功能催化剂并用于二甲醚水蒸气重整制氢反应,反应产物选择性高,但二甲醚转化率较低。专利CN106492810A公开了采用蒸氨浸渍法制备了一种Zn改性的Cu基催化剂,以CuO-ZnO-SiO2作为重整催化剂与γ-Al2O3复合用于二甲醚水蒸气重整制氢反应,所得催化剂活性良好。美国专利US6361757报道了以Cu、Fe、Co、Pb、Pt、Ir、Rh、Ni等作为金属催化剂,氧化铝、硅胶、分子筛作为固体酸催化剂,用于二甲醚水蒸气重整制氢反应,该催化剂贵金属活性组分含量较大,商业化成本较高,并且其催化活性不甚理想。
金属氧化物因其使用前无需还原,稳定性好等优点也被应用于二甲醚水蒸气重整制氢技术中(参见Applied Catalysis A:General,2012,433:26-34)。专利CN102794166A报道了ZnO-ZnM2O4(M=Cr、Al)作为重整催化剂与Ti2O3-Al2O3匹配用作二甲醚水蒸气重整制氢催化剂。ZnO基催化剂稳定性好,反应器出口CO含量低,但是反应最佳活性温度要高于400℃,且产氢率较低。专利CN104069845A报道了ZnO-Al2O3-ZrO2/γ-Al2O3用于二甲醚水蒸气重整制氢反应,反应活性好,但重整反应温度较高,反应温度区间为390~450℃。
目前,从现有报道来看,二甲醚水蒸气重整制氢锌基催化剂的重整温度普遍高于400℃,在450℃左右才能获得较好的催化活性,这带来了反应高能耗,催化剂热稳定性差的问题。而重整温度低于400℃、催化活性好、产氢率高、CO选择性低、稳定性优良的二甲醚水蒸气重整制氢锌基催化剂尚未见报道。
发明内容
针对现有ZnO基催化剂重整温度较高的缺陷,本发明首要目的是提供一种二甲醚水蒸气重整催化剂,该催化剂是一种最优重整温度低于400℃的锌基二甲醚水蒸气重整催化剂ZnO-ZrO2/γ-Al2O3。
本发明将呈弱酸弱碱性且对甲醇水蒸气重整反应具有良好活性的ZnO-ZrO2固溶体与二甲醚水解的固体酸催化剂γ-Al2O3混合,实现高效二甲醚水蒸气重整制氢。
本发明另一目的是提供一种二甲醚水蒸气重整制氢方法,该方法应用ZnO-ZrO2/γ-Al2O3催化剂,在固定床反应器上进行二甲醚水蒸气重整反应制氢。与现有二甲醚水蒸气重整催化剂相比,该方法反应温度为320~460℃,其中在380℃时催化反应性能最好,反应温区较低,二甲醚转化率高,产氢率高,且稳定性优良。
本发明的目的通过以下技术方案实现。
一种二甲醚水蒸气重整催化剂,该催化剂的组成为ZnO-ZrO2/γ-Al2O3,其中ZnO-ZrO2是固溶体,为重整活性组分;γ-Al2O3为水解活性组分。
优选的,ZnO-ZrO2固溶体中ZnO摩尔分数为13%~80%;ZnO-ZrO2与γ-Al2O3两种复合组分的质量比为0.5~5:1。
优选的,所述γ-Al2O3的粒径为10nm,比表面积为150~200m2·g-1。
优选的,所述ZnO-ZrO2固溶体按所需摩尔比采用传统共沉淀法制备。
优选的,所述ZnO-ZrO2/γ-Al2O3是组分ZnO-ZrO2与γ-Al2O3通过机械混合制备得到。
以上所述的一种二甲醚水蒸气重整催化剂应用于制氢的方法,包括以下步骤:
在固定床反应器中,装填组成为ZnO-ZrO2/γ-Al2O3的二甲醚水蒸气重整催化剂,以二甲醚和水为原料,N2为稀释气,将水汽化成水蒸气后与二甲醚混合,加热后通入固定床反应器中与二甲醚水蒸气重整催化剂接触进行重整反应制取氢气。
优选的,反应在常压下进行,反应的温度为320~460℃。
进一步优选的,所述反应的温度为380-390℃。
优选的,所述水与二甲醚的摩尔比为3~6:1。
优选的,所述反应的空速为3600~7200ml·gcat -1·h-1。
与已有技术相比,本发明具有如下优点和有益效果:
(1)本发明二甲醚水蒸气重整催化剂,与传统ZnO基催化剂相比,能够在380℃下达到最优活性,克服了ZnO基催化剂重整温度高的缺陷。
(2)本发明二甲醚水蒸气催化重整制氢,在反应条件下,二甲醚转化率可达95%,产氢率高达90%,CO选择性低,有微量甲烷生成,无明显积碳,稳定性好。
附图说明
图1为实施例11中二甲醚转化率随反应时间变化曲线图。
具体实施方式
下面通过实施例与附图对本发明的具体实施作进一步阐述,但本发明的保护范围不限于此。
以下实施例的试验操作过程中,室温为20~25℃。
实施例1
(1)将0.6g硝酸锌(Zn(NO3)2·6H2O)、5.8g硝酸锆(Zr(NO3)4·5H2O)溶于100ml去离子水中,称取3.06g(NH4)2CO3配制成100ml溶液。在70℃搅拌条件下,将(NH4)2CO3溶液缓慢滴加到混合硝酸盐溶液中形成沉淀;继续搅拌2h,冷却至室温,过滤,去离子水洗涤3次;所得沉淀物于空气气氛下110℃干燥4h,干燥完毕后于马弗炉中以1℃·min-1升温至500℃,在500℃恒温焙烧3h,获得金属氧化物固溶体重整活性组分ZnO-ZrO2,其中固溶体中ZnO的摩尔分数为13%,记作13%ZnO-ZrO2。
(2)将制得的13%ZnO-ZrO2和γ-Al2O3按质量比为2:1机械研磨混合均匀,压片筛分成40-60目,制得二甲醚水蒸气重整催化剂ZnO-ZrO2/γ-Al2O3。
(3)催化剂评价在固定床管式反应器中进行。取0.3g 40-60目二甲醚水蒸气重整催化剂ZnO-ZrO2/γ-Al2O3置于内径为5mm、长度为300mm的石英管中,常压下,反应温度为380℃,使用N2作为稀释气,在反应空速3600ml·gcat -1·h-1条件下向反应器通入摩尔比为3:1的水蒸气和二甲醚,进行反应,反应稳定后(约1小时),取样分析,结果见表1。
实施例2
按照实施例1的各个步骤,区别在于步骤(1)改为1.979g硝酸锌(Zn(NO3)2·6H2O),3.875g(NH4)2CO3。其中固溶体中ZnO的摩尔分数为33%,结果见表1。
实施例3
按照实施例1的各个步骤,区别在于步骤(1)改为4.02g硝酸锌(Zn(NO3)2·6H2O),5.2g(NH4)2CO3。其中固溶体中ZnO的摩尔分数为50%,结果见表1。
实施例4
按照实施例1的各个步骤,区别在于步骤(1)改为9.377g硝酸锌(Zn(NO3)2·6H2O),8.654g(NH4)2CO3。其中固溶体中ZnO的摩尔分数为70%,结果见表1。
实施例5
按照实施例1的各个步骤,区别在于步骤(1)改为16.076g硝酸锌(Zn(NO3)2·6H2O),12.981g(NH4)2CO3。其中固溶体中ZnO的摩尔分数为80%,结果见表1。
实施例6
按照实施例1的各个步骤,区别在于步骤(3)改为反应温度为360℃,结果见表2。
实施例7
按照实施例1的各个步骤,区别在于步骤(3)改为反应温度为400℃,结果见表2。
实施例8
按照实施例1的各个步骤,区别在于步骤(3)改为反应温度为420℃,结果见表2。
实施例9
按照实施例1的各个步骤,区别在于步骤(3)改为反应温度为440℃,结果见表2。
实施例10
按照实施例1的各个步骤,区别在于步骤(3)改为反应温度为460℃,结果见表2。
实施例11
按照实施例1的各个步骤,区别在于步骤(3)改为待反应稳定后,每隔1小时采样分析,实验持续9小时。结果见图1。
对比例1
(1)催化剂13%ZnO-ZrO2的制备,同实施例1步骤(1)。
(2)将上述所制催化剂压片筛分得40-60目13%ZnO-ZrO2催化剂。
(3)催化剂评价在固定床管式反应器中进行。取0.3g 40-60目催化剂置于内径为5mm、长度为300mm的石英管中,常压下,反应温度为380℃,使用N2作为载气,在反应空速3600ml·gcat -1·h-1下向反应器通入摩尔比为3:1的水蒸气和二甲醚,进行反应,反应稳定后(约1小时),取样分析,结果见表1。
对比例2
(1)将γ-Al2O3压片筛分得40-60目γ-Al2O3催化剂。
(2)催化剂评价同对比例1步骤(3)。
表1
表2
由表1、表2可知,本发明二甲醚水蒸气重整催化剂,与传统ZnO基催化剂相比,能够在380℃下达到最优活性,克服了ZnO基催化剂重整温度高的缺陷。而且本发明二甲醚水蒸气重整制氢催化剂,在反应条件下,二甲醚转化率可达95%,产氢率高达90%,CO选择性低,有微量甲烷生成,无明显积碳,稳定性好。
以上所述,仅是本发明实施例的较佳实施例,仅用作举例说明,并非对本发明实施例作任何形式上的限制,依据本发明实施例的技术实质对以上实施例所作的任何简单修改、变换与修饰,均应属于本发明技术方案的范围内。
Claims (7)
1.一种二甲醚水蒸气重整催化剂,其特征在于,该催化剂的组成为ZnO-ZrO2/γ-Al2O3,其中ZnO-ZrO2是固溶体,为重整活性组分;γ-Al2O3为水解活性组分;ZnO-ZrO2固溶体中ZnO摩尔分数为13%~80%;ZnO-ZrO2与γ-Al2O3两种复合组分的质量比为0.5~5:1。
2.根据权利要求1所述的一种二甲醚水蒸气重整催化剂,其特征在于,所述ZnO-ZrO2/γ-Al2O3是组分ZnO-ZrO2与γ-Al2O3通过机械混合制备得到。
3.权利要求1-2任一项所述的一种二甲醚水蒸气重整催化剂应用于制氢的方法,其特征在于,包括以下步骤:
在固定床反应器中,装填组成为ZnO-ZrO2/γ-Al2O3的二甲醚水蒸气重整催化剂,以二甲醚和水为原料,N2为稀释气,将水汽化成水蒸气后与二甲醚混合,加热后通入固定床反应器中与二甲醚水蒸气重整催化剂接触进行重整反应制取氢气。
4.根据权利要求3所述的方法,其特征在于,反应在常压下进行,反应的温度为320~460℃。
5.根据权利要求4所述的方法,其特征在于,所述反应的温度为380-390℃。
6.根据权利要求3所述的方法,其特征在于,所述水与二甲醚的摩尔比为3~6:1。
7.根据权利要求3所述的方法,其特征在于,所述反应的空速为3600~7200 ml·gcat -1·h-1。
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