CN108114724A - 一氧化碳水汽变换低温催化剂的制备方法 - Google Patents
一氧化碳水汽变换低温催化剂的制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 32
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000725 suspension Substances 0.000 claims abstract description 21
- 229910017518 Cu Zn Inorganic materials 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 17
- 230000001376 precipitating effect Effects 0.000 claims abstract description 17
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229940007718 zinc hydroxide Drugs 0.000 claims abstract description 16
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000000694 effects Effects 0.000 claims abstract description 6
- 150000001879 copper Chemical class 0.000 claims abstract description 5
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 15
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- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
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- 238000004448 titration Methods 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 239000011686 zinc sulphate Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
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- 239000000203 mixture Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
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- 238000000975 co-precipitation Methods 0.000 abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
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- 239000010453 quartz Substances 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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Abstract
本发明公开一种一氧化碳水汽变换低温催化剂的制备方法，属于催化技术领域。该方法具体内容是：将沉淀剂滴加到含有锌盐和载体γ‑Al2O3的溶液中制备氢氧化锌悬浊液。然后将沉淀剂溶液和铜盐溶液同时滴加到氢氧化锌悬浊液中，调节溶液的pH值并不断搅拌，再经过抽滤、洗涤、干燥、焙烧，得到Cu‑Zn/γ‑Al2O3催化剂；Cu含量为20‑40wt％，铜锌摩尔比为1:1。应用该方法制备的催化剂在典型的重整气中进行水汽变换反应，具有高的活性和稳定性，表现出比传统共沉淀法制备的催化剂更高的反应活性。
Description
技术领域：
本发明属于催化技术领域，具体涉及一种一氧化碳水汽变换低温催化剂的制备方法。
背景技术：
随着科技的进步和世界人口的增长，能源短缺问题已引起越来越多的关注。当前化石能源需求量的日益增加而储量日益减少，开发新型的可持续利用的能源迫切成为当今社会中人们最关注的问题之一。氢能作为一种新型能源，具有清洁无污染、燃烧热值高、导热性好、燃烧产物可循环等优点，因此也成为未来最有可能替代现今化石能源的新能源。其中，通过甲醇、天然气等化合物重整制氢用于燃料电池的氢源，一直备受研究者的关注。然而，重整气中通常会含有5％-20％的CO，这会导致质子交换膜燃料电池的铂电极产生中毒现象继而使电池性能严重下降。因此，有必要降低重整气中的CO含量，例如通过水汽变换反应(CO+H2O＝CO2+H2)。水汽变换反应在消除CO的同时也产生了相同体积的氢气。另外，水汽变换反应在合成氨、合成甲醇、汽油及调节合成汽油生产中的碳氢比例和城市煤气工业中得到了广泛的应用。商业用的变换催化剂主要分为高温变换催化剂、低温变换催化剂和宽温变换催化剂。低温变换催化剂一般为铜锌系催化剂，这类催化剂反应活性高，但存在热稳定性差、选择性差、接触空气易自然等缺点。目前催化剂主要采用共沉淀法制备，制备过程中的许多因素都会导致催化剂的重复性不高，例如常见的因素有pH值、沉淀剂、沉淀温度、老化时间等。鉴于水汽变化反应在工业过程中的重要性以及在燃料电池电动车上净化原料气氢气的应用前景，世界各国主要从生产工艺和催化剂的制备上进行了广泛的研究，以求合成活性高、稳定性好、重现性高的催化剂。针对现有催化剂的不足，中国专利(CN201510678685.X)中合成了一种具有良好的低温活性、耐热稳定性和长期稳定性的纳米复合结构Cu/ZnAl2O4低温水煤气变换催化剂。由此可见，研制出活性高、稳定性好的水汽变换低温催化剂成为此类型催化剂适用于更广范围的反应系统的关键之一。
发明内容：
本发明的目的在于提供一种良好的低温活性、稳定性的纳米Cu-Zn/γ-Al2O3低温水汽变换催化剂的制备方法。
本发明所提供的一氧化碳水汽变换低温催化剂的制备方法，所述催化剂活性组分为Cu、Zn，载体为γ-Al2O3，Cu含量为20-40wt％，铜锌摩尔比为1:1；通过分布沉淀法制备沉淀物，再经过抽滤、洗涤、干燥、焙烧，制得Cu-Zn/γ-Al2O3催化剂；该制备方法具体步骤如下：
(1)配制一定浓度的沉淀剂溶液，逐滴加入到含有锌盐和载体γ-Al2O3的溶液中并不断搅拌至pH值为9，得到氢氧化锌悬浊液，滴定完成后继续搅拌40min；
(2)配制一定浓度的铜盐溶液，将步骤(1)所述沉淀剂溶液和所述铜盐溶液同时缓慢地滴加到步骤(1)得到的所述氢氧化锌悬浊液中，不断搅拌并保持pH值为8，当铜盐滴加完毕后继续滴加所述沉淀剂溶液至pH值为9，得到的悬浊液在60℃水浴中继续搅拌2-4h，然后抽滤，用蒸馏水洗涤至pH值为7，固体在80℃烘箱中干燥12-24h，即得沉淀物前驱体；
(3)将所述沉淀物前驱体在氧化性气氛中400℃下煅烧2h，制得所述一氧化碳水汽变换低温催化剂Cu-Zn/γ-Al2O3。
所述铜盐为Cu(NO3)2·3H2O、CuSO4·5H2O或CuCl2·2H2O，浓度为0.06～0.15mol/L；所述锌盐为Zn(NO3)2·6H2O、ZnSO4·7H2O或ZnCl2，浓度为0.05～0.12mol/L；所述沉淀剂为氨水、碳酸钠、氢氧化钠、及碳酸氢钠中的任意一种，浓度为0.4mol/L；所述氧化性气氛为空气、氧气或氧气与氮气混合气的任意一种
本发明中所使用的具体催化剂评价方法为：评价装置采用固定床反应器；原料气为3％CO，12％H2O，N2平衡。催化剂装填量为0.06g；反应温度为150-300℃，空速为30000mL/(g·h)。反应在常压条件下进行，气体经过催化剂后用气相色谱仪在线检测。
本发明具有以下技术特点：
1、本发明的Cu-Zn/γ-Al2O3催化剂具有纳米复合结构，活性组分为CuO和ZnO。
2、本发明的Cu-Zn/γ-Al2O3催化剂与传统共沉淀法制备的催化剂相比，对水汽变换反应具有良好的低温活性、稳定性，应用前景良好。
附图说明：
图1为本发明分布沉淀法制备的Cu-Zn/γ-Al2O3催化剂和共沉淀法制备的Cu-Zn/γ-Al2O3催化剂在水汽变换反应中的催化活性。
图2为本发明分布沉淀法制备的Cu-Zn/γ-Al2O3催化剂和共沉淀法制备的Cu-Zn/γ-Al2O3催化剂在水汽变换反应中的稳定性。
具体实施方式：
以下结合附图和具体实施例详述本发明，但本发明不局限于下述实施例。
实施例1：
(1)称取4.242g Na2CO3放入100ml容量瓶中，加入蒸馏水摇匀定容，作为沉淀剂备用。称取1.175g Zn(NO3)2·6H2O置于100ml烧杯中，加入50ml蒸馏水溶解，再加入0.103g工业级γ-Al2O3。在室温下将Na2CO3溶液缓慢滴加到上述含有Zn盐溶液中，并不断搅拌至终点为pH＝9时停止滴加，得到氢氧化锌悬浊液。滴加完毕后继续搅拌40min。
(2)称取0.947g Cu(NO3)2·3H2O置于100ml烧杯中，加入50ml蒸馏水溶解。将沉淀剂Na2CO3溶液和上述Cu盐溶液同时缓慢滴加到氢氧化锌悬浊液中，在同时滴加的过程中不断搅拌，并控制pH为8左右。当铜盐滴加完毕后继续滴加沉淀剂Na2CO3溶液至pH为9。得到的悬浊液在60℃水浴中继续搅拌2h，然后抽滤，用蒸馏水洗涤至pH为7。固体在80℃烘箱中干燥12-24h，即得沉淀物前驱体。将沉淀物前驱体在空气气氛中400℃下煅烧2h，即得Cu-Zn/γ-Al2O3(SP)催化剂。
实施例2：
(1)称取4.247g Na2CO3放入100ml容量瓶中，加入蒸馏水摇匀定容，作为沉淀剂备用。称取1.155g ZnSO4·7H2O置于100ml烧杯中，加入50ml蒸馏水溶解，再加入0.105g工业级γ-Al2O3。在室温下将Na2CO3溶液缓慢滴加到上述含有Zn盐的溶液中，并不断搅拌至终点为pH＝9时停止滴加，得到氢氧化锌悬浊液。滴加完毕后继续搅拌40min。
(2)称取0.945g Cu(NO3)2·3H2O置于100ml烧杯中，加入50ml蒸馏水溶解。将沉淀剂Na2CO3溶液和上述Cu盐溶液同时缓慢滴加到氢氧化锌悬浊液中，在同时滴加的过程中不断搅拌，并控制pH为8左右。当铜盐滴加完毕后继续滴加沉淀剂Na2CO3溶液至pH为9。得到的悬浊液在60℃水浴中继续搅拌2h，然后抽滤，用蒸馏水洗涤至pH为7。固体在80℃烘箱中干燥12-24h，即得沉淀物前驱体。将沉淀物前驱体在空气气氛中400℃下煅烧2h，即得Cu-Zn/γ-Al2O3(SP)催化剂。
实施例3：
(1)称取4.243g Na2CO3放入100ml容量瓶中，加入蒸馏水摇匀定容，作为沉淀剂备用。称取0.688g ZnCl2·2H2O置于100ml烧杯中，加入50ml蒸馏水溶解，再加入0.102g工业级γ-Al2O3。在室温下将Na2CO3溶液缓慢滴加到上述含有Zn盐的溶液中，并不断搅拌至终点为pH＝9时停止滴加，得到氢氧化锌悬浊液。滴加完毕后继续搅拌40min。
(2)称取0.941g Cu(NO3)2·3H2O置于100ml烧杯中，加入50ml蒸馏水溶解。将沉淀剂Na2CO3溶液和上述Cu盐溶液同时缓慢滴加到氢氧化锌悬浊液中，在同时滴加的过程中不断搅拌，并控制pH为8左右。当铜盐滴加完毕后继续滴加沉淀剂Na2CO3溶液至pH为9。得到的悬浊液在60℃水浴中继续搅拌2h，然后抽滤，用蒸馏水洗涤至pH为7。固体在80℃烘箱中干燥12-24h，即得沉淀物前驱体。将沉淀物前驱体在空气气氛中400℃下煅烧2h，即得Cu-Zn/γ-Al2O3(SP)催化剂。
实施例4：
(1)称取4.242g Na2CO3放入100ml容量瓶中，加入蒸馏水摇匀定容，作为沉淀剂备用。称取1.178g Zn(NO3)2·6H2O置于100ml烧杯中，加入50ml蒸馏水溶解，再加入0.103g工业级γ-Al2O3。在室温下将Na2CO3溶液缓慢滴加到上述含有Zn盐的溶液中，并不断搅拌至终点为pH＝9时停止滴加，得到氢氧化锌悬浊液。滴加完毕后继续搅拌40min。
(2)称取1.003g CuSO4·3H2O置于100ml烧杯中，加入50ml蒸馏水溶解。将沉淀剂Na2CO3溶液和上述Cu盐溶液同时缓慢滴加到氢氧化锌悬浊液中，在同时滴加的过程中不断搅拌，并控制pH为8左右。当铜盐滴加完毕后继续滴加沉淀剂Na2CO3溶液至pH为9。得到的悬浊液在60℃水浴中继续搅拌2h，然后抽滤，用蒸馏水洗涤至pH为7。固体在80℃烘箱中干燥12-24h，即得沉淀物前驱体。将沉淀物前驱体在空气气氛中400℃下煅烧2h，即得Cu-Zn/γ-Al2O3(SP)催化剂。
实施例5：
(1)称取4.240g Na2CO3放入100ml容量瓶中，加入蒸馏水摇匀定容，作为沉淀剂备用。称取1.172g Zn(NO3)2·6H2O置于100ml烧杯中，加入50ml蒸馏水溶解，再加入0.103g工业级γ-Al2O3。在室温下将Na2CO3溶液缓慢滴加到上述含有Zn盐的溶液中，并不断搅拌至终点为pH＝9时停止滴加，得到氢氧化锌悬浊液。滴加完毕后继续搅拌40min。
(2)称取0.535g CuCl2·3H2O置于100ml烧杯中，加入50ml蒸馏水溶解。将沉淀剂Na2CO3溶液和上述Cu盐溶液同时缓慢滴加到氢氧化锌悬浊液中，在同时滴加的过程中不断搅拌，并控制pH为8左右。当铜盐滴加完毕后继续滴加沉淀剂Na2CO3溶液至pH为9。得到的悬浊液在60℃水浴中继续搅拌2h，然后抽滤，用蒸馏水洗涤至pH为7。固体在80℃烘箱中干燥12-24h，即得沉淀物前驱体。将沉淀物前驱体在空气气氛中400℃下煅烧2h，即得Cu-Zn/γ-Al2O3(SP)催化剂。
实施例6：
称取4.244g Na2CO3放入100ml容量瓶中，加入蒸馏水摇匀定容，作为沉淀剂备用。分别称取1.168g Zn(NO3)2·6H2O和0.946g Cu(NO3)2·3H2O放入100ml烧杯中，加入50ml蒸馏水溶解，再加入0.106g工业级γ-Al2O3。超声分散均匀后，在室温下用Na2CO3溶液缓慢滴加到上述含有Cu盐和Zn盐的溶液中，并不断搅拌至终点为pH＝9时停止滴加。滴定完毕后在60℃的水浴中加热搅拌4h，然后抽滤，用蒸馏水洗涤至pH为7。固体在80℃烘箱中干燥12-24h，然后在在空气气氛中400℃下煅烧2h，即得Cu-Zn/γ-Al2O3(CP)催化剂。
实施例7：
将上述所制得的催化剂进行筛分，称取颗粒度为20-40目的催化剂0.06g，在固定床石英管反应器上进行水汽变换反应性能测试。石英管内径为8mm，反应气空速为30000mL/(g·h)。反应气按体积比组成为：3％CO，12％H2O，85％N2。样品在反应性能测试前，先在30ml/min的空气气氛中从室温升至400℃，并保持2h。之后切换为Ar气氛进行样品的冷却。冷却至150℃以下再切换为反应气进行反应。反应过程中采用程序升温以1℃/min的速率从150℃升至300℃，在此期间采用福立9790气相色谱仪在线检测，TDX-01柱，TCD检测器。催化剂性能测试结果见附图1。采用分布沉淀法制备出的Cu-Zn/γ-Al2O3催化剂在低温时的水汽变换反应活性明显优于传统共沉淀法制备的催化剂。将反应温度固定在220℃进行催化剂的稳定性测试，见附图2。分布沉淀法制备出的Cu-Zn/γ-Al2O3催化剂在50h的稳定性测试中，始终保持90％的CO转化率。传统共沉淀法制备的催化剂在反应初始时的CO转化率为46％左右，随后提高到60％左右，并也可保持接近50h的稳定性。
Claims (2)
1.一种一氧化碳水汽变换低温催化剂的制备方法，其特征在于所述催化剂活性组分为Cu、Zn，载体为γ-Al2O3，Cu含量为20-40wt％，铜锌摩尔比为1:1；通过分布沉淀法制备沉淀物，再经过抽滤、洗涤、干燥、焙烧，制得Cu-Zn/γ-Al2O3催化剂；该制备方法具体步骤如下：
(1)配制一定浓度的沉淀剂溶液，逐滴加入到含有锌盐和载体γ-Al2O3的溶液中并不断搅拌至pH值为9，得到氢氧化锌悬浊液，滴定完成后继续搅拌40min；
(2)配制一定浓度的铜盐溶液，将步骤(1)所述沉淀剂溶液和所述铜盐溶液同时缓慢地滴加到步骤(1)得到的所述氢氧化锌悬浊液中，不断搅拌并保持pH值为8，当铜盐滴加完毕后继续滴加所述沉淀剂溶液至pH值为9，得到的悬浊液在60℃水浴中继续搅拌2-4h，然后抽滤，用蒸馏水洗涤至pH值为7，固体在80℃烘箱中干燥12-24h，即得沉淀物前驱体；
(3)将所述沉淀物前驱体在氧化性气氛中400℃下煅烧2h，制得所述一氧化碳水汽变换低温催化剂Cu-Zn/γ-Al2O3。
2.根据权利要求1所述的制备方法，其特征在于所述铜盐为Cu(NO3)2·3H2O、CuSO4·5H2O或CuCl2·2H2O，浓度为0.06～0.15mol/L；所述锌盐为Zn(NO3)2·6H2O、ZnSO4·7H2O或ZnCl2，浓度为0.05～0.12mol/L；所述沉淀剂为氨水、碳酸钠、氢氧化钠、及碳酸氢钠中的任意一种，浓度为0.4mol/L；所述氧化性气氛为空气、氧气或氧气与氮气混合气的任意一种。
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