CN111389399B - 一种用于水煤气变换反应的铜基催化剂及其制备方法 - Google Patents
一种用于水煤气变换反应的铜基催化剂及其制备方法 Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 130
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 29
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 17
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 4
- 238000001704 evaporation Methods 0.000 claims abstract description 3
- 230000008020 evaporation Effects 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 45
- 239000000725 suspension Substances 0.000 claims description 18
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
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- 238000003756 stirring Methods 0.000 claims description 10
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- 238000005406 washing Methods 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- ZZBBCSFCMKWYQR-UHFFFAOYSA-N copper;dioxido(oxo)silane Chemical compound [Cu+2].[O-][Si]([O-])=O ZZBBCSFCMKWYQR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 12
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- 229910021641 deionized water Inorganic materials 0.000 description 9
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
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- BHGBNDNKYPEAAT-UHFFFAOYSA-N 2-(ethoxymethyl)furan Chemical compound CCOCC1=CC=CO1 BHGBNDNKYPEAAT-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- 238000003723 Smelting Methods 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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Abstract
本发明公开了一种用于水煤气变换反应的铜基催化剂及其制备方法,该催化剂由Cu活性组分,SiO2载体构成;其具体是采用蒸氨‑水热法,将含硅原料分散在铜氨络合溶液中,在一定温度下进行蒸氨处理,再经水热、焙烧后获得催化剂前驱体CuO/SiO2,所得前驱体经还原制得Cu/SiO2催化剂。本发明的催化剂前驱体中CuO颗粒呈高度分散状态,且颗粒较小,同时生成了层状硅酸铜物种;前驱体经还原,获得了稳定的小尺寸金属Cu纳米晶和一价Cu物种,提高了催化剂解离水和吸附CO的能力,表现出良好的催化活性,将其应用于水煤气变换反应可获得较高的变换制氢效率。
Description
技术领域
本发明属于水煤气变换制氢技术领域,具体涉及一种用于水煤气变换反应的Cu/SiO2催化剂及其制备方法。
背景技术
随着氢气利用技术逐渐发展成熟,氢气因具有高能效、资源丰富、可再生等特点,在高能燃料、化工原料、冶炼金属和燃料电池等多方面表现出不可替代的重要作用。传统能源因为其不可再生的特性,势必会被新能源所取代,所以针对氢气的相关研究十分重要。制氢是氢气利用的基础,水煤气变换(Water-Gas Shift,WGS,CO+H2O⇌CO2+H2)反应是工业上制取氢气的重要步骤。该过程通过将碳氢燃料气化或重整产物中的CO与H2O反应,将H2O中的H转化为H2,同时降低CO浓度获得洁净H2。在此过程中,催化剂是提高反应效率和改变产物选择性的关键。
非贵金属铜作水煤气变换反应催化剂活性金属的应用已被广泛研究。美国专利(US 2002147103)描述了一种负载在氧化铈载体上的铜基催化剂,该催化剂在较低的温度下(低于220℃)具有较高的稳定性能。日本专利(JP 2003275590)描述了一种负载在Zn-Al氧化物上的Cu-碱金属催化剂,铜以单价铜离子的状态负载在锌铝双氧化物的表面上,具有高活性及高稳定性。中国专利(CN 1654121A)公开了一种铜锰基变换催化剂及其制备方法,催化剂通式为Cua(Mn)bO4-M,活性组分为Cua(Mn)bO4,M为热稳定助剂。中国专利(CN104014345A)公开了一种络合-沉淀法制备的Cu/CeO2催化剂,将Cu2+络合成[Cu(NH3)4]2+再沉积于CeO2载体表面,CuO微晶呈高度分散,对水煤气变换反应具有较高的活性,适用温区宽。
中国专利(CN 105107513A)公开了一种以介孔硅为模板制备Cu基水煤气变换催化剂的方法,采用介孔氧化硅为模板,可溶性铜盐、铈盐为活性组分,制得催化剂比表面积大,热稳定性好,活性高。中国专利(CN 110871071A)公开了一种Cu/SiO2催化剂及其在催化草酸二甲酯加氢制备乙醇酸甲酯反应中的应用,该催化剂采用物理溅射法一步制备获得,所制备的催化剂中铜物种为零价铜。中国专利(CN 109985626A)公开了一种二氧化硅载体负载金属Cu催化剂在糠醛液相加氢制乙基糠基醚中的应用,其采用蒸氨法负载铜,铜负载量优选为15-40%,氨水(10-20wt%)的用量与铜的质量比为5-50:1。中国专利(CN11050828A)公开了一种二氧化铈、二氧化锆或二氧化钛改性的Cu/SiO2催化剂应用于水煤气变换反应,该催化剂中同时存在金属Cu和Cu2O两种活性物种,同时助剂表面氧空位对提高催化剂的性能起到较好的促进作用。但现有的Cu基催化剂中活性物种大多为单一的金属Cu物种;而对于金属铜和一价铜共存的催化剂体系中,二者的比例固定不可调节。
发明内容
本发明为克服现有的Cu基水煤气变换反应催化剂活性Cu物种结构单一的缺陷,提供了一种用于水煤气变换反应,其活性Cu物种金属铜和一价铜共存,且比例可调、活性高、适用温区宽和耐热稳定性优异的Cu/SiO2催化剂及其制备方法。
为实现上述目的,本发明采用如下技术方案:
一种用于铜基水煤气变换反应的铜基催化剂,其是由Cu活性组分,SiO2载体构成;以质量百分比计,铜的含量为7-20%,SiO2的含量为80-93%,两者之和为100%。
所述铜基催化剂的制备方法包括如下步骤:
1)在室温下,将质量浓度为25%的氨水溶液逐滴加入铜盐溶液中,得到Cu2+与NH3的摩尔比为1:(2-6.5)的铜氨络合溶液;
2)将含硅原料加入到上述铜氨络合溶液中,并调节pH为8-12,然后以300-500 r/min搅拌4-12h,得到悬浮液;
3)将所得悬浮液在油浴中加热至60-90℃,蒸氨处理1-7h;
4)将蒸氨处理后的混合溶液于120-190℃水热釜中水热处理6-36h;
5)水热产物经冷却、离心、洗涤后,于80-120℃干燥后,再于400-600℃焙烧1-8h,制得催化剂前驱体CuO/SiO2;
6)在所得前驱体在还原性气氛中、于250-550℃还原2-8h,制得Cu/SiO2催化剂。
步骤1)所述铜盐溶液为硫酸铜、硝酸铜、氯化铜中一种或几种的水溶液。
步骤2)所述含硅原料为正硅酸乙酯、硅酸钠、四甲氧基硅烷、硅溶胶中的一种或几种。
步骤6)所述还原性气氛为5-10%的H2/N2混合气。
本发明的显著优点在于:
Cu/SiO2催化剂的活性组分为Cu,Cu晶粒的尺寸以及物相对其变换性能影响显著。本发明通过蒸氨-水热法制得的催化剂前驱体中存在高分散、小尺寸的氧化铜和层状硅酸铜物种;其经还原后,高分散、小尺寸的氧化铜还原为金属铜(Cu0)纳米颗粒,层状硅酸铜还原为一价铜(Cu+)物种,实现Cu0和Cu+物种的稳定共存;并通过控制还原温度,可获得Cu0和Cu+比例可控的Cu/SiO2催化剂。Cu0和Cu+物种在水煤气变换反应中均有吸附CO和解离水的能力,其中Cu+物种对CO吸附的能力较Cu0强;而Cu0物种对水的解离能力较Cu+强;二者共存可以大大提高水煤气变换反应过程两个基元步骤(CO吸附和水解离)的反应速率,从而提高催化剂的催化活性;通过调节Cu0和Cu+比例还可进一步提高其催化性能。同时,由于SiO2载体的比表面积大,且存在较强的铜物种与载体间的相互作用,从而可起到稳定活性物种Cu0和Cu+的作用,进而表现出优异的催化稳定性,达到较好的水煤气变换反应效果,提高了变换制氢的效率。
附图说明
图1为实施例5和对比例1-2所制得催化剂的XRD图。
图2为实施例3、5和6所得Cu/SiO2催化剂的俄歇电子能谱图。
图3为实施例5所得Cu/SiO2催化剂在250℃下水煤气变换反应50h的稳定性图。
具体实施方式
下面对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
1)称取5.36g(0.0314mol)CuCl2·2H2O,加入100mL去离子水溶解;然后滴入5mL质量浓度为25%的氨水溶液并搅拌30min,形成铜氨络合溶液,其中Cu2+与NH3的摩尔比为1:2.1;
2)在步骤1)所得铜氨络合溶液中滴加20g四甲氧基硅烷,并调节混合液的pH值约为11,然后在300 r/min的转速下机械搅拌6h,得到悬浊液;
3)将步骤2)所得悬浊液在90℃油浴中蒸氨处理1h;
4)将步骤3)反应后的溶液放入水热釜中,在190℃下水热反应6h,待水热釜自然冷却至室温后经离心洗涤,烘箱中120℃干燥4h,马弗炉中静态空气下400℃焙烧4h,制得催化剂前驱体CuO/SiO2;
5)将步骤4)所得前驱体在300℃、5% H2/N2混合气条件下还原8h,制得Cu/SiO2催化剂,其中Cu含量20 wt%。
实施例2
1)称取2.14g(0.0125mol)CuCl2·2H2O,加入100mL去离子水溶解;然后滴入5mL质量浓度为25%的氨水溶液并搅拌30min,形成铜氨络合溶液,其中Cu2+与NH3的摩尔比为1:5.3;
2)在步骤1)所得铜氨络合溶液中滴加19g硅酸钠,并调节混合液的pH值约为11,然后在300 r/min的转速下机械搅拌12h,得到悬浊液;
3)将步骤2)所得悬浊液在90℃油浴中蒸氨处理1h;
4)将步骤3)反应后的溶液放入水热釜中,在190℃下水热反应6h,待水热釜自然冷却至室温后经离心洗涤,烘箱中80℃干燥4h,马弗炉中静态空气下500℃焙烧8h,制得催化剂前驱体CuO/SiO2;
5)将步骤4)所得前驱体在550℃、5% H2/N2混合气条件下还原5h,制得Cu/SiO2催化剂,其中Cu含量7.4 wt%。
实施例3
1)称取5.32g(0.0312mol) CuCl2·2H2O,加入100mL去离子水溶解;然后滴入15mL质量浓度为25%的氨水溶液并搅拌30min,形成铜氨络合溶液,其中Cu2+与NH3的摩尔比为1:6.4;
2)在步骤1)所得铜氨络合溶液中滴加27g硅溶胶,并调节混合液的pH值约为8,然后在300 r/min的转速下机械搅拌12h,得到悬浊液;
3)将步骤2)所得悬浊液在90℃油浴中蒸氨处理1h;
4)将步骤3)反应后的溶液放入水热釜中,在150℃下水热反应21h,待水热釜自然冷却至室温后经离心洗涤,烘箱中120℃干燥4h,马弗炉中静态空气下500℃焙烧1h,制得催化剂前驱体CuO/SiO2;
5)将步骤4)所得前驱体在550℃、5% H2/N2混合气条件下还原5h,制得Cu/SiO2催化剂,其中Cu含量18.8 wt%。
实施例4
1)称取7.85g(0.0314mol)CuSO4·5H2O,加入100mL去离子水溶解;然后滴入15mL质量浓度为25%的氨水溶液并搅拌30min,形成铜氨络合溶液,其中Cu2+与NH3的摩尔比为1:6.4;
2)在步骤1)所得铜氨络合溶液中滴加25g硅溶胶,并调节混合液的pH值约为12,然后在400 r/min的转速下机械搅拌8h,得到悬浊液;
3)将步骤2)所得悬浊液在90℃油浴中蒸氨处理1h;
4)将步骤3)反应后的溶液放入水热釜中,在120℃下水热反应36h,待水热釜自然冷却至室温后经离心洗涤,烘箱中120℃干燥4h,马弗炉中静态空气下500℃焙烧4h,制得催化剂前驱体CuO/SiO2;
5)将步骤4)所得前驱体在350℃、5% H2/N2混合气条件下还原5h,制得Cu/SiO2催化剂,其中Cu含量20 wt%。
实施例5
1)称取7.60g(0.0314mol)Cu(NO3)2·3H2O,加入100mL去离子水溶解;然后滴入10mL质量浓度为25%的氨水溶液并搅拌30min,形成铜氨络合溶液,其中Cu2+与NH3的摩尔比为1:4.3;
2)在步骤1)所得铜氨络合溶液中滴加25g硅溶胶,并调节混合液的pH值约为11,然后在300 r/min的转速下机械搅拌6h,得到悬浊液;
3)将步骤2)所得悬浊液在75℃油浴中蒸氨处理4h;
4)将步骤3)反应后的溶液放入水热釜中,在150℃下水热反应21h,待水热釜自然冷却至室温后经离心洗涤,烘箱中120℃干燥4h,马弗炉中静态空气下500℃焙烧4h,制得催化剂前驱体CuO/SiO2;
5)将步骤4)所得前驱体在300℃、10% H2/N2混合气条件下还原2h,制得Cu/SiO2催化剂,其中Cu含量20 wt%。
实施例6
1)称取7.60g(0.0314mol)Cu(NO3)2·3H2O,加入100mL去离子水溶解;然后滴入10mL质量浓度为25%的氨水溶液并搅拌30min,形成铜氨络合溶液,其中Cu2+与NH3的摩尔比为1:4.3;
2)在步骤1)所得铜氨络合溶液中滴加28g正硅酸乙酯,并调节混合液的pH值约为11,然后在500 r/min的转速下机械搅拌4h,得到悬浊液;
3)将步骤2)所得悬浊液在60℃油浴中蒸氨处理7h;
4)将步骤3)放入水热釜中,在120℃下水热反应36h,待水热釜自然冷却至室温后经离心洗涤,烘箱中100℃干燥4h,马弗炉中静态空气下600℃焙烧4h,制得催化剂前驱体CuO/SiO2;
5)将步骤4)所得前驱体在250℃、10% H2/N2混合气条件下还原8h,制得Cu/SiO2催化剂,其中Cu含量20 wt%。
对比例1
1)称取15.20g(0.0629mol)Cu(NO3)2·3H2O,加入100mL去离子水溶解;然后滴入20mL质量浓度为25%氨水溶液并搅拌30min,形成铜氨络合溶液,其中Cu2+与NH3的摩尔比为1:4.3;
2)在步骤1)所得铜氨络合溶液中滴加25g硅溶胶,并调节混合液的pH值约为11,然后在300 r/min的转速下机械搅拌6h,得到悬浊液;
3)将步骤2)所得悬浊液在75℃油浴中蒸氨处理4h;
4)将步骤3)反应后的溶液放入水热釜中,在150℃下水热反应21h,待水热釜自然冷却至室温后经离心洗涤,烘箱中120℃干燥4h,马弗炉中静态空气下500℃焙烧4h,制得催化剂前驱体CuO/SiO2;
5)将质量浓度为68%的硝酸溶液与去离子水以体积比1:9的比例混合,取4mL滴加到2.0 g步骤4)所得前驱体上,静置5h,然后经过滤、洗涤直至上层清液的pH为中性,在120℃下干燥12h;
6)将步骤5)所得前驱体在300℃下、10% H2/N2混合气条件下还原2h,制得Cu/SiO2催化剂,其中Cu含量18.3 wt%。
对比例2
1)称取25g硅溶胶,在烘箱中120℃干燥4h,然后在马弗炉中静态空气下500℃焙烧4h,研磨后即得SiO2载体;
2)称取7.60g(0.0314mol)Cu(NO3)2·3H2O,加入6mL去离子水溶解,得到硝酸铜溶液;
3)将步骤1)所得SiO2载体分散于步骤2)所得硝酸铜溶液中,并搅拌均匀;
4)将步骤3)所得产物在烘箱中120℃干燥4h,然后在马弗炉中静态空气下500℃焙烧4h,得到催化剂前驱体CuO/SiO2;
5)将步骤4)所得前驱体在300℃下、10% H2/N2混合气条件下还原2h,制得Cu/SiO2催化剂,其中Cu含量20 wt%。
采用X’ pert Pro衍射仪(荷兰Panalytic公司)进行X射线粉末衍射分析:X’Celerator探测器,Cu-Kα(λ=0.1542 nm)靶辐射,管压40 kV,管流40 mA,扫描步长为0.0167°,每步10 s,扫描范围为2θ=10~90°。
活性测试条件为:原料气组成为(体积分数)15% CO、55% H2、7% CO2、23% N2,反应汽气比为1:1,质量空速4500 mL/(g·h),催化剂活性测试温区为200~450℃。
稳定性测试条件为:原料气组成为(体积分数)15% CO、55% H2、7% CO2、23% N2,反应汽气比为1:1,质量空速4500 mL/(g·h),测试温度250℃。
催化剂的活性用CO转化率表示,其计算方法如下:
CO转化率=(1-VCO'/VCO)/(1+VCO)×100%,
其中,VCO'为反应器出口气中CO的体积百分数,VCO为原料气中CO的体积百分数。
图1为实施例5和对比例1、2所制得催化剂的XRD图,其中a为实施例5所得Cu/SiO2催化剂样品,b为对比例1所得Cu/SiO2催化剂样品,c为实施例2所得Cu/SiO2催化剂样品。由图1可见,对比例1所得样品中活性金属Cu在体相的主要物种为Cu2O;对比例2所得样品中活性金属Cu在体相的主要物种为金属态Cu;而实施例5所制备的催化剂同时含有Cu0和Cu+物种,且峰型弥散,说明Cu0和Cu+物种的晶粒尺寸较小。
图2为实施例3、5和6 所得Cu/SiO2催化剂的俄歇电子能谱图。由图中可见,经不同温度还原的催化剂中Cu+和Cu0的比例有所差异,高温还原(550℃)使更多的Cu+被还原为Cu0,而适度的还原温度(300℃)有利于获得较多的Cu+物种。
实施例及对比例的活性评价结果如表1。
表1 实施例及对比例催化剂样品的催化活性评价结果
从表中数据可以看出,采用蒸氨水热法制备的Cu0和Cu+共存的催化剂(实施例1-6)表现出较含有单一Cu0或Cu+的催化剂(对比例1和2)更高的水煤气变换反应活性;实施例2铜含量较低CO转化率相对不高;经较低温度还原(250或300℃)制得的Cu/SiO2催化剂(实施例5和6)含有较高的Cu+,而经550℃还原的催化剂Cu+比例较低,其中300℃还原制得的催化剂(实施例5)中的Cu+比例最高,CO转化率也相对最高。
图3为实施例5所得Cu/SiO2催化剂在250℃下,经50h水煤气变换反应的稳定性评价结果。由图2可见,在50h的稳定性测试中,CO转化率没有发生明显的下降,说明所得Cu/SiO2催化剂具有良好的水煤气变换反应稳定性能。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (7)
1.一种铜基催化剂在水煤气变换反应中的应用,其特征在于,所述铜基催化剂由Cu活性组分,SiO2载体构成;以质量百分比计,铜的含量为20%,SiO2的含量为80%;其制备方法包括如下步骤:
1)在室温下,将氨水溶液逐滴加入铜盐溶液中,得到铜氨络合溶液;
2)将含硅原料加入到上述铜氨络合溶液中,并调节pH,然后以300-500r/min搅拌4-12h,得到悬浮液;
3)将所得悬浮液在油浴中加热,进行蒸氨处理;
4)将蒸氨处理后的混合溶液进行水热处理;
5)水热产物经冷却、离心、洗涤、干燥、焙烧,制得催化剂前驱体CuO/SiO2;
6)将所得前驱体在还原性气氛中进行还原,制得Cu/SiO2催化剂;
步骤4)所述水热处理的温度为150℃,时间为21h;
步骤6)所述还原性气氛为10%的H2/N2混合气,还原的温度为300℃,时间为2h。
2.根据权利要求1所述的铜基催化剂在水煤气变换反应中的应用,其特征在于,步骤1)所述铜盐溶液为硫酸铜、硝酸铜、氯化铜中一种或几种的水溶液;所述氨水溶液的质量浓度为25%。
3.根据权利要求1所述的铜基催化剂在水煤气变换反应中的应用,其特征在于,步骤1)所得铜氨络合溶液中Cu2+与NH3的摩尔比为1:(2-6.5)。
4.根据权利要求1所述的铜基催化剂在水煤气变换反应中的应用,其特征在于,步骤2)所述含硅原料为正硅酸乙酯、硅酸钠、四甲氧基硅烷、硅溶胶中的一种或几种。
5.根据权利要求1所述的铜基催化剂在水煤气变换反应中的应用,其特征在于,步骤2)调节后混合液的pH值为8-12。
6.根据权利要求1所述的铜基催化剂在水煤气变换反应中的应用,其特征在于,步骤3)所述蒸氨处理的温度为60-90℃,时间为1-7h。
7.根据权利要求1所述的铜基催化剂在水煤气变换反应中的应用,其特征在于,步骤5)所述干燥的温度为80-120℃;所述焙烧的温度为400-600℃,时间为1-8h。
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