CN112517017B - 一种醋酸甲酯加氢的掺杂型硅酸铜纳米管催化剂及其制备方法与应用 - Google Patents
一种醋酸甲酯加氢的掺杂型硅酸铜纳米管催化剂及其制备方法与应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 136
- ZZBBCSFCMKWYQR-UHFFFAOYSA-N copper;dioxido(oxo)silane Chemical compound [Cu+2].[O-][Si]([O-])=O ZZBBCSFCMKWYQR-UHFFFAOYSA-N 0.000 title claims abstract description 38
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 title claims abstract description 37
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002071 nanotube Substances 0.000 title claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010949 copper Substances 0.000 claims abstract description 19
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000007791 liquid phase Substances 0.000 claims abstract description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 31
- 238000001291 vacuum drying Methods 0.000 claims description 29
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 28
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- 239000000843 powder Substances 0.000 claims description 21
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 235000019270 ammonium chloride Nutrition 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000000084 colloidal system Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
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- 239000002244 precipitate Substances 0.000 claims description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 11
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- 238000002791 soaking Methods 0.000 claims description 9
- 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 6
- 239000000047 product Substances 0.000 claims description 6
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
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- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 4
- 150000001340 alkali metals Chemical class 0.000 abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
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- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明提供一种醋酸甲酯加氢的掺杂型硅酸铜纳米管催化剂,包括载体、主催化剂和助催化剂,所述载体为二氧化硅,主催化剂为Cu的氧化物,助催化剂为金属X的氧化物,所述金属X为碱金属或碱土金属或稀土元素中的一种;所述主催化剂占载体质量的30‑40%,所述助催化剂占载体质量的0.5‑10%。同时,本发明还提供所述催化剂的制备方法及其用于醋酸甲酯加氢制备乙醇的应用。所述本发明提供的催化剂具有管状形貌结构,稳定性好,且在较低氢酯比的条件下,醋酸甲酯液相空速为0.5h‑1时,较低的反应温度235℃下,能维持醋酸甲酯92%以上的转化率,乙醇选择性95%以上,将极大降低设备投资成本。
Description
技术领域
本发明属于醋酸甲酯加氢催化剂技术领域,具体涉及一种醋酸甲酯加氢的掺杂型硅酸铜纳米管催化剂及其制备方法与应用。
背景技术
随着经济的持续发展,人们对能源的需求也日益增加,从而出现供不应求的现象,各国之间的能源之争也愈发激烈。在一次能源消费结构中,化石能源占主要地位,而在2016年我国的一次能源消费已占全球消费总量的23%,因此,我国能源结构的调整对世界未来能源的规划和布局具有重要作用。乙醇作为一种新型的可替代清洁能源,不但可以直接作为燃料,也可作为汽油的添加品改善汽油的性能,缓解人类对石油的依赖性,从而受到了越来越多研究者的关注。
现有的乙醇生产工艺主要有生物质发酵法、乙烯水合法以及合成气法。目前世界上燃料乙醇的生成基本都是以粮食作物或糖作物为原料。以玉米、小麦、木薯等粮食作物通过发酵生产酒精。目前以粮食发酵制乙醇工艺是我国应用最广的燃料乙醇生产工艺,该工艺的发展可以解决“陈化粮”问题,还能提高农民收入。但仍存在如下问题:(1)产生“与民争粮”问题,同时发展该路径有可能推高粮食价格。(2)工艺流程长,设备投资高,产品成本较高。而工业上采用的乙烯水合法是乙烯和水在硅藻土负载磷酸的催化下直接反应生成乙醇。但磷酸易被反应物料带走,需不断向反应体系中补充磷酸以满足催化效率。而且乙烯单程转化率较低(5%左右),为提高经济效益而常把乙烯循环使用,但此过程会产生乙醚、丁烯等副产物。
我国石油和天然气资源相对短缺,煤炭资源较为丰富的资源结构,发展煤基乙醇路线具有非常重要的意义。合成气经过二甲醚,醋酸甲酯,再加氢生产乙醇路线,具有原料易得,反应条件温和、原子经济性高等优点,具有很好的工业应用前景。而且我国醋酸工艺较为成熟,在过去10年间,我国醋酸产能大幅度增长,年均增长率达到17.7%。截止2016年,醋酸总生产能力已突破1000万t,成为世界上最大的醋酸生产国,约占世界总生产能力的50%。醋酸生产能力急剧扩张的同时,需求量却增长有限,导致行业装置整体开工率并不高,醋酸经醋酸甲酯加氢生产乙醇有望实现规模化和大型化。
目前,公开的醋酸甲酯加氢的催化剂主要有均相和非均相体系。如专利US4892955A、US4346240A、US5021589A和专利DE3401896A等分别采用Ru、Rh、Pd等贵金属均相催化体系,反应条件也较为苛刻。在非均相体系中多采用铜基催化体系,如专利CN101934228A、CN102093162A、CN102327774A、CN103288594A、CN108404918A等多采用二氧化硅为载体,金属铜为活性组分,添加助剂为Zn、Mn、Co、Ca、Ba、Mg中的一种或几种,此类催化剂具有较高优异的加氢性能和乙醇高选择性的特点,表现出良好的工业应用前景。
发明内容
针对现有技术的缺陷,本发明公开一种醋酸甲酯加氢的掺杂型硅酸铜纳米管催化剂及其制备方法与应用,所述催化剂稳定性好,在低氢酯比的条件下,原料的转化率高,产物的选择性高。
一种醋酸甲酯加氢的掺杂型硅酸铜纳米管催化剂,包括载体、主催化剂和助催化剂,所述载体为二氧化硅,主催化剂为Cu的氧化物,助催化剂为金属X的氧化物,所述金属X为碱金属或碱土金属或稀土元素中的一种;所述主催化剂占载体质量的30-40%,所述助催化剂占载体质量的0.5-10%。
优选地,所述碱金属为K;所述碱土金属为Mg、Ca或Sr;所述稀土元素为La、Ce、Y。
优选地,所述金属X为碱土金属Sr。
优选地,所述催化剂的比表面积为300-450m2/g,孔容为0.7-1.5cm3/g,平均孔径为9.0-11.5nm。
所述催化剂的制备方法,包括以下步骤:
(1)将硝酸铜、氯化铵加入水中配置成水溶液,硝酸铜与氯化铵摩尔比为1:(4-6),向其中滴加氨水至溶液pH为9-12,室温下搅拌0.5-1h,形成蓝色悬浊液;
(2)向所述蓝色悬浊液中加入硅溶胶,在室温下搅拌1-3h,形成蓝色胶体溶液;
(3)在180-250℃下水热晶化24-48h;
(4)冷却后,过滤,将固体沉淀物洗涤至滤液的pH为中性,真空干燥,得到层状硅酸铜催化剂粉末;
(5)将所述层状硅酸铜催化剂粉末加入到金属X的硝酸盐水溶液中,搅拌2-6h后,通过旋转蒸发浸渍,得到改性催化剂前驱体;
(6)将所述改性催化剂前驱体真空干燥,然后在空气气氛下焙烧;
(7)压片、破碎、筛分。
优选地,所述旋转蒸发的条件为在旋转蒸发仪中在80-100℃下保持0.5-3h。
优选地,步骤(4)所述真空干燥的条件为在60-80℃下真空干燥12-24h;步骤(6)所述真空干燥的条件为在80-100℃下真空干燥12-24h。
优选地,所述焙烧的条件为:焙烧温度400-550℃,焙烧时间3-6h。
优选地,所述焙烧的温度为450℃。
优选地,所述筛分过20-40目筛。
所述催化剂的应用,所述应用为将所述催化剂用于醋酸甲酯加氢制备乙醇,制备方法具体如下:
(一)采用固定床反应器,装填所述催化剂,在氢气流量100-250mL/min、300-350℃、常压下还原处理3-6h;
(二)醋酸甲酯经过气化后,由氢气载入进行反应,调节氢气流量,维持醋酸甲酯的液相空速为0.5-2.5 h-1,H2与醋酸甲酯摩尔比为(10-20):1;
(三)在180-250℃、压力为2-5MPa下反应,气液分离,收集液相产物。
优选地,所述固定床反应器的反应器内径为6-10mm,长度为40-60cm,装填所述催化剂0.5-2g。
本发明的优点:
1. 本发明提供的催化剂具有管状形貌结构,有助于延长中间产物的加氢路径,乙醇选择性提高;
2. 本发明提供的催化剂,铜硅界面相互作用增强,通过限域很好地抑制铜物种烧结,能解决传统Cu/SiO2催化剂快速失活的现象;
3. 本发明中,所述助催化剂能显著提高催化剂的活性,降低反应温度,增加了所述催化剂表面铜物种的稳定性,所述催化剂在稳定运行320h,无明显失活现象;
4. 在较大醋酸甲酯液相空速下催化剂耐受性强,且在较低氢酯比的条件下,醋酸甲酯液相空速为0.5h-1时,较低的反应温度235℃下,能维持醋酸甲酯92%以上的转化率,乙醇选择性95%以上,将极大降低设备投资成本,降低生产能耗,有利于工业化生产。
附图说明
图1 催化剂稳定评价数据;
图2 实施例3提供的催化剂的形貌;
图3 实施例3提供的催化剂的等温吸脱附曲线和孔径分布图。
具体实施方式
实施例1
1. 一种醋酸甲酯加氢的掺杂型硅酸铜纳米管催化剂,包括载体、主催化剂和助催化剂,所述载体为二氧化硅,主催化剂为Cu的氧化物,助催化剂为稀土元素Ce的氧化物;所述主催化剂占载体质量的30%,所述助催化剂占载体质量的5%。
2. 所述催化剂的制备方法,包括以下步骤:
(1)将4.95g三水合硝酸铜、4.58g氯化铵加入120mL水中配置成水溶液,向其中滴加28wt%的氨水至溶液pH为9.5,室温下搅拌0.5h,形成蓝色悬浊液;
(2)向所述蓝色悬浊液中缓慢滴加入1.728g硅溶胶,在室温下搅拌1h,形成蓝色胶体溶液;
(3)在200℃下水热晶化40h;
(4)冷却后,过滤,将固体沉淀物洗涤至滤液的pH为中性,在60℃下真空干燥24h,得到层状硅酸铜催化剂粉末;
(5)取0.217g六水合硝酸铈溶解于50mL去离子水中,向其中加入1g所述层状硅酸铜催化剂粉末,搅拌4h后,通过旋转蒸发浸渍,得到改性催化剂前驱体;其中,所述旋转蒸发是在旋转蒸发仪中在80℃下保持3h;
(6)将所述改性催化剂前驱体在100℃下真空干燥12h,然后在空气气氛下,在450℃下焙烧4h;
(7)压片、破碎、筛分过20-40目筛。
实施例2
1. 一种醋酸甲酯加氢的掺杂型硅酸铜纳米管催化剂,包括载体、主催化剂和助催化剂,所述载体为二氧化硅,主催化剂为Cu的氧化物,助催化剂为稀土元素La的氧化物;所述主催化剂占载体质量的30%,所述助催化剂占载体质量的3%。
2. 所述催化剂的制备方法,包括以下步骤:
(1)将4.95g三水合硝酸铜、4.58g氯化铵加入120mL水中配置成水溶液,向其中滴加28 wt%的氨水至溶液pH为9.5,室温下搅拌0.5h,形成蓝色悬浊液;
(2)向所述蓝色悬浊液中缓慢滴加入1.728g硅溶胶,在室温下搅拌1h,形成蓝色胶体溶液;
(3)在200℃下水热晶化40h;
(4)冷却后,过滤,将固体沉淀物洗涤至滤液的pH为中性,在60℃下真空干燥24h,得到层状硅酸铜催化剂粉末;
(5)取0.131g六水合硝酸镧溶解于50mL去离子水中,向其中加入1g所述层状硅酸铜催化剂粉末,搅拌4h后,通过旋转蒸发浸渍,得到改性催化剂前驱体;其中,所述旋转蒸发是在旋转蒸发仪中在80℃下保持3h;
(6)将所述改性催化剂前驱体在100℃下真空干燥12h,然后在空气气氛下,在450℃下焙烧4h;
(7)压片、破碎、筛分过20-40目筛。
实施例3
1. 一种醋酸甲酯加氢的掺杂型硅酸铜纳米管催化剂,包括载体、主催化剂和助催化剂,所述载体为二氧化硅,主催化剂为Cu的氧化物,助催化剂为碱土金属Sr的氧化物;所述主催化剂占载体质量的35%,所述助催化剂占载体质量的5%。
2. 所述催化剂的制备方法,包括以下步骤:
(1)将5.78g三水合硝酸铜、5.34g氯化铵加入120mL水中配置成水溶液,向其中滴加28 wt%的氨水至溶液pH为9.5,室温下搅拌0.5h,形成蓝色悬浊液;
(2)向所述蓝色悬浊液中缓慢滴加入1.728g硅溶胶,在室温下搅拌1h,形成蓝色胶体溶液;
(3)在200℃下水热晶化40h;
(4)冷却后,过滤,将固体沉淀物洗涤至滤液的pH为中性,在60℃下真空干燥24h,得到层状硅酸铜催化剂粉末;
(5)取0.0595 g硝酸锶溶解于50mL去离子水中,向其中加入1g所述层状硅酸铜催化剂粉末,搅拌4h后,通过旋转蒸发浸渍,得到改性催化剂前驱体;其中,所述旋转蒸发是在旋转蒸发仪中在80 oC下保持3h;
(6)将所述改性催化剂前驱体在100℃下真空干燥12h,然后在空气气氛下,在450℃下焙烧4h;
(7)压片、破碎、筛分过20-40目筛。
实施例4
1. 一种醋酸甲酯加氢的掺杂型硅酸铜纳米管催化剂,包括载体、主催化剂和助催化剂,所述载体为二氧化硅,主催化剂为Cu的氧化物,助催化剂为碱金属K的氧化物;所述主催化剂占载体质量的35%,所述助催化剂占载体质量的1%。
2. 所述催化剂的制备方法,包括以下步骤:
(1)将5.78g三水合硝酸铜、5.34g氯化铵加入120mL水中配置成水溶液,向其中滴加28 wt%的氨水至溶液pH为9.5,室温下搅拌0.5h,形成蓝色悬浊液;
(2)向所述蓝色悬浊液中缓慢滴加入1.728g硅溶胶,在室温下搅拌1h,形成蓝色胶体溶液;
(3)在200℃下水热晶化40h;
(4)冷却后,过滤,将固体沉淀物洗涤至滤液的pH为中性,在60℃下真空干燥24h,得到层状硅酸铜催化剂粉末;
(5)取0.036g硝酸钾溶解于50 mL去离子水中,向其中加入1g所述层状硅酸铜催化剂粉末,搅拌4h后,通过旋转蒸发浸渍,得到改性催化剂前驱体;其中,所述旋转蒸发是在旋转蒸发仪中在80℃下保持3h;
(6)将所述改性催化剂前驱体在100℃下真空干燥12h,然后在空气气氛下,在450℃下焙烧4h;
(7)压片、破碎、筛分过20-40目筛。
实施例5
1. 一种醋酸甲酯加氢的掺杂型硅酸铜纳米管催化剂,包括载体、主催化剂和助催化剂,所述载体为二氧化硅,主催化剂为Cu的氧化物,助催化剂为碱土金属Ca的氧化物;所述主催化剂占载体质量的35%,所述助催化剂占载体质量的7%。
2. 所述催化剂的制备方法,包括以下步骤:
(1)将5.78g三水合硝酸铜、5.34g氯化铵加入120mL水中配置成水溶液,向其中滴加28wt%的氨水至溶液pH为9.5,室温下搅拌0.5h,形成蓝色悬浊液;
(2)向所述蓝色悬浊液中缓慢滴加入1.728g硅溶胶,在室温下搅拌1h,形成蓝色胶体溶液;
(3)在200℃下水热晶化40h;
(4)冷却后,过滤,将固体沉淀物洗涤至滤液的pH为中性,在60℃下真空干燥24h,得到层状硅酸铜催化剂粉末;
(5)取0.289 g四水合硝酸钙溶解于50 mL去离子水中,向其中加入1g所述层状硅酸铜催化剂粉末,搅拌4h后,通过旋转蒸发浸渍,得到改性催化剂前驱体;其中,所述旋转蒸发是在旋转蒸发仪中在80℃下保持3 h;
(6)将所述改性催化剂前驱体在100℃下真空干燥12h,然后在空气气氛下,在450℃下焙烧4h;
(7)压片、破碎、筛分过20-40目筛。
实施例6
1. 一种醋酸甲酯加氢的掺杂型硅酸铜纳米管催化剂,包括载体、主催化剂和助催化剂,所述载体为二氧化硅,主催化剂为Cu的氧化物,助催化剂为碱土元素Mg的氧化物;所述主催化剂占载体质量的40%,所述助催化剂占载体质量的0.5%。
2. 所述催化剂的制备方法,包括以下步骤:
(1)将6.61g三水合硝酸铜、6.1g氯化铵加入120mL水中配置成水溶液,向其中滴加28wt%的氨水至溶液pH为9,室温下搅拌1h,形成蓝色悬浊液;
(2)向所述蓝色悬浊液中缓慢滴加入1.728g硅溶胶,在室温下搅拌1h,形成蓝色胶体溶液;
(3)在180℃下水热晶化48h;
(4)冷却后,过滤,将固体沉淀物洗涤至滤液的pH为中性,在70℃下真空干燥20h,得到层状硅酸铜催化剂粉末;
(5)取0.046g六水合硝酸镁溶解于50mL去离子水中,向其中加入1g所述层状硅酸铜催化剂粉末,搅拌2h后,通过旋转蒸发浸渍,得到改性催化剂前驱体;其中,所述旋转蒸发是在旋转蒸发仪中在100℃下保持0.5h;
(6)将所述改性催化剂前驱体在80℃下真空干燥24h,然后在空气气氛下,在400℃下焙烧6h;
(7)压片、破碎、筛分过20-40目筛。
实施例7
1. 一种醋酸甲酯加氢的掺杂型硅酸铜纳米管催化剂,包括载体、主催化剂和助催化剂,所述载体为二氧化硅,主催化剂为Cu的氧化物,助催化剂为稀土元素Y的氧化物;所述主催化剂占载体质量的30%,所述助催化剂占载体质量的10%。
2. 所述催化剂的制备方法,包括以下步骤:
(1)将4.95g三水合硝酸铜、4.58g氯化铵加入120mL水中配置成水溶液,向其中滴加28wt%的氨水至溶液pH为12,室温下搅拌1h,形成蓝色悬浊液;
(2)向所述蓝色悬浊液中缓慢滴加入1.728g硅溶胶,在室温下搅拌2h,形成蓝色胶体溶液;
(3)在250℃下水热晶化24h;
(4)冷却后,过滤,将固体沉淀物洗涤至滤液的pH为中性,在80℃下真空干燥12h,得到层状硅酸铜催化剂粉末;
(5)取1.37g六水合硝酸钇溶解于50 mL去离子水中,向其中加入1g所述层状硅酸铜催化剂粉末,搅拌6h后,通过旋转蒸发浸渍,得到改性催化剂前驱体;其中,所述旋转蒸发是在旋转蒸发仪中在90℃下保持2h;
(6)将所述改性催化剂前驱体在80℃下真空干燥24h,然后在空气气氛下,在550℃下焙烧3h;
(7)压片、破碎、筛分过20-40目筛。
比较例1
1. 一种醋酸甲酯加氢的掺杂型硅酸铜纳米管催化剂,包括载体、主催化剂,所述载体为二氧化硅,主催化剂为Cu的氧化物,所述主催化剂占载体质量的35%。
2. 所述催化剂的制备方法,包括以下步骤:
(1)将5.78g三水合硝酸铜、5.34g氯化铵加入120mL水中配置成水溶液,向其中滴加28wt%的氨水至溶液pH为9.5,室温下搅拌0.5h,形成蓝色悬浊液;
(2)向所述蓝色悬浊液中缓慢滴加入1.728g硅溶胶,在室温下搅拌1h,形成蓝色胶体溶液;
(3)在200℃下水热晶化48h;
(4)冷却后,过滤,将固体沉淀物洗涤至滤液的pH为中性,在60℃下真空干燥24h,得到层状硅酸铜催化剂粉末;
(5)在空气气氛下,在450℃下焙烧4h;
(7)压片、破碎、筛分过20-40目筛。
一. 应用
将本发明实施例提供的催化剂用于醋酸甲酯加氢制备乙醇,制备方法具体如下:
(一)采用固定床反应器,反应器内径为7mm,长度为48cm,装填所述催化剂0.5g,用石英砂稀释至2mL,在氢气流量100mL/min、350℃、常压下还原处理4h;
(二)醋酸甲酯经过气化后,由氢气载入进行反应,调节氢气流量,维持醋酸甲酯的液相空速为0.5-2.5h-1,H2与醋酸甲酯摩尔比为15:1;
(三)在235℃、2.5MPa下反应,气液分离,收集液相产物。
将收集的液相产物采用配置OV1701色谱柱和氢火焰检测器的SP7890气相色谱进行分析,各催化剂的反应评价见表1。
表1 催化剂的评价结果
由表1可知,本发明提供的催化剂,且在较低氢酯比的条件下,较低的反应温度235oC下,能维持醋酸甲酯92%以上的转化率,乙醇选择性95%以上。
比较例1和实施例3在醋酸甲酯的液相空速为1.0h-1时,评价催化剂的稳定性,醋酸甲酯的转化率和乙醇的选择性见图1。
由图1可知,本发明实施例3提供的催化剂,能稳定运行320h,无明显失活现象。
二. 催化剂形貌分析
对实施例3提供的催化剂做扫描电镜和透射电镜,其SEM图和TEM图分别见图2中a和b,所述催化剂经过氢气还原,即经过所述应用中步骤(一)还原后,HRTEM图见图2中c。
由图2中a和b可知,本发明提供的催化剂呈现均匀的纳米管状的形貌,由图2中c可知,还原后的催化剂同时出现Cu0的(111)和Cu2O的(200)的晶面,说明经过还原后形成两种价态的铜物种均匀分布在载体的表面。
三.催化剂孔结构分析
对实施案提供的例催化剂进行结构性质分析,检测其比表面积(
S BET)、孔容(
V p)和平均孔径(
D p),结果见表2。
表2催化剂的结构性质
对实施例3得到的催化剂,检测其等温吸脱附性能和孔径分布,结果见图3。
由图3可知,本发明提供的制备方法合成的催化剂均呈现典型的IV型吸附等温线和H1型滞后环,说明催化剂为典型的一维孔道结构的介孔材料。同时,催化剂的孔径均表现为双孔分布,主要集中于3nm处,同时在30-100nm之间有较宽的分布。在3nm处的小孔是由于在制备过程中形成了层状硅酸铜结构。
Claims (8)
1.一种醋酸甲酯加氢的掺杂型硅酸铜纳米管催化剂,其特征在于:包括载体、主催化剂和助催化剂,所述载体为二氧化硅,主催化剂为Cu的氧化物,助催化剂为金属X的氧化物,所述金属X为碱土金属Sr;所述主催化剂占载体质量的30-40%,所述助催化剂占载体质量的0.5-10%;
所述催化剂是通过以下方法制备得到的:
(1)将硝酸铜、氯化铵加入水中配置成水溶液,硝酸铜与氯化铵摩尔比为1:(4-6),向其中滴加氨水至溶液pH为9-12,室温下搅拌0.5-1h,形成蓝色悬浊液;
(2)向所述蓝色悬浊液中加入硅溶胶,在室温下搅拌1-3h,形成蓝色胶体溶液;
(3)在180-250℃下水热晶化24-48h;
(4)冷却后,过滤,将固体沉淀物洗涤至滤液的pH为中性,真空干燥,得到层状硅酸铜催化剂粉末;
(5)将所述层状硅酸铜催化剂粉末加入到金属X的硝酸盐水溶液中,搅拌2-6h后,通过旋转蒸发浸渍,得到改性催化剂前驱体;
(6)将所述改性催化剂前驱体真空干燥,然后在空气气氛下焙烧;
(7)压片、破碎、筛分。
2.根据权利要求1所述醋酸甲酯加氢的掺杂型硅酸铜纳米管催化剂,其特征在于:所述催化剂的比表面积为300-450m2/g,孔容为0.7-1.5cm3/g,平均孔径为9.0-11.5nm。
3.权利要求1-2任一项所述催化剂的制备方法,其特征在于:包括以下步骤:
(1)将硝酸铜、氯化铵加入水中配置成水溶液,硝酸铜与氯化铵摩尔比为1:(4-6),向其中滴加氨水至溶液pH为9-12,室温下搅拌0.5-1h,形成蓝色悬浊液;
(2)向所述蓝色悬浊液中加入硅溶胶,在室温下搅拌1-3h,形成蓝色胶体溶液;
(3)在180-250℃下水热晶化24-48h;
(4)冷却后,过滤,将固体沉淀物洗涤至滤液的pH为中性,真空干燥,得到层状硅酸铜催化剂粉末;
(5)将所述层状硅酸铜催化剂粉末加入到金属X的硝酸盐水溶液中,搅拌2-6h后,通过旋转蒸发浸渍,得到改性催化剂前驱体;
(6)将所述改性催化剂前驱体真空干燥,然后在空气气氛下焙烧;
(7)压片、破碎、筛分。
4.根据权利要求3所述催化剂的制备方法,其特征在于:所述旋转蒸发的条件为在旋转蒸发仪中在80-100℃下保持0.5-3 h。
5.根据权利要求3所述催化剂的制备方法,其特征在于:步骤(4)所述真空干燥的条件为在60-80℃下真空干燥12-24h;步骤(6)所述真空干燥的条件为在80-100℃下真空干燥12-24h。
6.根据权利要求3所述催化剂的制备方法,其特征在于:所述焙烧的条件为:焙烧温度400-550℃,焙烧时间3-6h。
7.根据权利要求3所述催化剂的制备方法,其特征在于:所述筛分过20-40目筛。
8.权利要求1-2任一项所述催化剂的应用,所述应用为将所述催化剂用于醋酸甲酯加氢制备乙醇,制备方法具体如下:
(一)采用固定床反应器,装填所述催化剂,在氢气流量100-250mL/min、300-350℃、常压下还原处理3-6h;
(二)醋酸甲酯经过气化后,由氢气载入进行反应,调节氢气流量,维持醋酸甲酯的液相空速为0.5-2.5h-1,H2与醋酸甲酯摩尔比为(10-20):1;
(三)在180-250℃、压力为2-5MPa下反应,气液分离,收集液相产物。
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