CN116328776A - 一种醋酸甲酯加氢制备乙醇的催化剂 - Google Patents
一种醋酸甲酯加氢制备乙醇的催化剂 Download PDFInfo
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 title claims abstract description 23
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 21
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 24
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- 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 7
- 239000012266 salt solution Substances 0.000 claims description 7
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- 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
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Abstract
本发明提供了一种用于醋酸甲酯加氢制备乙醇的催化剂。该催化剂以CuO‑ZnO为活性组分,Al2O3‑SiO2为载体,助剂A选自一种IVB族的元素化合物,助剂B选自一种ⅠA族、ⅡA族中的元素化合物,催化剂中CuO的质量分数为18%~59%,ZnO的质量分数为16%~23%,助剂A的质量分数为0.2%~1.3%,助剂B的质量分数为0.3%~0.8%,剩余的为载体Al2O3‑SiO2;所述催化剂的制备步骤包括共沉淀得到前驱体,载体改性,然后成型、干燥、水蒸气焙烧得到最终催化剂。本发明提供的催化剂具有优异的加氢活性、选择性及长周期运行的稳定性。
Description
技术领域
本发明属于化学催化剂领域,涉及一种用于加氢反应的催化剂。
背景技术
用于醋酸甲酯加氢制乙醇反应的非贵金属催化剂多集中在铜基催化剂,由铜颗粒在高温条件下容易发生的聚集和烧结,易导致催化剂活性下降,因此,开发出具有高催化活性和稳定性良好的铜基催化剂,对醋酸甲酯加氢制乙醇技术至关重要。
专利CN101934228A公开了一种醋酸酯加氢制乙醇的催化剂,所述催化剂主要组分为Cu或CuO,载体为SiO2或Al2O3,醋酸酯转化率大于80%,乙醇选择性大于90%,但是由于该催化剂需要在较低的空速和较高的氢酯比下反应,而且转化率较低,未反应的醋酸酯需要循环处理;专利CN102327774A公开了一种醋酸酯加氢制乙醇的催化剂及其制备方法和应用,所述催化剂的主要组分为Cu,载体为SiO2和Al2O3,醋酸酯转化率70~85%,乙醇选择性70~91%,所述催化剂虽然操作条件比较温和,但转化率、选择性较低,需要繁琐的后处理;CN102872878和CN103230795分别公开了一种醋酸甲酯加氢制乙醇的铜基催化剂及其制备方法,用共沉淀法将沉淀剂加入含有助剂的Cu盐溶液中至PH=6~8或PH=8~9,ZnO为载体,该催化剂制备方法简单,但活性组分Cu用量大,醋酸甲酯加氢温度稍高;因此需要开发一种具有高催化活性和良好稳定性的醋酸甲酯加氢催化剂。
发明内容
针对现有醋酸甲酯加氢制乙醇的催化剂,在高温条件下容易发生的聚集和烧结,导致催化剂活性易下降,催化活性不高、选择性低、稳定性差等缺点,本发明提供了一种醋酸甲酯加氢制备乙醇的催化剂。该催化剂制备过程简单,能将醋酸甲酯高效的转化为乙醇,具有较好的工业应用前景。
本发明的技术方案如下:
一种醋酸甲酯加氢制备乙醇的催化剂,其特征在于:该催化剂以CuO-ZnO为活性组分,以A和B为助剂,Al2O3-SiO2为载体;助剂A选自一种IVB族的元素化合物,助剂B选自一种ⅠA族、ⅡA族中的元素化合物,催化剂中CuO的质量分数为18%~59%,ZnO的质量分数为16%~23%,助剂A的质量分数为0.2%~1.3%,助剂B的质量分数为0.3%~0.8%,剩余的为载体Al2O3-SiO2。
所述的催化剂,其特征在于:所述的助剂A为TiO2,助剂B为CaO。
所述催化剂的制备包括以下步骤:
(1)将含Cu、Zn、Ti、Ca的化合物按比例溶于去离子水中,然后搅拌均匀,得到一定浓度的盐溶液;
(2)将步骤(1)得到的盐溶液和沉淀剂在一定温度下,同时缓慢滴入三口烧瓶,控制溶液pH值,待达到沉淀终止pH值时停止加入沉淀剂,然后将所得胶体进行超声处理,处理完毕后,静置陈化;
(3)将硅溶胶与Al2O3混合均匀,在60℃养护8h,喷涂质量分数为0.5%的硝酸铜溶液,于800℃焙烧,制得Al2O3-SiO2改性载体;
(4)将步骤(2)得到的陈化的胶体用去离子水进行洗涤,洗涤完毕后加入一定量的步骤(3)得到的Al2O3-SiO2改性载体和粘结剂成型、干燥;
(5)将步骤(4)得到的催化剂置于管式马弗炉中,并在水蒸汽与空气的混合气氛下焙烧得到最终催化剂。
所述的催化剂,其特征在于;所述催化剂的更优组成是CuO的质量分数为55%,ZnO的质量分数为18%,助剂A的质量分数为0.8%,助剂B的质量分数为0.6%,余下为Al2O3-SiO2。
所述的催化剂,其特征在于:含Zn的化合物为硝酸锌,含Ti的化合物为TiCl4,含Ca的化合物为Ca(OH)2,含Cu的化合物为硝酸铜、硫酸铜中的一种,盐溶液中盐的质量浓度为187g/L~286g/L。
所述的催化剂,其特征在于:所述的沉淀温度为75℃,所述的沉淀剂为Na2CO3溶液,沉淀终止pH值为8~9,超声处理时间为10min,陈化时间为8h。
所述的催化剂,其特征在于:所述沉淀剂Na2CO3溶液浓度为0.8mol/L~1.1mol/L。
所述的催化剂,其特征在于:所述的混合气氛中水蒸气与空气的体积比为1:6,混合气的体积空速为4000h-1,焙烧温度为450℃,焙烧时间为4h。
本发明提供的一种醋酸甲酯加氢生产乙醇的催化剂具有以下优点:
1、通过催化剂载体的改性,制备的催化剂具有有序孔道结构,特定孔径,能较好的分散活性金属。在载体的制备过程中喷涂质量分数为0.5%Cu(NO3)2溶液经800℃焙烧,让少量的亚铜离子负载于载体上;Al2O3-SiO2载体吸附亚铜离子改性后制备的催化剂,能克服铜系催化剂在使用过程中铜原子晶格聚积,防止致的铜催化剂的晶粒变大,催化剂的活性下降;
2、研究结果表明,通过共沉淀法引入助剂CaO和TiO2制备的催化剂,使活性组分分散的更加均匀,提高了催化剂的活性,CaO的引入抑制了催化剂上裂解、积碳等副反应,提高了乙醇的选择性,TiO2的引入提高了催化剂的热稳定性,克服铜原子晶格聚积导致催化剂失活。本发明提供的催化剂具有优异的加氢活性及乙醇选择性,能长周期使用。
具体实施方式
下面结合具体的实施案例进一步阐明本发明所述催化剂,列举的实例用来说明催化剂的组成、制备过程,但不限定本发明具有更优的催化剂组成、制备过程。
实施例1
称取146.1g的CuSO4・5H2O、46.1g的Zn(NO3)2・6H2O、0.83g的Ca(OH)2、2.43g的TiCl4溶于1189ml去离子水中,搅拌均匀;然后和1.1mol/L的Na2CO3溶液同时缓慢滴入三口烧瓶中至PH值为8.5,沉淀温度为75℃,继续搅拌2h,然后超声处理10min,接着静置陈化8h,然后过滤、洗涤;取18g(含有SiO2为20wt%)硅溶胶与14.4g的Al2O3混合均匀,在60℃养护8h,喷涂质量分数为0.5%的硝酸铜溶液18ml,于800℃焙烧,制得Al2O3-SiO2改性载体;将洗涤完毕的活性组分和制得的Al2O3-SiO2改性载体混合均匀,成型、干燥,最后将上述催化剂置于管式马弗炉中,通入水蒸气和空气的混合气氛(1:6),控制焙烧温度450℃,混合气氛体积空速为4000h-1,焙烧4h得到催化剂Cat1。
实施例2
称取173g的Cu(NO3)2・6H2O、55.6g的Zn(NO3)2・6H2O、0.66g的Ca(OH)2、1.6g的TiCl4溶于888ml去离子水中,搅拌均匀;然后和1.0mol/L的Na2CO3溶液同时缓慢滴入三口烧瓶中至PH值为8,沉淀温度为75℃,继续搅拌2h,然后超声处理10min,接着静置陈化8h,然后过滤、洗涤;取21.65g(含有SiO2为20wt%)硅溶胶与17.3g的Al2O3混合均匀,在60℃养护8h,喷涂质量分数为0.5%的硝酸铜溶液21.6ml,于800℃焙烧,制得Al2O3-SiO2改性载体;将洗涤完毕的活性组分和制得的Al2O3-SiO2改性载体混合均匀,成型、干燥,最后将上述催化剂置于管式马弗炉中,通入水蒸气和空气的混合气氛(1:6),控制焙烧温度450℃,混合气氛体积空速为4000h-1,焙烧4h得到催化剂Cat2。
实施例3
称取173g的Cu(NO3)2・6H2O、217.2g的Zn(NO3)2・6H2O、1.02g的Ca(OH)2、1.23g的TiCl4溶于1372ml去离子水中,搅拌均匀;然后和0.9mol/L的Na2CO3溶液同时缓慢滴入三口烧瓶中至PH值为8,沉淀温度为75℃,继续搅拌2h,然后超声处理10min,接着静置陈化8h,然后过滤、洗涤;取151.2g(含有SiO2为20wt%)硅溶胶与121g的Al2O3混合均匀,在60℃养护8h,喷涂质量分数为0.5%的硝酸铜溶液151.2ml,于800℃焙烧,制得Al2O3-SiO2改性载体;将洗涤完毕的活性组分和制得的Al2O3-SiO2改性载体混合均匀,成型、干燥,最后将上述催化剂置于管式马弗炉中,通入水蒸气和空气的混合气氛(1:6),控制焙烧温度450℃,混合气氛体积空速为4000h-1,焙烧4h得到催化剂Cat3。
实施例4
称取173g的Cu(NO3)2・6H2O、55.6g的Zn(NO3)2・6H2O、0.66g的Ca(OH)2溶于888ml去离子水中,搅拌均匀;然后和1.0mol/L的Na2CO3溶液同时缓慢滴入三口烧瓶中至PH值为8,沉淀温度为75℃,继续搅拌2h,然后超声处理10min,接着静置陈化8h,然后过滤、洗涤;取21.65g(含有SiO2为20wt%)硅溶胶与17.3g的Al2O3混合均匀,在60℃养护8h,于800℃焙烧,制得Al2O3-SiO2未改性载体;将洗涤完毕的活性组分和制得的Al2O3-SiO2未改性载体混合均匀,成型、干燥,最后将上述催化剂置于管式马弗炉中,通入水蒸气和空气的混合气氛(1:6),控制焙烧温度450℃,混合气氛体积空速为4000h-1,焙烧4h得到催化剂Cat4。
本实施例对上述实施例1~4的醋酸甲酯加氢制乙醇催化剂活性进行评价分析。
将各实施例制备的催化剂分别取6ml装入Φ6×2.0的反应管,催化剂床层高度12mm,所用原料油为工业醋酸甲酯。
选用分析仪器:采用安捷伦气相色谱仪进行分析。取6ml催化剂装入固定床反应器,进行器内活化,通入氢气,调整系统压力为0.7MP,氢气量为200ml/min,以10℃/min升温至230℃,恒温4h使催化剂完全活化。活化结束后,泵入工业级醋酸甲酯,进油空速为1.0h-1,反应温度为210℃,反应压力为5.0MPa,氢气/油摩尔比20:1的条件下,进行醋酸甲酯加氢制乙醇实验,加氢后产品进行醋酸甲酯、乙醇、甲醇、醋酸乙酯和乙醚、乙烷等副产物及水含量分析。记录反应结果如表1所示:
表1 醋酸甲酯加氢制备乙醇性能分析
催化剂型号 | 醋酸甲酯 | 醋酸乙酯 | 甲醇 | 乙醇 | 副反应 | 副产水 |
Cat1 | 0.89% | 0.91% | 30.3% | 67.27% | 0.35% | 0.28% |
Cat 2 | 1.2% | 1.08% | 29.5% | 67.66% | 0.43% | 0.13% |
Cat 3 | 0.62% | 0.68% | 31.2% | 67.21% | 0.23% | 0.06% |
Cat 4 | 1.18% | 1.06% | 28.9% | 67.31% | 1.3% | 0.25% |
从表1的数据可知,Cat1,Cat2,Cat3,三种加氢催化剂以工业醋酸甲酯作为原料进行加氢制备乙醇实验,均表现出较高的转化率和较好的选择性。
表2 醋酸甲酯催化剂长周期实验性能
发明人还采用了上述方法对实施例所得的催化剂Cat2和Cat4进行了长周期实验。由表2可以看出,催化剂Cat2在2400h的运转周期内,选择性和转化率基本未变,长周期实验运行,显示出优异稳定性与选择性。催化剂Cat4在480h的运转周期内,选择性和转化率是不断下降的过程,在2400h,随着运行时间的延长,选择性和转化率持续下降,且下降的趋势越来越明显。这主要是因为Cat2的催化剂的载体改性后,催化剂在使用过程中未出现铜原子晶格聚积,铜催化剂的晶粒变大的情况,同时催化剂在制备过程中,引入助剂CaO和TiO2制备的催化剂,使活性组分更加均匀,提高了催化剂的活性,CaO的引入抑制了催化剂上裂解、积碳等副反应提高了乙醇的选择性,TiO2的引入提高了催化剂的热稳定性,催化剂Cat2具备较好的活性和稳定性。
对上述实施例中的催化剂的的孔结构进行分析,分析结果如表3。
表3不同催化剂的孔结构分析
催化剂 | 比表面积/m 2 •g -1 | 孔容/cm3•g -1 | 平均孔径/nm |
Cat 1 | 102.9 | 0.335 | 13.0 |
Cat 2 | 94.3 | 0.260 | 11.1 |
Cat 3 | 85.6 | 0.314 | 14.7 |
Cat 4 | 104.3 | 0.330 | 13.2 |
经2400h运行后Cat 2 | 94.2 | 0.261 | 11.0 |
经2400h运行后Cat 4 | 73.3 | 0.191 | 9.8 |
从表3可以看出本发明提供的催化剂Cat4的载体未进行改性,经过长周期运行后,催化剂孔径减小,孔体积降低,表明催化剂在使用过程出现铜晶粒的聚积导致孔堵塞,同时在醋酸甲酯加氢过程中,会出现甲醇等的裂解导致催化剂积碳,导致催化剂的孔容降低。催化剂Cat2中载体经改性后,引入亚铜离子,相比未改性的Cat4,经2400h运行催化剂的孔径与孔容均未发生减小,显示Cat2催化剂在长周期实验运行中表现出更优异的性能。
Claims (6)
1.一种醋酸甲酯加氢制备乙醇的催化剂,其特征在于:该催化剂以CuO-ZnO为活性组分,以A和B为助剂,Al2O3-SiO2为载体;助剂A选自一种IVB族的元素化合物,助剂B选自一种ⅠA族、ⅡA族中的元素化合物,催化剂中CuO的质量分数为18%~59%,ZnO的质量分数为16%~23%,助剂A的质量分数为0.2%~1.3%,助剂B的质量分数为0.3%~0.8%,剩余的为载体Al2O3-SiO2;
所述的助剂A为TiO2,助剂B为CaO;
所述催化剂的制备包括以下步骤:
⑴将含Cu、Zn、Ti、Ca的化合物按比例溶于去离子水中,然后搅拌均匀,得到一定浓度的盐溶液;
⑵将步骤(1)得到的盐溶液和沉淀剂在一定温度下,同时缓慢滴入三口烧瓶,控制溶液pH值,待达到沉淀终止pH值时停止加入沉淀剂,然后将所得胶体进行超声处理,处理完毕后,静置陈化;
⑶将硅溶胶与Al2O3混合均匀,在60℃养护8h,喷涂质量分数为0.5%的硝酸铜溶液,于800℃焙烧,制得Al2O3-SiO2改性载体;
⑷将步骤(2)得到的陈化的胶体用去离子水进行洗涤,洗涤完毕后加入一定量的步骤(3)得到的Al2O3-SiO2改性载体和粘结剂成型、干燥;
⑸将步骤(4)得到的催化剂置于管式马弗炉中,并在水蒸汽与空气的混合气氛下焙烧得到最终催化剂。
2.根据权利要求1所述的催化剂,其特征在于:所述催化剂的更优组成是CuO的质量分数为55%,ZnO的质量分数为18%,助剂A的质量分数为0.8%,助剂B的质量分数为0.6%,余下为Al2O3-SiO2。
3.根据权利要求1所述的催化剂,其特征在于:含Zn的化合物为硝酸锌,含Ti的化合物为TiCl4,含Ca的化合物为Ca(OH)2,含Cu的化合物为硝酸铜、硫酸铜中的一种,盐溶液中盐的质量浓度为187g/L~286g/L。
4.根据权利要求1所述的催化剂,其特征在于:所述的沉淀温度为75℃,所述的沉淀剂为Na2CO3溶液,沉淀终止pH值为8~9,超声处理时间为10min,陈化时间为8h。
5.根据权利要求1或4所述的催化剂,其特征在于:所述沉淀剂Na2CO3溶液浓度为0.8mol/L~1.1mol/L。
6.根据权利要求1所述的催化剂,其特征在于:所述的混合气氛中水蒸气与空气的体积比为1:6,混合气的体积空速为4000h-1,焙烧温度为450℃,焙烧时间为4h。
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