CN108465468B - 一种合成气制低碳醇催化剂的制备方法 - Google Patents
一种合成气制低碳醇催化剂的制备方法 Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 26
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- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims abstract description 58
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000725 suspension Substances 0.000 claims abstract description 44
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 34
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- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 6
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Abstract
本发明公开的合成气制备低碳醇催化剂及其制备方法,该催化剂采用以下方法制得:步骤一,处理载体碳纳米管;步骤二,称取前驱物硝酸铜、硝酸铁、硝酸镍、硝酸铬,得到混合物A,将混合物A溶于去离子水中,得到混合溶液B;步骤三,称取步骤一处理后的载体碳纳米管分散于混合溶液B中,得到分散液C;步骤四,向分散液C中滴加10wt%NH3·H2O,将分散液C的pH调节至8~9,再加入聚乙二醇,得到悬浊液D;步骤五,将悬浊液D在40℃温度下反应1h,得到悬浊液E;步骤六,将悬浊液E转移高压反应釜中,在100~160℃温度下,反应24h,待冷却至室温后经离心、洗涤、干燥,并在350~550℃温度下焙烧4h,得催化剂。催化剂的原料廉价易得。
Description
技术领域
本发明属于低碳醇制备技术领域,涉及一种合成气制低碳醇催化剂的制备方法。
背景技术
随着石油资源的日渐枯竭,未来能源结构将转向以煤和天然气为主。中国能源禀赋为“富煤、缺油、少气”,从资源有效利用角度来看,通过天然气或煤气化生产合成气制低碳混合醇(低碳混合醇是指C2~C6的醇类混合物),是优质的环境友好型的动力燃料,而且可以作为清洁汽油添加剂取代MTBE,同时作为化学产品和大宗化工生产原料具有十分广阔的应用前景。
CO加氢合成低碳醇反应十分复杂,过程中常伴随着F-T合成、甲醇合成以及水煤气变换等多个副反应,导致总醇选择性不高,醇产物碳数分布宽,这不仅增加了分离难度,而且也严重影响了整体工艺的经济性,因此越来越多的研究者都致力于催化剂的开发。目前研究相对比较集中的催化剂体系主要有:改性的甲醇合成催化剂,此类催化剂虽然活性较高,产物中异丁醇含量高,但反应条件苛刻,C2+醇选择性低,产物中含水量高;MoS2催化剂,具有抗硫性,产物含水少,C2+醇含量较高,但该类催化剂对原料气的氢碳比要求苛刻,H2/CO须在1.10~1.11之间,且催化剂稳定性差和寿命短;Rh基催化剂,Rh化合物较贵,催化剂易被CO2毒化,其活性和选择性一般达不到工业生产的要求,因此研究相对较少;Cu-Co基催化剂,具有反应活性高、C2+醇选择性好、操作条件温和等优点,但产物中含水多。
针对各催化体系的不足,目前研究主要集中在制备工艺的改进、助剂和载体的选择等方面,希望开发适合工业应用的合成低碳醇用催化剂。现有的专利文件《合成低碳混合醇的铜基催化剂及制法和应用》(申请号:2012年9月17日,公开号:CN102872881A,公开日:2013年1月16日),采用微乳液法制备的纳米催化剂,提高催化剂的稳定性,但制备工艺复杂,催化剂不适用的再生方法。专利文件《铜基复合氧化物催化剂及其制法和应用》(申请号:2013年1月17日,公开号:CN103084181A,公开日:2013年5月8日),通过反相微乳液法制备铜基复合氧化物催化剂,其总醇的选择性可达60%以上,但其重复性差且制备工艺较复杂。专利文件《一种合成低碳醇的催化剂及其制备方法》(申请号:2014年12月11日,公开号:CN105727982A,公开日:2016年7月6日),采用分步沉淀法制备Mn、Ce、Ni改性的CuZr催化剂,其总醇选择性可高达85.3%,异丁醇的选择性较好,但反应条件苛刻且CO转化率不到20%。专利文件《一种合成气制乙醇和高级醇的均匀分布的CoCu催化剂》(申请号:2016年5月23日,公开号:CN105903472A,公开日:2016年8月31日),以ZnAl复合物为载体制得均匀分布的CoCu催化剂,其催化合成气转化醇的选择性较高,C5+醇含量高达30%左右,但CO转化率仅为31.8%。
发明内容
本发明的目的在于提供一种合成气制备低碳醇催化剂的制备方法,该方法制备的催化剂机械强度高、性能稳定,且制备工艺简单,成本低。
本发明所采用的技术方案是:
一种合成气制备低碳醇催化剂的制备方法,包括以下步骤:
步骤一,处理载体碳纳米管;将载体碳纳米管置于HNO3溶液并超声波处理5h,并将酸洗后的碳纳米管用蒸馏水洗涤至中性,再经抽滤、烘干得到处理后的碳纳米管;
步骤二,称取前驱物硝酸铜、硝酸铁、硝酸镍、硝酸铬,得到混合物A,将混合物A溶于去离子水中,得到混合溶液B;
步骤三,称取步骤一处理后的载体碳纳米管碳纳米管分散于混合溶液B中,得到分散液C;
步骤四,向分散液C中滴加10wt%NH3·H2O,将分散液C的pH调节至8~9,再加入聚乙二醇,得到悬浊液D;
步骤五,将悬浊液D在40℃温度下反应1h,得到悬浊液E;
步骤六,将悬浊液E转移至高压反应釜中,在100~160℃温度下,反应24h,待冷却至室温后经离心、洗涤、干燥,并在350~550℃温度下焙烧4h,制得催化剂。
本发明的另一特点还在于,
步骤二中混合物A中硝酸铜、硝酸铁、硝酸镍、硝酸铬摩尔比为硝酸铜:硝酸铁=1:0.1~10,硝酸铜:硝酸镍=1:0.071~0.57,硝酸铜:硝酸铬=1:0.071~0.57。
步骤二中混合物A中硝酸铜、硝酸铁、硝酸镍、硝酸铬摩尔比为硝酸铜:硝酸铁=1:0.1~5,硝酸铜:硝酸镍=1:0.071~0.4,硝酸铜:硝酸铬=1:0.071~0.35。
步骤二中混合物A中硝酸铜、硝酸铁、硝酸镍、硝酸铬摩尔比为硝酸铜:硝酸铁=1:0.1~3,硝酸铜:硝酸镍=1:0.071~0.3,硝酸铜:硝酸铬=1:0.071~0.28。
步骤一中HNO3溶液的质量浓度为5~40%。
步骤二中制得的混合溶液B金属离子浓度为0.25~1.0mol·L-1。
步骤二中制得的混合溶液B金属离子浓度为0.3~0.8mol·L-1。
步骤三中载体碳纳米管占预制得催化剂总量的20~40%。
步骤四的聚乙二醇占预制得催化剂总量的0~20%。
聚乙二醇选用聚乙二醇2000。
本发明的有益效果是:本发明的提供合成气制备低碳醇催化剂的制备方法,该方法以碳纳米管为载体,提高了催化剂中有效组分的分散度,同时采用沉淀法及水热合成法相结合制得的催化剂,粒度小,分布均匀,能有效减轻颗粒催化剂制备过程中常见的颗粒团聚与烧结问题,有利于提高催化剂的活性。该催化剂的原料廉价易得;催化剂机械强度高、性能稳定、活性高。制得的催化剂催化合成气制低碳醇中烃类的选择性低,CO转化率可达38.91%醇的选择性较高,尤其是丙醇含量高达12%~25.5%,具有较好的经济效益,本方法制备工艺简单、且成本低。
具体实施方式
本发明提供了一种合成气制备低碳醇催化剂的制备方法,包括以下步骤:
步骤一,处理载体碳纳米管;将载体碳纳米管置于HNO3溶液并超声波处理5h,并将酸洗后的碳纳米管用去离子水洗涤至中性,再经抽滤、烘干得到处理后的碳纳米管;
步骤二,称取前驱物硝酸铜、硝酸铁、硝酸镍、硝酸铬,得到混合物A,将混合物A溶于去离子水中,得到混合溶液B;
步骤三,称取步骤一处理后的载体碳纳米管碳纳米管分散于混合溶液B中,得到分散液C;
步骤四,向分散液C中滴加10wt%NH3·H2O,将分散液C的pH调节至8~9,再加入聚乙二醇,得到悬浊液D;
步骤五,将悬浊液D在40℃温度下反应1h,得到悬浊液E;
步骤六,将悬浊液E转移至高压反应釜中,在100~160℃温度下,反应24h,待冷却至室温后经离心、洗涤、干燥,并在350~550℃温度下焙烧4h,制得催化剂。
步骤二中混合物A中硝酸铜、硝酸铁、硝酸镍、硝酸铬摩尔比为硝酸铜:硝酸铁=1:0.1~10,硝酸铜:硝酸镍=1:0.071~0.57,硝酸铜:硝酸铬=1:0.071~0.57。
步骤二中混合物A中硝酸铜、硝酸铁、硝酸镍、硝酸铬摩尔比为硝酸铜:硝酸铁=1:0.1~5,硝酸铜:硝酸镍=1:0.071~0.4,硝酸铜:硝酸铬=1:0.071~0.35。
步骤二中混合物A中硝酸铜、硝酸铁、硝酸镍、硝酸铬摩尔比为硝酸铜:硝酸铁=1:0.1~3,硝酸铜:硝酸镍=1:0.071~0.3,硝酸铜:硝酸铬=1:0.071~0.28。
步骤一中HNO3溶液的质量浓度为5~40%。
步骤二中制得的混合溶液B金属离子浓度为0.25~1.0mol·L-1。
步骤二中制得的混合溶液B金属离子浓度为0.3~0.8mol·L-1。
步骤三中载体碳纳米管占预制得催化剂总量的20~40%。
步骤四中聚乙二醇占预制得催化剂总量的0~20%,所述的聚乙二醇选用聚乙二醇2000。
实施例1
将载体碳纳米管分散于浓度为5%的HNO3溶液,超声5h后,将酸洗后的碳纳米管用蒸馏水洗涤至中性,再经抽滤、烘干处理得到处理后的碳纳米管;处理后的碳纳米管表面被修饰,碳纳米管的表面孔径增大。称取3.94g硝酸铜Cu(NO3)2·3H2O,1.65g硝酸铁Fe(NO3)3·9H2O,0.466g硝酸铬Cr(NO3)3·9H2O及0.339g硝酸镍Cr(NO3)3·9H2O得到混合物A,将混合物A溶于91mL去离子水,制得金属离子总浓度为0.25mol·L-1的混合溶液B,称取1.2g经处理的载体碳纳米管分散于混合溶液B中,得到分散液C,再向分散液C中滴加10wt%NH3·H2O,调节至pH为8,得到悬浊液D;将悬浊液D在40℃恒温下搅拌1h得到悬浊液E;将悬浊液E转移至高压反应釜中,100℃恒温反应24h,自然冷却至室温,离心后弃去上清液,用无水乙醇洗涤,并在350℃焙烧4h,制得催化剂总量为3g,其中载体碳纳米管占催化剂总量的40wt%,Cu、Fe、Cr及Ni的摩尔比为,Cu:Fe为1:0.25,Cu:Cr为1:0.071,Cu:Ni为1:0.071。
合成气制备低碳醇反应是在固定床反应器中完成的,反应前用含10%H2的H2/N2混合气对催化剂进行还原处理(T=300℃,t=6h),随后切换合成气进行反应。反应条件:催化剂用量为0.5g,H2与CO的流量之比为2:1,反应温度320℃,反应压力4MPa,空速5000h-1,以冰水冷却后收集液相产物,反应所得液体和气相产物分别用气相色谱仪进行分析。结果见表1。
实施例2
将载体碳纳米管分散于浓度为40%的HNO3溶液,超声5h后,将酸洗后的碳纳米管用蒸馏水洗涤至中性,再经抽滤、烘干处理得到处理后的碳纳米管;称取1.51g硝酸铜,7.59g硝酸铁,1.43g硝酸铬及0.510g硝酸镍得到混合物A,将混合物A溶于30mL去离子水,制得金属离子总浓度为1.0mol·L-1的混合溶液B,称取0.6g经处理的载体碳纳米管分散于混合溶液B中,得到分散液C,再向分散液C中滴加10wt%NH3·H2O,调节至pH为9,加入0.6g聚乙二醇2000,得到悬浊液D;将悬浊液D在40℃恒温下搅拌1h得到悬浊液E;将悬浊液E转移至高压反应釜中,160℃恒温反应24h,自然冷却至室温,离心后弃去上清液,用无水乙醇洗涤,并在550℃焙烧4h,制得催化剂总量为3g,其中载体碳纳米管占催化剂总量的20wt%,Cu、Fe、Cr及Ni的摩尔比为,Cu:Fe为1:3,Cu:Cr为1:0.57,Cu:Ni为1:0.28。
按照实施例1对制得的催化剂进行催化合成反应,结果见表1。
实施例3
将载体碳纳米管分散于浓度为10%的HNO3溶液,超声5h后,将酸洗后的碳纳米管用蒸馏水洗涤至中性,再经抽滤、烘干处理得到处理后的碳纳米管。称取0.583g硝酸铜,8.99g硝酸铁,0.267g硝酸铬及0.375g硝酸镍得到混合物A,将混合物A溶于88mL去离子水,制得金属离子总浓度为0.3mol·L-1的混合溶液B,称取0.9g经处理的载体碳纳米管分散于混合溶液B中,得到分散液C,再向分散液C中滴加10wt%NH3·H2O,调节至pH为8,加入0.3g聚乙二醇2000,得到悬浊液D;将悬浊液D在40℃恒温下搅拌1h得到悬浊液E;将悬浊液E转移至高压反应釜中,150℃恒温反应24h,自然冷却至室温,离心后弃去上清液,用无水乙醇洗涤,并在500℃焙烧4h,制得催化剂总量为3g,其中载体碳纳米管占催化剂总量的30wt%,Cu、Fe、Cr及Ni的摩尔质量比为,Cu:Fe为1:10,Cu:Cr为1:0.3,Cu:Ni为1:0.57。
按照实施例1对制得的催化剂进行催化合成反应,结果见表1。
实施例4
将载体碳纳米管分散于浓度为30%的HNO3溶液,超声5h后,将酸洗后的碳纳米管用蒸馏水洗涤至中性,再经抽滤、烘干处理得到处理后的碳纳米管;称取0.89g硝酸铜,7.47g硝酸铁,0.370g硝酸铬及0.430g硝酸镍得到混合物A,将混合物A溶于31mL去离子水,制得金属离子总浓度为0.8mol·L-1的混合溶液B,称取1.05g经处理的载体碳纳米管分散于混合溶液B中,得到分散液C,再向分散液C中滴加10wt%NH3·H2O,调节至pH为8,加入0.3g聚乙二醇2000,得到悬浊液D;将悬浊液D在40℃恒温下搅拌1h得到悬浊液E;将悬浊液E转移至高压反应釜中,120℃恒温反应24h,自然冷却至室温,离心后弃去上清液,用无水乙醇洗涤,并在400℃焙烧4h,制得催化剂总量为3g,其中载体碳纳米管占催化剂总量的35wt%,Cu、Fe、Cr及Ni的摩尔质量比为,Cu:Fe为1:5,Cu:Cr为1:0.25,Cu:Ni为1:0.4。
按照实施例1对制得的催化剂进行催化合成反应,结果见表1。
实施例5
将载体碳纳米管分散于浓度为30%的HNO3溶液,超声5h后,将酸洗后的碳纳米管用蒸馏水洗涤至中性,再经抽滤、烘干处理得到处理后的碳纳米管;称取3.21g硝酸铜,2.31g硝酸铁,0.75g硝酸铬及0.54g硝酸镍得到混合物A,将混合物A溶于46ml去离子水,制得金属离子总浓度为0.50mol·L-1的混合溶液B;将1.20g经处理的载体碳纳米管分散于混合溶液B,得到分散液C,然后向分散液C中滴加10wt%NH3·H2O,调节至pH为8,加入0.4g聚乙二醇2000,得到悬浊液D;将悬浊液D在40℃恒温下搅拌1h得到悬浊液E;将悬浊液E转移至高压反应釜中,120℃恒温反应24h,自然冷却至室温,离心后弃去上清液,用无水乙醇洗涤,并在350℃焙烧4h,制得催化剂总量为3g,其中载体碳纳米管占催化剂总量的40wt%,Cu、Fe、Cr及Ni的摩尔质量比为,Cu:Fe为1:0.43,Cu:Cr为1:0.14,Cu:Ni为1:0.14。
按照实施例1对制得的催化剂进行催化合成反应,结果见表1。
实施例6
将载体碳纳米管分散于体积分数为30%HNO3溶液,超声5h后,将酸洗后的碳纳米管用蒸馏水洗涤至中性,再经抽滤、烘干处理得到处理后的碳纳米管;称取3.35g硝酸铜,2.41g硝酸铁,3.17g硝酸铬及0.29g硝酸镍得到混合物A,将混合物A溶于57ml去离子水,制得金属离子总浓度为0.50mol·L-1的混合溶液B,将0.75g处理后的载体碳纳米管分散于混合溶液B,得到分散液C,然后向分散液C中滴加10wt%NH3·H2O,调节至pH为9,加入0.40g聚乙二醇2000,得到悬浊液D;将悬浊液D在40℃恒温下搅拌1h得到悬浊液E;将悬浊液E转移至高压反应釜中,130℃恒温反应24h,自然冷却至室温,离心后弃去上清液,用无水乙醇洗涤,并在400℃焙烧4h,制得催化剂总量为3g,其中载体碳纳米管占催化剂总量的25wt%,
Cu:Fe=1:0.43,
Cu:Cr=1:0.57,Cu:Ni=1:0.071。
按照实施例1对制得的催化剂进行催化合成反应,结果见表1。
实施例7
将载体碳纳米管分散于体积分数为30%HNO3溶液,超声5h后,将酸洗后的碳纳米管用蒸馏水洗涤至中性,再经抽滤、烘干处理得到处理后的碳纳米管;称取2.50g硝酸铜,3.85g硝酸铁,0.40g硝酸铬及1.72g硝酸镍得到混合物A,将混合物A溶于54ml去离子水制得金属离子总浓度为0.50mol·L-1的混合溶液B,并将0.7g处理后载体碳纳米管分散于混合溶液B中,得到分散液C,然后向分散液C中滴加10wt%NH3·H2O,调节至pH为9,加入0.90g聚乙二醇2000,得到悬浊液D;将悬浊液D在40℃恒温下搅拌1h得到悬浊液E;将悬浊液E转移至高压反应釜中,140℃恒温反应24h,自然冷却至室温,离心后弃去上清液,用无水乙醇洗涤,并在450℃焙烧4h,制得催化剂总量为3g,其中载体碳纳米管占催化剂总量的30wt%,Cu:Fe=1:0.92,Cu:Cr=1:0.096,Cu:Ni=1:0.57。
按照实施例1~7对制得的催化剂进行催化合成反应,结果见表1。
表1催化剂活性评价结果
按照实施例1~7对制得的催化剂比表面积、孔径及孔容表,结果见表2。
表2催化剂的比表面积、孔径及孔容表
本发明提供一种合成气制备低碳醇催化剂的制备方法,该方法以碳纳米管为载体,提高了催化剂中有效组分的分散度,同时采用沉淀法及水热合成法相结合制得的催化剂,粒度小,分布均匀,能有效减轻颗粒催化剂制备过程中常见的颗粒团聚与烧结问题,有利于提高催化剂的活性。
本发明提供一种合成气制备低碳醇催化剂的制备方法,该催化剂的原料廉价易得;催化剂机械强度高、性能稳定、活性高。制得的催化剂催化合成气制低碳醇中烃类的选择性低,CO转化率可达38.91%醇的选择性较高,尤其是丙醇含量高达12%~25.5%,具有较好的经济效益。
Claims (5)
1.一种合成气制备低碳醇催化剂的制备方法,包括以下步骤:
步骤一,处理载体碳纳米管;
将载体碳纳米管置于质量浓度为5~40%的HNO3溶液并超声波处理5 h,再将酸洗后的碳纳米管用蒸馏水洗涤至中性,再经抽滤、烘干得到处理后的碳纳米管;
步骤二,称取前驱物硝酸铜、硝酸铁、硝酸镍、硝酸铬,得到混合物A,将混合物A溶于去离子水中,得到混合溶液B,所述混合物A中硝酸铜、硝酸铁、硝酸镍、硝酸铬摩尔比为硝酸铜:硝酸铁=1:0.1~10,硝酸铜:硝酸镍=1:0.071~0.57,硝酸铜:硝酸铬=1:0.071~0.57,制得的混合溶液B中金属离子浓度为0.25~1.0 mol•L-1;
步骤三,称取步骤一处理后的载体碳纳米管分散于混合溶液B中,得到分散液C;
步骤四,向分散液C中滴加10wt%NH3·H2O,将分散液C的pH调节至8~9,再加入聚乙二醇,得到悬浊液D;
步骤五,将悬浊液D在40℃温度下,静置1 h,得到悬浊液E;
步骤六,将悬浊液E转移至高压反应釜中,在100~160℃温度下,静置24 h,待冷却至室温后依次经离心、洗涤、干燥后,在350~550℃温度下焙烧4h,即制得催化剂。
2.如权利要求1所述的合成气制备低碳醇催化剂的制备方法,其特征在于,所述步骤二中混合物A中硝酸铜、硝酸铁、硝酸镍、硝酸铬摩尔比为硝酸铜:硝酸铁=1:0.1~5,硝酸铜:硝酸镍=1:0.071~0.4,硝酸铜:硝酸铬=1:0.071~0.35。
3.如权利要求1所述的合成气制备低碳醇催化剂的制备方法,其特征在于,所述步骤二中混合物A中硝酸铜、硝酸铁、硝酸镍、硝酸铬摩尔比为硝酸铜:硝酸铁=1:0.1~3,硝酸铜:硝酸镍=1:0.071~0.3,硝酸铜:硝酸铬=1:0.071~0.28。
4.如权利要求2所述的合成气制备低碳醇催化剂的制备方法,其特征在于,所述步骤二中制得的混合溶液B中金属离子浓度为0.3~0.8mol•L-1。
5.如权利要求3所述的合成气制备低碳醇催化剂的制备方法,其特征在于,所述步骤二中制得的混合溶液B中金属离子浓度为0.5~0.75mol·L-1。
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