CN114471558A - 一种用于二氧化碳加氢制甲醇的催化剂的制备方法 - Google Patents
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- -1 carboxylate ions Chemical class 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 230000009919 sequestration Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
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- 230000008929 regeneration Effects 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- 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
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Abstract
本发明公开一种用于二氧化碳加氢制甲醇的催化剂的制备方法,属于催化剂制备技术领域。本发明所述方法为称取Cu(NO3)2·3H2O和Zr(NO3)2·5H2O,用去离子水溶解,得到金属离子总浓度为0.5mol/L的硝酸盐溶液;将柠檬酸加入到硝酸盐溶液中,搅拌至形成蓝色透明的溶液,且硝酸盐溶液与柠檬酸溶液的摩尔比为1:1;然后将得到的溶液放入水浴锅中,调节初始pH为3.0~6.7,搅拌至其形成黏稠的凝胶;将凝胶转移至干燥箱中进行干燥得到干凝胶,然后在马弗炉中焙烧,焙烧后研磨得到催化剂。本发明所述方法可以通过调节反应溶液pH值,从而调控干凝胶中金属离子的配位方式进而调控催化剂的性能。
Description
技术领域
本发明涉及一种用于二氧化碳加氢制甲醇的催化剂的制备方法,属于催化剂制备技术领域。
背景技术
大量化石燃料的燃烧导致作为温室气体的CO2的排放量不断提高,为了减少大气中CO2含量,改善全球温室效应,实现能源环境可持续发展,人们提出了碳捕获利用与封存策略,将生产过程中产生的CO2合理利用,以减少工业生产中新增的CO2排放。该策略中的最优方面在于封存CO2同时,并将CO2资源化、能源化,还能产生经济效益。CO2资源化利用制取的高附加值化学品主要包括甲醇、烯烃、甲酸、高碳醇、二甲醚、液体燃料等。甲醇(Methanol又称羟基甲烷,是一种有机化合物,有毒;它是结构最为简单的饱和一元醇,同时也是一种重要的化工基础原材料和燃料替代品,因此寻找一种新的用于二氧化碳加氢制甲醇的催化剂的制备方法是非常必要的。
发明内容
本发明的目的在于提供一种用于二氧化碳加氢制甲醇的催化剂的制备方法,具体包括以下步骤:
(1)称取Cu(NO3)2·3H2O和Zr(NO3)2·5H2O,用去离子水溶解,得到金属离子总浓度为0.5mol/L的硝酸盐溶液,其中 Cu2+:Zr4+的摩尔比为1:1。
(2)将柠檬酸加入到硝酸盐溶液中,搅拌至形成蓝色透明的溶液,且硝酸盐溶液与柠檬酸溶液的摩尔比为1:1。
(3)然后将得到的溶液放入水浴锅中,调节初始pH为3.0~6.7,搅拌至其形成黏稠的凝胶。
(4)将凝胶转移至干燥箱中进行干燥得到干凝胶,然后在马弗炉中焙烧,焙烧后研磨得到催化剂。
优选的,本发明步骤(3)中水浴加热的条件为:90℃。
优选的,本发明步骤(3)中调节初始pH所用试剂为氨水。
优选的,本发明步骤(4)中的烘干温度为80℃。
优选的,本发明步骤(4)中焙烧的条件为:400℃焙烧4h。
本发明的有益效果:本发明所述方法可以通过调节反应溶液pH值,从而调控干凝胶中金属离子的配位方式进而调控催化剂的性能,当柠檬酸配位数为1时,CA-CZr1中金属离子以单齿、双齿与柠檬酸中的羧酸根离子配位形成以Cu2+为中心的三维立体网络结构;在焙烧过程中有利于金属离子分散开来,不容易联结造成CuO的平均晶粒尺寸增大,促进催化剂还原过程的进行,从而CO2的转化率最好为11.8%,甲醇选择性76.8%。
附图说明
图1为干凝胶FTIR谱图。
具体实施方式
下面结合具体实施例对本发明作进一步详细说明,但本发明的保护范围并不限于所述。
实施例1
(1)称取一定量Cu(NO3)2·3H2O、Zr(NO3)2·5H2O,用去离子水溶解,得到金属离子总浓度为0.5mol/L的硝酸盐溶液(金属离子的摩尔比为Cu2+∶Zr4+=1∶1)。
(2)将柠檬酸加入到硝酸盐溶液中,搅拌至形成蓝色透明的溶液,且硝酸盐溶液与柠檬酸溶液的摩尔比为1:1。
(3)然后将得到的溶液放入90℃水浴锅中,用氨水调节初始pH,搅拌至其形成黏稠的凝胶。
(4)将凝胶转移至已预热到80℃的烘箱中干燥得到干凝胶,最后在马弗炉中将得到的干凝胶在400℃焙烧4h,焙烧后研磨得到催化剂。
本实施例中用氨水调节初始pH分别为3.13、4.76、6.40,对应不同干凝胶标记为PCA-CZr1(配位数为1)、PCA-CZr2(配位数为2) 、PCA-CZr3(配位数为3),其配位方式如表1所示,不同催化剂的催化性能如表2所示。
表1不同pH条件下干凝胶的配位方式
表2 不同pH条件下催化剂的催化性能
从表2可以看出,柠檬酸配位数的增加不利于配位形式多样化,进而不利于形成以Cu2+为中心的三维立体网络结构;当柠檬酸配位数为1时,CA-CZr1中金属离子以单齿、双齿与柠檬酸中的羧酸根离子配位形成以Cu2+为中心的三维立体网络结构。在焙烧过程中有利于金属离子分散开来,不容易联结造成CuO的平均晶粒尺寸增大,促进催化剂还原过程的进行,从而CO2的转化率最好为11.8%,甲醇选择性为76.8%。
图1为干凝胶FTIR谱图,由图可以看出,3441cm-1和3143cm-1附近的峰值分别对应羧酸中O-H的伸缩振动峰和NH3中N-H伸缩振动峰;而干凝胶均出现了3143cm-1的吸收峰,这是因为干凝胶中的N-H伸缩振动峰来自于制备过程中添加的氨水;在1300-1950cm-1区域的峰为C═O振动特征峰。作为对照的柠檬酸,在 1700-1800cm-1出现双重吸收峰,归属于羧基的C═O伸缩振动。其中,1766cm-1处为游离态羧基C═O伸缩振动峰,而1578cm-1处为形成分子间氢键后的C═O伸缩振动峰。
PCA-CZr在1766m-1左右出现吸收峰,说明干凝胶中存在未与金属配位的游离羧酸。干凝胶在1390和1600cm-1处出现强双重吸收峰,分别为羰基中C═O的反对称和对称伸缩振动峰;与柠檬酸对比,干凝胶的C═O伸缩振动峰向低波数移动,表明羧基与金属离子之间发生了配位作用。
Claims (5)
1.一种用于二氧化碳加氢制甲醇的催化剂的制备方法,其特征在于,具体包括以下步骤:
(1)称取Cu(NO3)2·3H2O和Zr(NO3)2·5H2O,用去离子水溶解,得到金属离子总浓度为0.5mol/L的硝酸盐溶液,其中 Cu2+:Zr4+的摩尔比为1:1;
(2)将柠檬酸加入到硝酸盐溶液中,搅拌至形成蓝色透明的溶液,且硝酸盐溶液与柠檬酸溶液的摩尔比为1:1;
(3)然后将得到的溶液放入水浴锅中,调节初始pH为3.0~6.7,搅拌至其形成黏稠的凝胶;
(4)将凝胶转移至干燥箱中进行干燥得到干凝胶,然后在马弗炉中焙烧,焙烧后研磨得到催化剂。
2.根据权利要求1所述用于二氧化碳加氢制甲醇的催化剂的制备方法,其特征在于:步骤(3)中水浴加热的条件为:90℃。
3.根据权利要求1所述用于二氧化碳加氢制甲醇的催化剂的制备方法,其特征在于:步骤(3)中调节初始pH所用试剂为氨水。
4.根据权利要求1所述用于二氧化碳加氢制甲醇的催化剂的制备方法,其特征在于:步骤(4)中的烘干温度为80℃。
5.根据权利要求1所述用于二氧化碳加氢制甲醇的催化剂的制备方法,其特征在于:步骤(4)中焙烧的条件为:400℃焙烧4h。
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