CN106994367A - 硫掺杂石墨烯负载的镉钼基催化剂及其制备方法和应用 - Google Patents
硫掺杂石墨烯负载的镉钼基催化剂及其制备方法和应用 Download PDFInfo
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 59
- 239000011593 sulfur Substances 0.000 title claims abstract description 59
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 49
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 48
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 239000011733 molybdenum Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 45
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 35
- 239000010439 graphite Substances 0.000 claims abstract description 35
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 24
- 239000004964 aerogel Substances 0.000 claims abstract description 21
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 15
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000002604 ultrasonography Methods 0.000 claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 11
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001661 cadmium Chemical class 0.000 claims abstract description 8
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims abstract description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 24
- 239000012498 ultrapure water Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 16
- 238000000967 suction filtration Methods 0.000 claims description 15
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- 230000033228 biological regulation Effects 0.000 claims description 9
- 230000003213 activating effect Effects 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 3
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 3
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 28
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000010959 commercial synthesis reaction Methods 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract description 2
- 229960004424 carbon dioxide Drugs 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000011160 research Methods 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000004575 stone Substances 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- -1 Carbon olefin Chemical class 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- AJVCUHHHRPBRHU-UHFFFAOYSA-N cadmium nitric acid Chemical compound [Cd].[N+](=O)(O)[O-] AJVCUHHHRPBRHU-UHFFFAOYSA-N 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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Abstract
本发明涉及催化和环保领域,具体涉及硫掺杂石墨烯负载的镉钼基催化剂及其制备方法和应用,本发明使用氧化石墨、硫化氢、镉盐、钼酸盐、硫酸铈作为原料制备硫掺杂石墨烯负载的镉钼基催化剂;本发明制备方法简单,将氧化石墨超声剥离成氧化石墨烯,低温冻干制备成氧化石墨烯气凝胶,硫化氢与其表面含氧官能团发生还原和掺杂,一步合成硫掺杂石墨烯气凝胶;镉盐沉积于硫掺杂石墨烯表面;钼和铈通过离子交换及高温条件与镉复合,最终制得高负载、比表面积大的硫掺杂石墨烯负载的镉钼基催化剂;该催化剂催化活性高,选择性好,对附加价值更高的乙醇具有特别好的选择性,催化反应条件相对温和,在二氧化碳工业合成低碳醇中具备良好的应用前景。
Description
技术领域
本发明涉及催化和环保领域,具体涉及一种硫掺杂石墨烯负载的镉钼基催化剂及其制备方法和应用。
背景技术
近年来,温室气体二氧化碳排放量与日俱增,二氧化碳的固定研究已日益引起人们的关注。现有技术中,对二氧化碳的固定研究较多的是利用二氧化碳加氢合成甲醇;此外,也有研究利用二氧化碳加氢合成其它低碳醇和低碳烯烃。利用二氧化碳合成低碳醇、低碳烯烃在石油资源日益枯竭的当代意义重大。
二氧化碳作为一种稳定的小分子,改善其反应活性合成低碳非常困难,目前对于二氧化碳催化合成低碳醇的研究较少,其中多为二氧化碳加氢合成甲醇的研究,对于经济价值更高的低碳醇研究更少。现有技术中,二氧化碳合成低碳醇的催化剂的活性组分主要集中于Cu,Mo,Rh,Ru,Zr等过渡金属及双金属,但现有的催化剂合成方法较为复杂,且催化反应活性低,低碳醇选择性差等缺陷。
发明内容
本发明是解决现有技术中对二氧化碳合成低碳醇的催化剂研究较少,催化剂合成方法较为复杂,催化反应活性低,低碳醇选择性差的技术问题。
为解决上述问题,本发明的技术方案如下:
硫掺杂石墨烯负载的镉钼基催化剂,包括以下重量配比的原料,
氧化石墨:15-20份;
硫化氢:5-10份;
镉盐:10-15份;
钼酸盐:4-6份。
优选地,所述镉盐为氯化镉、硫酸镉或硝酸镉中的一种。
优选地,所述钼酸盐为钼酸铵或钼酸钾。
优选地,所述硫掺杂石墨烯负载的镉钼基催化剂,包括以下重量配比的原料,
氧化石墨:15-20份;
硫化氢:5-10份;
镉盐:10-15份;
钼酸盐:4-6份。
硫酸铈:2份。
优选地,所述硫掺杂石墨烯负载的镉钼基催化剂,包括以下重量配比的原料,
氧化石墨:18份;
硫化氢:8份;
镉盐:12份;
钼酸盐:5份;
硫酸铈:2份。
优选地,所述硫掺杂石墨烯负载的镉钼基催化剂的载体为硫掺杂的石墨烯,硫的质量分数为1.5%-1.7%;活化组分为镉/钼,质量分数为20%-40%;铈为助剂,质量分数为0.5%-2%。
硫掺杂石墨烯负载的镉钼基催化剂的制备方法,包括以下步骤:
步骤一,将所述氧化石墨中加入1000倍重量的超纯水中,超声剥离4-8小时,得到均匀分散的氧化石墨烯;
步骤二,将所述氧化石墨烯在-80℃--50℃条件下冷冻干燥8-10小时,得到氧化石墨烯气凝胶;
步骤三,将所述氧化石墨烯气凝胶在氮气氛围下,加热至1100-1200℃,通入硫化氢气体,反应4-6小时,得到硫掺杂石墨烯;
步骤四,将所述硫掺杂石墨烯气凝胶研磨成粉末,加入100倍重量的超纯水中,超声分散30-60分钟,剧烈搅拌下加入所述镉盐溶液,调节pH为8-8.5,超声2-4小时;
步骤五,将步骤四所得溶液抽滤,洗涤后,将固体重新转移至0.3倍重量的超纯水中,加热至100-120℃,在搅拌速度为200-300r/min条件下,滴加所述钼酸盐,反应18-24小时,抽滤、洗涤、烘干。
优选地,所述步骤五中,滴加钼酸盐的同时,滴加硫酸铈。
优选地,所述步骤五中,烘干条件为100-120℃温度下焙烤5-7小时。
上述硫掺杂石墨烯负载的镉钼基催化剂可用于二氧化碳合成低碳醇。
将上述硫掺杂石墨烯负载的镉钼基催化剂在固定床微催反应器进行二氧化碳加氢合成低碳混合醇反应活性评价,反应条件为:反应温度170℃,压力5.0MPa,体积空速4500h-1,原料气中H2与CO2体积比为4:1;液体产物经冷井冷凝收集后用气相色谱检测,所述液体产物中包括甲醇、乙醇、丙醇。
相对于现有技术,本发明的优点如下,
本发明使用氧化石墨、硫化氢、镉盐、钼酸盐、硫酸铈作为原料制备硫掺杂石墨烯负载的镉钼基催化剂,反应原料廉价易得,为工业化使用奠定基础;
本发明制备方法简单,易规模化生产;反应过程中,首先将氧化石墨超声剥离成氧化石墨烯,低温冻干制备成氧化石墨烯气凝胶,多孔结构的氧化石墨烯气凝胶具有非常大的比较面积,在氮气氛围及高温条件下,硫化氢与其表面含氧官能团发生还原和掺杂,一步合成硫掺杂石墨烯气凝胶;镉盐通过调节体系pH产生微沉淀,在超声条件下沉积于硫掺杂石墨烯表面;钼和铈通过离子交换及高温条件与镉复合,最终制得高负载、比表面积大的硫掺杂石墨烯负载的镉钼基催化剂。
本发明制备得到的硫掺杂石墨烯负载的镉钼基催化剂以硫掺杂石墨烯为载体,镉/钼为活化组分,铈为助剂;硫掺杂石墨烯作为载体,一方面具有大的比表面积、独特的二维结构、优良的导电和导热性、高的机械强度等石墨烯固有的优势,提高活化组分和助剂的负载量,增加活化组分的表面积,为催化反应提供良好的稳定性;另一方面掺杂的硫原子在石墨烯表面诱导形成高的局域电荷/自旋密度,与活化组分镉/钼具备良好的相互作用,从而影响催化反应的动力学机理,提高催化活性;铈作为助剂具有较高的负载量,与硫掺杂的石墨烯共同作用,影响活化组分的电子性质,提供酸碱位与二氧化碳配位,在催化过程中,消除非目标产物的反应活性,提高催化活性和选择性。
本发明制备得到的硫掺杂石墨烯负载的镉钼基催化剂用于二氧化碳合成低碳醇,催化活性高,选择性好,对附加价值更高的乙醇具有特别好的选择性,催化反应条件相对温和,在二氧化碳工业合成低碳醇中具备良好的应用前景。
具体实施方式
实施例1:
硫掺杂石墨烯负载的镉钼基催化剂的制备方法,包括以下步骤:
原料组成(重量份)
氧化石墨:18份;硫化氢:8份;氯化镉:12份;钼酸钾:5份;
步骤一,将所述氧化石墨中加入1000倍重量的超纯水中,超声剥离4-8小时,得到均匀分散的氧化石墨烯;
步骤二,将所述氧化石墨烯在-80℃--50℃条件下冷冻干燥8-10小时,得到氧化石墨烯气凝胶;
步骤三,将所述氧化石墨烯气凝胶在氮气氛围下,加热至1100-1200℃,通入硫化氢气体,反应4-6小时,得到硫掺杂石墨烯;
步骤四,将所述硫掺杂石墨烯气凝胶研磨成粉末,加入100倍重量的超纯水中,超声分散30-60分钟,剧烈搅拌下加入所述氯化镉溶液,调节pH为8-8.5,超声2-4小时;
步骤五,将步骤四所得溶液抽滤,洗涤后,将固体重新转移至0.3倍重量的超纯水中,加热至100-120℃,在搅拌速度为200-300r/min条件下,滴加所述钼酸钾,反应18-24小时,抽滤、洗涤、100-120℃温度下焙烤5-7小时。
实施例2:
硫掺杂石墨烯负载的镉钼基催化剂的制备方法,包括以下步骤:
原料组成(重量份)
氧化石墨:18份;硫化氢:8份;氯化镉:12份;钼酸钾:5份;硫酸铈:2份;
步骤一,将所述氧化石墨中加入1000倍重量的超纯水中,超声剥离4-8小时,得到均匀分散的氧化石墨烯;
步骤二,将所述氧化石墨烯在-80℃--50℃条件下冷冻干燥8-10小时,得到氧化石墨烯气凝胶;
步骤三,将所述氧化石墨烯气凝胶在氮气氛围下,加热至1100-1200℃,通入硫化氢气体,反应4-6小时,得到硫掺杂石墨烯;
步骤四,将所述硫掺杂石墨烯气凝胶研磨成粉末,加入100倍重量的超纯水中,超声分散30-60分钟,剧烈搅拌下加入所述氯化镉溶液,调节pH为8-8.5,超声2-4小时;
步骤五,将步骤四所得溶液抽滤,洗涤后,将固体重新转移至0.3倍重量的超纯水中,加热至100-120℃,在搅拌速度为200-300r/min条件下,滴加所述钼酸钾和硫酸铈,反应18-24小时,抽滤、洗涤、100-120℃温度下焙烤5-7小时。
实施例3:
硫掺杂石墨烯负载的镉钼基催化剂的制备方法,包括以下步骤:
原料组成(重量份)
氧化石墨:15份;硫化氢:5份;硫酸镉:10份;钼酸钾:4份;硫酸铈:2份;
步骤一,将所述氧化石墨中加入1000倍重量的超纯水中,超声剥离4-8小时,得到均匀分散的氧化石墨烯;
步骤二,将所述氧化石墨烯在-80℃--50℃条件下冷冻干燥8-10小时,得到氧化石墨烯气凝胶;
步骤三,将所述氧化石墨烯气凝胶在氮气氛围下,加热至1100-1200℃,通入硫化氢气体,反应4-6小时,得到硫掺杂石墨烯;
步骤四,将所述硫掺杂石墨烯气凝胶研磨成粉末,加入100倍重量的超纯水中,超声分散30-60分钟,剧烈搅拌下加入所述硫酸镉溶液,调节pH为8-8.5,超声2-4小时;
步骤五,将步骤四所得溶液抽滤,洗涤后,将固体重新转移至0.3倍重量的超纯水中,加热至100-120℃,在搅拌速度为200-300r/min条件下,滴加所述钼酸钾,反应18-24小时,抽滤、洗涤、100-120℃温度下焙烤5-7小时。
实施例4:
硫掺杂石墨烯负载的镉钼基催化剂的制备方法,包括以下步骤:
原料组成(重量份)
氧化石墨:20份;硫化氢:10份;硝酸镉:15份;钼酸铵:6份;硫酸铈:2份;
步骤一,将所述氧化石墨中加入1000倍重量的超纯水中,超声剥离4-8小时,得到均匀分散的氧化石墨烯;
步骤二,将所述氧化石墨烯在-80℃--50℃条件下冷冻干燥8-10小时,得到氧化石墨烯气凝胶;
步骤三,将所述氧化石墨烯气凝胶在氮气氛围下,加热至1100-1200℃,通入硫化氢气体,反应4-6小时,得到硫掺杂石墨烯;
步骤四,将所述硫掺杂石墨烯气凝胶研磨成粉末,加入100倍重量的超纯水中,超声分散30-60分钟,剧烈搅拌下加入所述硝酸镉溶液,调节pH为8-8.5,超声2-4小时;
步骤五,将步骤四所得溶液抽滤,洗涤后,将固体重新转移至0.3倍重量的超纯水中,加热至100-120℃,在搅拌速度为200-300r/min条件下,滴加所述钼酸铵,反应18-24小时,抽滤、洗涤、100-120℃温度下焙烤5-7小时。
对比例1
石墨烯负载的镉钼基催化剂的制备方法,包括以下步骤:
原料组成(重量份)
氧化石墨:18份;硼氢化钠:8份;氯化镉:12份;钼酸钾:5份;硫酸铈:2份;
步骤一,将所述氧化石墨中加入1000倍重量的超纯水中,超声剥离4-8小时,得到均匀分散的氧化石墨烯;
步骤二,将所述氧化石墨烯加入所述硼氢化钠,100℃条件下反应24小时,冷却后,在-80℃--50℃条件下冷冻干燥8-10小时,得到氧化石墨烯气凝胶;
步骤三,将所述石墨烯气凝胶研磨成粉末,加入100倍重量的超纯水中,超声分散30-60分钟,剧烈搅拌下加入所述氯化镉溶液,调节pH为8-8.5,超声2-4小时;
步骤四,将步骤三所得溶液抽滤,洗涤后,将固体重新转移至0.3倍重量的超纯水中,加热至100-120℃,在搅拌速度为200-300r/min条件下,滴加所述钼酸钾和硫酸铈,反应18-24小时,抽滤、洗涤、100-120℃温度下焙烤5-7小时。
对比例2
硫掺杂石墨烯负载的镉钼基催化剂的制备方法,包括以下步骤:
原料组成(重量份)
氧化石墨:18份;硫化氢:8份;氯化镍:12份;钼酸钾:5份;硫酸铈:2份;
步骤一,将所述氧化石墨中加入1000倍重量的超纯水中,超声剥离4-8小时,得到均匀分散的氧化石墨烯;
步骤二,将所述氧化石墨烯在-80℃--50℃条件下冷冻干燥8-10小时,得到氧化石墨烯气凝胶;
步骤三,将所述氧化石墨烯气凝胶在氮气氛围下,加热至1100-1200℃,通入硫化氢气体,反应4-6小时,得到硫掺杂石墨烯;
步骤四,将所述硫掺杂石墨烯气凝胶研磨成粉末,加入100倍重量的超纯水中,超声分散30-60分钟,剧烈搅拌下加入所述氯化镍溶液,调节pH为8-8.5,超声2-4小时;
步骤五,将步骤四所得溶液抽滤,洗涤后,将固体重新转移至0.3倍重量的超纯水中,加热至100-120℃,在搅拌速度为200-300r/min条件下,滴加所述钼酸钾和硫酸铈,反应18-24小时,抽滤、洗涤、100-120℃温度下焙烤5-7小时。
实施例5:
采用ICP检测硫掺杂石墨烯负载的镉钼基催化剂中镉、钼、铈含量
表一 硫掺杂石墨烯负载的镉钼基催化剂中镉、钼、铈含量
组别 | 硫含量% | 镉含量% | 钼含量% | 铈含量% |
实施例1 | 1.6 | 24.4 | 18.9 | - |
实施例2 | 1.7 | 23.8 | 17.3 | 1.9 |
实施例3 | 1.5 | 20.7 | 15.1 | 0.5 |
实施例4 | 1.6 | 15.4 | 19.5 | 1.2 |
实施例6:
将上述硫掺杂石墨烯负载的镉钼基催化剂在固定床微催反应器进行二氧化碳加氢合成低碳混合醇反应活性评价,反应条件为:反应温度170℃,压力5.0MPa,体积空速4500h-1,原料气中H2与CO2体积比为4:1;液体产物经冷井冷凝收集后用气相色谱检测,所述液体产物中包括甲醇、乙醇、丙醇。
表二催化剂用于二氧化碳合成低碳醇的催化活性、选择性
从表二可知,实施例1-实施例4所制备的硫掺杂石墨烯负载的镉钼基催化剂在二氧化碳合成低碳醇的反应过程中,CO2转化率高达42%,醇选择性高达91%,混合醇中,乙醇含量高达80%,说明催化剂具备较高的催化活性,总醇选择性高,且乙醇选择性高;其中加入以铈朱助剂的催化剂(实施例2-实施例4)的性能更优。
对比例1采用硼氢化钠还原的氧化石墨烯作为载体,没有掺杂硫,二氧化碳几乎未转化,说明,对比例1制得的产物不具备催化活性;对比例2将活性组分镉改为镍,催化剂的催化活性及选择性均不及实施例1-4,说明本催化剂的催化过程中载体硫掺杂石墨烯、助剂铈、活化组分镉/钼的协同作用。
需要说明的是上述实施例仅仅是本发明的较佳实施例,并没有用来限定本发明的保护范围,在上述基础上做出的等同替换或者替代均属于本发明的保护范围。
Claims (9)
1.硫掺杂石墨烯负载的镉钼基催化剂,其特征在于,包括以下重量配比的原料,
氧化石墨:15-20份;
硫化氢:5-10份;
镉盐:10-15份;
钼酸盐:4-6份。
2.如权利要求1所述的硫掺杂石墨烯负载的镉钼基催化剂,其特征在于,所述镉盐为氯化镉、硫酸镉或硝酸镉中的一种。
3.如权利要求2所述的硫掺杂石墨烯负载的镉钼基催化剂,其特征在于,所述钼酸盐为钼酸铵或钼酸钾。
4.如权利要求3所述的硫掺杂石墨烯负载的镉钼基催化剂,其特征在于,包括以下重量配比的原料,
氧化石墨:15-20份;
硫化氢:5-10份;
镉盐:10-15份;
钼酸盐:4-6份;
硫酸铈:2份。
5.如权利要求4所述的硫掺杂石墨烯负载的镉钼基催化剂,其特征在于,所述催化剂的载体为硫掺杂的石墨烯,硫的质量分数为1.5%-1.7%;活化组分为镉/钼,镉质量分数为15%-25%,钼质量分数为15%-20%;铈为助剂,质量分数为0.5%-2%。
6.如权利要求1-5任一项所述的硫掺杂石墨烯负载的镉钼基催化剂的制备方法,其特征在于,包括以下步骤:
步骤一,将所述氧化石墨中加入1000倍重量的超纯水中,超声剥离4-8小时,得到均匀分散的氧化石墨烯;
步骤二,将所述氧化石墨烯在-80℃--50℃条件下冷冻干燥8-10小时,得到氧化石墨烯气凝胶;
步骤三,将所述氧化石墨烯气凝胶在氮气氛围下,加热至1100-1200℃,通入硫化氢气体,反应4-6小时,得到硫掺杂石墨烯;
步骤四,将所述硫掺杂石墨烯气凝胶研磨成粉末,加入100倍重量的超纯水中,超声分散30-60分钟,剧烈搅拌下加入所述镉盐溶液,调节pH为8-8.5,超声2-4小时;
步骤五,将步骤四所得溶液抽滤,洗涤后,将固体重新转移至0.3倍重量的超纯水中,加热至100-120℃,在搅拌速度为200-300r/min条件下,滴加所述钼酸盐,反应18-24小时,抽滤、洗涤、烘干。
7.如权利要求6所述的硫掺杂石墨烯负载的镉钼基催化剂的制备方法,其特征在于,所述步骤五中,滴加钼酸盐的同时,滴加硫酸铈。
8.如权利要求6所述的硫掺杂石墨烯负载的镉钼基催化剂的制备方法,其特征在于,所述步骤五中,烘干条件为100-120℃温度下焙烤5-7小时。
9.如权利要求1-5任一项所述的硫掺杂石墨烯负载的镉钼基催化剂用于二氧化碳合成低碳醇。
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