CN114797881B - 一种碳材料负载钴基催化剂及其制备和应用 - Google Patents
一种碳材料负载钴基催化剂及其制备和应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 19
- 239000010941 cobalt Substances 0.000 title claims abstract description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 13
- 239000002041 carbon nanotube Substances 0.000 claims description 13
- 238000012512 characterization method Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- SCNCIXKLOBXDQB-UHFFFAOYSA-K cobalt(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Co+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SCNCIXKLOBXDQB-UHFFFAOYSA-K 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 claims description 2
- 239000012263 liquid product Substances 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 238000005470 impregnation Methods 0.000 abstract description 7
- 230000003993 interaction Effects 0.000 abstract description 2
- 239000002923 metal particle Substances 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000011278 co-treatment Methods 0.000 description 9
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 9
- 239000007791 liquid phase Substances 0.000 description 9
- 238000011068 loading method Methods 0.000 description 9
- 238000005070 sampling Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000006641 stabilisation Effects 0.000 description 8
- 238000011105 stabilization Methods 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910020521 Co—Zn Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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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- 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
- B01J23/84—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 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/864—Cobalt and chromium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/889—Manganese, technetium or rhenium
- B01J23/8896—Rhenium
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Abstract
一种碳材料负载钴基催化剂及其制备和应用。本发明涉及一种碳材料负载型钴基催化剂制备方法及其在CO2加氢中的应用。以碳材料为载体,通过等体积浸渍的方法负载金属Co和助剂Ru、Cr、Re、Zr、Zn中一种或两种以上,并焙烧制备而成。其通过双金属的复合作用与载体的相互作用,使金属颗粒分布更加均匀,分散度更高,制备方法简单。本发明的催化剂用于CO2加氢制取C5+烃,具有高选择性。
Description
技术领域
本发明属于化工催化剂技术领域,具体涉及一种合成气制清洁燃料的催化剂及其制备与应用。更具体地,该催化剂的一般组成形式为Co-X-C,是一种以碳材料为载体的负载型Co基催化剂,辅助添加Ru、Cr、Re、Au、Zn等助剂以提高催化剂活性、产物中C5+烃类及混合醇的选择性并延长催化剂的使用寿命。
背景技术
将温室气体二氧化碳转化为高附加值烃具有广泛的应用前景,不仅可以缓解大气中二氧化碳浓度增加造成的气候变化,还可以减轻化石燃料消耗的压力,实现碳资源的有效循环。钴基催化剂是常用的催化二氧化碳加氢制长链烃的催化剂。但是目前单组分的钴基催化剂上高附加值烃产率偏低,催化剂稳定性较差。
助剂加入使二氧化碳的吸附增强,反应中生成的低碳烯烃更易在催化剂表面二次吸附。烯烃二次加氢使产物中C5+烷烃选择性增加。
发明内容
本发明的目的是,针对现有技术存在的不足,开发一种高活性Co-X-C催化剂,催化剂活性显著提高,C5+烃选择性达到40%以上。
为实现上述目标,本发明所采用的技术方案具体包括:
本发明所述一种碳材料负载型钴基催化剂,表示为Co-X-C,其中助剂X为Ru、Cr、Cd、Au、Zn中的一种或二种以上;催化剂中金属Co的含量为催化剂重量的5-35wt%(优选10-30wt%),助剂X含量为催化剂重量的0.01-10wt%(优选0.1-5wt%);载体C为活性炭、碳纳米管、炭黑、碳纤维中的一种或二种以上。
本发明所述的碳材料负载型钴基催化剂的制备方法,制备方法包括以下步骤:
(1)首先,将含有钴的可溶性盐中的一种或二种以上、助剂的可溶性盐中的一种或二种以上的水溶液浸渍碳材料载体,浸渍后的催化剂在室温下放置6-12h(优选8-10h),随后在303-393K(优选313-383K)空气条件下烘干8-48h(优选10-40h),制得半干基催化剂前驱体;
钴的可溶性盐为甲酸钴、乙酸钴、硝酸钴、草酸钴、氯化钴、硫酸钴、柠檬酸钴中的一种或二种以上;助剂X的可溶性盐为金属的甲酸盐、乙酸盐、硝酸盐、氯化物、硫酸盐、柠檬酸盐中的一种或二种以上;碳材料载体为活性炭、碳纳米管、炭黑、碳纤维中的一种或二种以上。
(2)半干基催化剂前驱体在氮气、氩气或氦气中的一种或二种以上气氛下,温度373-773K(优选400-700K),压力为常压,空速100-3000h-1(优选500-2500h-1),焙烧5-30h(优选8-28h),得到干基催化剂;
(3)干基催化剂在含氢气氛中还原活化,其中含氢气氛为纯H2或H2/保护气,含氢气氛中H2体积含量为10-100%(优选:其中H2/保护气中H2体积含量为10-90%),保护气为氮气、氩气或氦气中的一种或二种以上,还原活化温度473-873K(优选500-800K),压力0.1-3.0MPa(优选0.2-2.8MPa),空速500-10000h-1(优选1000-8000h-1),还原活化1-100h(优选5-80h),制备得活化催化剂Co-X-C。
本发明所述的碳材料负载型钴基催化剂进行CO2脉冲化学吸附表征,计算得到催化剂分散度为9-15%。
本发明所述的碳材料负载型钴基催化剂应用在CO2加氢反应中。
本发明所述的碳材料负载型钴基催化剂应用在CO2加氢反应反应器形式采用固定床反应器或浆态床反应器,反应条件为:温度453-573K,压力0.1-7.0MPa,空速500-10000h-1,H2/CO2摩尔比0.5-5.0。
本发明所述的碳材料负载型钴基催化剂应用在CO2加氢反应,其中原料气(CO2和H2)的进料方式采取连续进料,在催化剂床层连续进行F-T合成反应,反应产生的气体产物和液体产物连续出料,用在反应器后的热罐收集高沸点的重质组分,用在热罐后的冷罐收集低沸点的轻质组分,热罐加热温度维持在373-403K,冷罐温度维持在273-283K。
本发明通过双金属助剂的复合作用与载体的相互作用,使金属颗粒分散度更高,制备方法简单。本发明的催化剂用于CO2加氢制取C5+烃,具有高选择性。
本发明与现有技术相比具有以下优点:
采用本发明提供的催化剂,可以提高CO2转化率,提高产物中C5+烃类的选择性,使C5+烃类在产物中的选择性可以超过40%。从CO2出发直接制备高质量清洁燃料具有重要的实际意义。
具体实施方式
下面通过实施例及对比例进一步说明本发明,但是本发明不限于所列举的实例。
实施例1
制备Co-Ru-活性碳催化剂。具体实施方法为:
(1)选择活性炭为载体。将4.94g六水合硝酸钴、0.12g三氯化钌溶于10g水中,制成浸渍液。用该浸渍液在室温298K下浸渍10g活性炭载体后室温下放置在12h,随后置于313K烘箱中烘干24h.
(2)取出后在氩气中,逐渐升温至523K焙烧16h,空速1000h-1。
取出催化剂装入浆态床反应器中,填充量为10mL。催化剂在氢气中逐渐升温至673K还原20h,空速1000h-1,降温至423K,切换气体(H2/CO2=3:1,体积比),压力3.0MPa,升温至483K进行F-T合成反应,空速2000h-1。经过24h的稳定期后,每隔24小时取样分析尾气中各组分浓度、液相产物分布。所得结果列于附表1。
通过对催化剂进行CO2脉冲化学吸附表征,计算得到的分散度见表1。
实施例2
制备Co-Cr-碳纳米管催化剂。具体实施方法为:
(1)选择碳纳米管为载体。将4.94g六水合硝酸钴、0.22g九水合硝酸铬溶于10g水中,制成浸渍液。用该浸渍液在室温298K下浸渍10g碳纳米管载体后在室温下放置12h,随后置于313K烘箱中烘干24h.
(2)取出后在氩气中,逐渐升温至523K焙烧16h,空速1000h-1。
取出催化剂装入浆态床反应器中,填充量为10mL。催化剂在氢气中逐渐升温至673K还原20h,空速1000h-1,降温至423K,切换气体(H2/CO2=3:1,体积比),压力3.0MPa,升温至483K进行F-T合成反应,空速2000h-1。经过24h的稳定期后,每隔24小时取样分析尾气中各组分浓度、液相产物分布。所得结果列于附表1。
通过对催化剂进行CO2脉冲化学吸附表征,计算得到的分散度见表1。
实施例3
制备Co-Re-石墨烯催化剂。具体实施方法为:
(1)选择石墨烯为载体。将4.94g六水合硝酸钴、0.18g高铼酸铵溶于10g水中,制成浸渍液。用该浸渍液在室温298K下浸渍10g石墨烯载体后在室温下放置12h,随后置于313K烘箱中烘干24h.
(2)取出后在氩气中,逐渐升温至523K焙烧16h,空速1000h-1。
取出催化剂装入浆态床反应器中,填充量为10mL。催化剂在氢气中逐渐升温至673K还原20h,空速1000h-1,降温至423K,切换气体(H2/CO2=3:1,体积比),压力3.0MPa,升温至483K进行F-T合成反应,空速2000h-1。经过24h的稳定期后,每隔24小时取样分析尾气中各组分浓度、液相产物分布。所得结果列于附表1。
通过对催化剂进行CO2脉冲化学吸附表征,计算得到的分散度见表1。
实施例4
制备Co-Ru-Re-炭黑催化剂。具体实施方法为:
(1)选择炭黑为载体。将4.94g六水合硝酸钴、0.13g三氯化钌和0.1g高铼酸铵溶于10g水中,制成浸渍液。用该浸渍液在室温298K下浸渍10g炭黑载体后在室放置温下12h,随后置于313K烘箱中烘干24h.
(2)取出后在氩气中,逐渐升温至523K焙烧16h,空速1000h-1。
取出催化剂装入浆态床反应器中,填充量为10mL。催化剂在氢气中逐渐升温至673K还原20h,空速1000h-1,降温至423K,切换气体(H2/CO2=3:1,体积比),压力3.0MPa,升温至483K进行F-T合成反应,空速2000h-1。经过24h的稳定期后,每隔24小时取样分析尾气中各组分浓度、液相产物分布。所得结果列于附表1。
通过对催化剂进行CO2脉冲化学吸附表征,计算得到的分散度见表1。
实施例5
制备Co-Zn-活性炭催化剂。具体实施方法为:
(1)选择活性炭为载体。将4.94g六水合硝酸钴、0.15g六水合硝酸锌溶于10g水中,制成浸渍液。用该浸渍液在室温298K下浸渍10g活性炭载体后室温下放置在12h,随后置于313K烘箱中烘干24h.
(2)取出后在氩气中,逐渐升温至523K焙烧16h,空速1000h-1。
取出催化剂装入浆态床反应器中,填充量为10mL。催化剂在氢气中逐渐升温至673K还原20h,空速1000h-1,降温至423K,切换气体(H2/CO2=3:1,体积比),压力3.0MPa,升温至483K进行F-T合成反应,空速2000h-1。经过24h的稳定期后,每隔24小时取样分析尾气中各组分浓度、液相产物分布。所得结果列于附表1。
通过对催化剂进行CO2脉冲化学吸附表征,计算得到的分散度见表1。
实施例6
制备Co-Au-碳纳米管催化剂。具体实施方法为:
(1)选择碳纳米管为载体。将4.94g六水合硝酸钴、0.10g氯化金溶于10g水中,制成浸渍液。用该浸渍液在室温298K下浸渍8.95g碳纳米管载体后室温下放置在12h,随后置于313K烘箱中烘干24h.
(2)取出后在氩气中,逐渐升温至523K焙烧16h,空速1000h-1。
取出催化剂装入浆态床反应器中,填充量为10mL。催化剂在氢气中逐渐升温至673K还原20h,空速1000h-1,降温至423K,切换气体(H2/CO2=3:1,体积比),压力3.0MPa,升温至483K进行F-T合成反应,空速2000h-1。经过24h的稳定期后,每隔24小时取样分析尾气中各组分浓度、液相产物分布。所得结果列于附表1。
通过对催化剂进行CO2脉冲化学吸附表征,计算得到的分散度见表1。
实施例7
制备Co-Ru-Au-石墨烯催化剂。具体实施方法为:
(1)选择石墨烯为载体。将4.94g六水合硝酸钴、0.12g三氯化钌和0.10g的氯化金溶于10g水中,制成浸渍液。用该浸渍液在室温298K下浸渍10g石墨烯载体后室温下放置在12h,随后置于313K烘箱中烘干24h.
(2)取出后在氩气中,逐渐升温至523K焙烧16h,空速1000h-1。
取出催化剂装入固定床反应器中,填充量为2mL。催化剂在氢气中逐渐升温至673K还原20h,空速1000h-1,降温至423K,切换气体(H2/CO2=3:1,体积比),压力3.0MPa,升温至483K进行F-T合成反应,空速2000h-1。经过24h的稳定期后,每隔24小时取样分析尾气中各组分浓度、液相产物分布。所得结果列于附表1。
通过对催化剂进行CO2脉冲化学吸附表征,计算得到的分散度见表1。
实施例8
制备Co-Zn-石墨烯催化剂。具体实施方法为:
(1)选择石墨烯为载体。将4.94g六水合硝酸钴、0.15g六水合硝酸锌溶于10g水中,制成浸渍液。用该浸渍液在室温298K下浸渍10g石墨烯载体后在室温下放置12h,随后置于313K烘箱中烘干24h.
(2)取出后在氩气中,逐渐升温至523K焙烧16h,空速1000h-1。
取出催化剂装入固定床反应器中,填充量为2mL。催化剂在氢气中逐渐升温至673K还原20h,空速1000h-1,降温至423K,切换气体(H2/CO2=3:1,体积比),压力3.0MPa,升温至483K进行F-T合成反应,空速2000h-1。经过24h的稳定期后,每隔24小时取样分析尾气中各组分浓度、液相产物分布。所得结果列于附表1。
通过对催化剂进行CO2脉冲化学吸附表征,计算得到的分散度见表1。
对比例1
制备Co-碳纳米管催化剂。具体实施方法为:
(1)选择碳纳米管为载体。将4.94g六水合硝酸钴、溶于10g水中,制成浸渍液。用该浸渍液在室温298K下浸渍8.95g碳纳米管载体后在室温下放置12h,随后置于313K烘箱中烘干24h.
(2)取出后在氩气中,逐渐升温至523K焙烧16h,空速1000h-1。
取出催化剂装入浆态床反应器中,填充量为10mL。催化剂在氢气中逐渐升温至673K还原20h,空速1000h-1,降温至423K,切换气体(H2/CO2=3:1,体积比),压力3.0MPa,升温至483K进行F-T合成反应,空速2000h-1。经过24h的稳定期后,每隔24小时取样分析尾气中各组分浓度、液相产物分布。所得结果列于附表1。
通过对催化剂进行CO2脉冲化学吸附表征,计算得到的分散度见表1。
表1.催化剂CO2加氢催化性能、产物分析及分散度
本专利的结果可以看出,本专利提供的催化剂具有较高的二氧化碳加氢活性,同时,具有较高的C5+烃类选择性。因此,本发明提供了一种从二氧化碳出发直接制备高质量清洁燃料的新方法。
Claims (4)
1.一种碳材料负载型钴基催化剂在用于CO2加氢制取C5+烃的应用,其特征在于,催化剂中的助剂X为Ru、Cr、Re、Au、Zn中的一种或二种以上;催化剂中金属Co的含量为催化剂重量的5-35wt%,助剂X含量为催化剂重量的0.01-10wt%;载体C为活性炭、碳纳米管、炭黑、石墨烯、碳纤维中的一种或二种以上;
所述催化剂的制备方法包括以下步骤:
(1)首先,将含有钴的可溶性盐中的一种或二种以上、助剂的可溶性盐中的一种或二种以上的水溶液浸渍碳材料载体,浸渍后的催化剂在室温下放置6-12 h,随后在 303-393 K空气条件下烘干8-48 h,制得半干基催化剂前驱体;
钴的可溶性盐为甲酸钴、乙酸钴、硝酸钴、草酸钴、氯化钴、硫酸钴、柠檬酸钴中的一种或二种以上;助剂X的可溶性盐为助剂对应金属的甲酸盐、乙酸盐、硝酸盐、氯化物、硫酸盐、柠檬酸盐中的一种或二种以上;碳材料载体为活性炭、碳纳米管、炭黑、碳纤维中的一种或二种以上;
(2)半干基催化剂前驱体在氮气、氩气或氦气中的一种或二种以上气氛下,温度373-773 K,压力为常压,空速100-3000 h-1,焙烧5-30 h,得到干基催化剂;
(3)干基催化剂在含氢气氛中还原活化,其中含氢气氛为纯H2或H2/保护气,含氢气氛中H2体积含量为10-100%,保护气为氮气、氩气或氦气中的一种或二种以上,还原活化温度473-873 K,压力0.1-3.0 MPa,空速500-10000 h-1,还原活化1-100 h,制备得活化催化剂Co-X-C。
2.按照权利要求1所述的应用,碳材料负载型钴基催化剂进行CO2脉冲化学吸附表征,计算得到催化剂Co分散度为9-15%。
3.按照权利要求1所述的应用,其特征在于:CO2加氢反应反应器形式采用固定床反应器或浆态床反应器,反应条件为:温度453-573 K,压力0.1-7.0 MPa,空速500-10000 h-1,H2/CO2摩尔比0.5-5.0。
4.按照权利要求3所述的应用,其特征在于:原料气CO2和H2的进料方式采取连续进料,在催化剂床层连续进行反应,反应产生的气体产物和液体产物连续出料,用连接在反应器后的热罐收集高沸点的重质组分,用连接在热罐后的冷罐收集低沸点的轻质组分,热罐加热温度维持在373-403 K,冷罐温度维持在273-283 K。
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CN102266778A (zh) * | 2010-06-04 | 2011-12-07 | 中国海洋石油总公司 | 一种用于co加氢合成c2-c25高碳伯醇的催化剂及其制备方法 |
CN102861583A (zh) * | 2011-07-04 | 2013-01-09 | 中国石油化工股份有限公司 | 一种钴基费托合成催化剂及其制备方法 |
CN106268816A (zh) * | 2015-06-12 | 2017-01-04 | 中国科学院大连化学物理研究所 | 活性炭负载钴基合成油催化剂及其制备方法和应用 |
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CN102266778A (zh) * | 2010-06-04 | 2011-12-07 | 中国海洋石油总公司 | 一种用于co加氢合成c2-c25高碳伯醇的催化剂及其制备方法 |
CN102861583A (zh) * | 2011-07-04 | 2013-01-09 | 中国石油化工股份有限公司 | 一种钴基费托合成催化剂及其制备方法 |
CN106268816A (zh) * | 2015-06-12 | 2017-01-04 | 中国科学院大连化学物理研究所 | 活性炭负载钴基合成油催化剂及其制备方法和应用 |
CN108067235A (zh) * | 2016-11-15 | 2018-05-25 | 中国科学院大连化学物理研究所 | 一种合成气制烯烃联产高碳醇的催化剂及其制备与应用 |
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