CN115555021A - 一种二氧化碳加氢制液体烃联产低碳烯烃的催化剂制备方法 - Google Patents
一种二氧化碳加氢制液体烃联产低碳烯烃的催化剂制备方法 Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 36
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 36
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 21
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 20
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 19
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 16
- 239000007788 liquid Substances 0.000 title claims abstract description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title claims 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000843 powder Substances 0.000 claims abstract description 47
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052742 iron Inorganic materials 0.000 claims abstract description 28
- 238000004108 freeze drying Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 150000001447 alkali salts Chemical class 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 16
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052748 manganese Inorganic materials 0.000 claims description 14
- 239000011572 manganese Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 238000012216 screening Methods 0.000 claims description 11
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 235000011181 potassium carbonates Nutrition 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- -1 alkali metal alkaline salt Chemical class 0.000 claims description 2
- 229910052595 hematite Inorganic materials 0.000 claims description 2
- 239000011019 hematite Substances 0.000 claims description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 2
- ZWXOQTHCXRZUJP-UHFFFAOYSA-N manganese(2+);manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+3].[Mn+3] ZWXOQTHCXRZUJP-UHFFFAOYSA-N 0.000 claims description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 5
- 239000012752 auxiliary agent Substances 0.000 abstract description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 238000009736 wetting Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 241000282326 Felis catus Species 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction 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
- B01J23/76—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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J23/74—Iron group metals
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- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
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- C—CHEMISTRY; METALLURGY
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- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
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Abstract
本发明提供了一种二氧化碳加氢制液体烃联产低碳烯烃的催化剂制备方法,利用天然铁矿石粉制备二氧化碳加氢催化剂,催化剂原料易得,制备方法简单,活性组分和载体氧化铝混合均匀后直接浸渍助剂碱金属的碱性盐或氢氧化物,通过冷冻干燥脱除水分,无需高温焙烧,可保持活性组分的晶体结构不发生改变。催化剂具有较好的二氧化碳加氢催化性能,在适当条件下单程转化率可达40%以上,产物中甲烷和一氧化碳的选择性均低于10%,液体烃和低碳烯烃的选择性高。
Description
技术领域
本发明涉及二氧化碳催化加氢技术领域,具体涉及一种二氧化碳加氢制备液体烃联产低碳烯烃的催化剂制备方法。
背景技术
煤、石油、天然气等化石燃料的使用造成大量二氧化碳的排放,从而导致温室效应日益加重。为了应对气候变化,除了从根源上节能减排外,还要对二氧化碳进行捕集、封存和利用。
二氧化碳作为自然界唾手可得的可再生碳源,利用其合成有价值的产品,既可以缓解温室效应,又能减少对化石燃料的依赖。在二氧化碳利用中,通过富余电能和来自可再生能源的电力进行电解水制氢,然后利用二氧化碳催化加氢生成烃类化合物,是最可行且最有潜力的研究方向。既可作为当前的有效储能技术,又可在将来化石能源枯竭之后,作为可持续提供烃类燃料和有机化学品的关键技术,实现碳的绿色循环。
二氧化碳加氢制备烃类化合物一般采用铁基催化剂,通过连续催化逆水煤气反应,以及费托合成反应生成长链烃。但是目前有关二氧化碳加氢的铁基催化剂制备方法繁琐,催化剂活性重现性和稳定性差,如文献报道的过饱和浸渍法、共沉淀法、有机燃烧法等制备的铁基二氧化碳催化剂活性差异较大,不利于实际的工业应用。
浸渍法难以提高载体上活性金属铁的负载量,即使采用过饱和浸渍法,也难以保证载体上的活性金属均匀分布。共沉淀法等制备的铁氧化物的晶粒细小,热稳定性差,虽然处于粉末状态时表面积较高具有较高的活性,但是如果通过挤条、压片等方法制成大颗粒催化剂,会由于小晶粒之间的团聚和互相遮盖,造成催化剂的有效表面积大幅减小,影响催化剂的整体活性。
发明内容
本发明的目的在于提供一种简单、实用的二氧化碳加氢催化剂制备方法。考虑到化学合成的铁氧化物的晶粒尺寸一般较小,晶体结构不稳定,合成产物性质难以精确控制,造成铁基催化剂的活性重现性和稳定性差的问题,本发明采用具有一定纯度的天然铁矿石粉和氧化锰粉制备二氧化碳加氢催化剂,以不同孔容的氧化铝作为载体,碱金属的碱性盐或氢氧化物作为助剂。将铁矿石粉、氧化锰粉和载体氧化铝按照一定比例混合均匀后直接浸渍负载助剂,然后通过冷冻干燥脱除水分,无需高温焙烧,可保持活性组分的晶体结构不发生改变。
天然铁矿石粉的晶体结构稳定,从而可以保证所制备的铁基催化剂活性具备很好的重现性和活性稳定性。孔容较小的氧化铝粘结性好有利于提高催化剂的强度,孔容较大的氧化铝可以有效分隔活性金属组分,丰富的孔道结构可以提高催化剂的有效表面积,并可提供反应物和产物的扩散通道,从而有利于提高活性金属的利用效率,提高催化剂的整体活性。采用浸渍法负载碱金属的碱性盐或氢氧化物助剂,可以保证其在活性金属和载体氧化铝上的均匀分布,有利于发挥碱性助剂促进二氧化碳吸附的作用。所制备的催化剂在实际应用中表现出很好的二氧化碳加氢反应活性,以及较好的液体烃和低碳烯烃选择性。
本发明的目的通过如下措施来达到:首先称量质量百分含量15%-45%的天然铁矿石粉、0%-30%的氧化锰粉和25%-85%的载体氧化铝粉,将其充分研磨混合均匀。同时称取上述混合物质量百分数10%-25%的碱金属的碱性盐或氢氧化物,配制成水溶液均匀加入上述混合物中,之后将混合物放入冷冻干燥机的冷阱中冷冻4~8小时后,再转入干燥室干燥10-24h。将干燥好的催化剂取出后研磨,用压片机在5~20MPa的压力下压片成型,并破碎、筛分出10-20目颗粒,即可得到二氧化碳加氢催化剂。
所述的天然铁矿石为天然磁铁矿、赤铁矿、褐铁矿中的一种或二种以上组合,其中铁的质量百分含量为62-72%,颗粒直径为1-150μm。所述的氧化锰为天然或化学合成的二氧化锰、三氧化二锰、四氧化三猛、一氧化锰中的一种或二种以上组合,天然的氧化锰包括软锰矿、硬锰矿、水锰矿、黑锰矿、褐锰矿、方锰矿中的一种或二种以上组合,其中锰的质量百分含量为60-77%,颗粒直径为1-150μm。载体氧化铝为孔容 0.2-0.6cm3/g的氧化铝和孔容0.8-1.2cm3/g的氧化铝中的一种或二种组合,二者质量比优选5:1-1:5。助剂碱金属的碱性盐或氢氧化物为碳酸钾、碳酸氢钾、氢氧化钾、碳酸钠、碳酸氢钠、氢氧化钠中的一种或二种以上组合。
本发明的有益效果为:
(1)本发明采用性质稳定的天然矿物制备铁基二氧化碳加氢催化剂,方法简单、实用且成本低廉,易于工业实现;
(2)催化剂机械强度高,稳定性好且催化活性较高,CO2的单程转化率可达40%以上,产物中甲烷和一氧化碳的选择性均低于10%,低碳烯烃和液体烃的选择性相对较高。
具体实施方式
下面结合具体实施方式,对本发明作进一步描述,本发明的保护范围不受下列实施例限制。
本发明所采用的催化剂评价过程如下:
采用固定床反应器进行二氧化碳催化加氢的反应评价,催化剂填装量20mL,反应产物经2℃冷凝,接取液体烃类产物和水,根据水生成量估算二氧化碳单程转化率。不能冷凝的气相产物通过装有TCD和FID检测器的在线气相色谱进行含量分析,通过采用氮气内标法得到一氧化碳、甲烷和低碳烯烃的选择性。
进行二氧化碳加氢反应前,催化剂需首先进行还原和碳化。还原过程具体为:反应器通入氢气充压至2-4MPa,调整氢气空速为200~600mL/(h·g cat),以1℃/min的速度升温至350-450℃并持续还原4-10小时。碳化过程具体为:氢气还原后将反应器温度降低至100℃,通入二氧化碳,调整H2/CO2摩尔比为2.0-4.0,总气体空速500~ 800mL/(h·g cat),保持压力2-4MPa,以1℃/min的速度升温至250-350℃碳化4-10小时。
碳化结束后调整反应条件进行二氧化碳加氢:保持H2/CO2摩尔比2.0-4.0,反应温度250-350℃,压力2-4MPa,通入10mL/min的高纯氮气作为内标气体,总气体空速 500~1000mL/(h·g cat),采用低温恒温槽控制反应装置中的冷凝罐、高压和低压分离罐的温度为2℃。反应持续24h之后,接取冷凝的液体烃类产物和水,同时用在线色谱分析不能冷凝的气体组成。
实施例1
将13.05g天然磁铁矿粉(铁质量百分含量69%),4.24g孔容0.2-0.6cm3/g的氧化铝粉和12.71g孔容0.8-1.2cm3/g的氧化铝粉,充分搅拌混合均匀。称取4.50g碳酸钾溶于14mL水中,将溶液均匀加入上述混合物中至完全润湿。浸渍好的样品经冷冻干燥 16h,用压片机在10MPa的压力下压片,压片经破碎、筛分后得到10-20目的催化剂颗粒。
实施例2
将7.05g天然磁铁矿粉(铁质量百分含量69%),5.70g化学合成的质量百分含量98%的市售二氧化锰,3.45g孔容0.2-0.6cm3/g的氧化铝粉和13.80g孔容0.8-1.2cm3/g的氧化铝粉,充分搅拌混合均匀。称取4.50g碳酸钾溶于14mL水中,将溶液均匀加入上述混合物中至完全润湿。浸渍好的样品经冷冻干燥16h,用压片机在10MPa的压力下压片,压片经破碎、筛分后得到10-20目的催化剂颗粒。
实施例3
将7.05g天然磁铁矿粉(铁质量百分含量69%),5.70g软锰矿粉(锰质量百分含量62%),3.45g孔容0.2-0.6cm3/g的氧化铝粉和13.80g孔容0.8-1.2cm3/g的氧化铝粉,充分搅拌混合均匀。称取6.00g碳酸氢钾溶于15mL水中,将溶液均匀加入上述混合物中至完全润湿。浸渍好的样品经冷冻干燥18h,用压片机在10MPa的压力下压片,压片经破碎、筛分后得到10-20目的催化剂颗粒。
实施例4
将7.29g天然赤铁矿粉(铁质量百分含量65%),5.21g硬锰矿粉(锰质量百分含量60%),5.80g孔容0.2-0.6cm3/g的氧化铝粉和11.70g孔容0.8-1.2cm3/g的氧化铝粉,充分搅拌混合均匀。称取3.60g氢氧化钾溶于15mL水中,将溶液均匀加入上述混合物中至完全润湿。浸渍好的样品经冷冻干燥18h,用压片机在10MPa的压力下压片,压片经破碎、筛分后得到10-20目的催化剂颗粒。
实施例5
将9.75g天然褐铁矿粉(铁质量百分含量62%),4.65g方锰矿粉(锰质量百分含量76%),7.80g孔容0.2-0.6cm3/g的氧化铝粉和7.80g孔容0.8-1.2cm3/g的氧化铝粉,充分搅拌混合均匀。称取4.50g碳酸钠溶于12mL水中,将溶液均匀加入上述混合物中至完全润湿。浸渍好的样品经冷冻干燥14h,用压片机在10MPa的压力下压片,压片经破碎、筛分后得到10-20目的催化剂颗粒。
实施例6
将9.05g天然磁铁矿粉(铁质量百分含量69%),3.00g黑锰矿粉(锰质量百分含量70%),11.95g孔容0.2-0.6cm3/g的氧化铝粉和6.00g孔容0.8-1.2cm3/g的氧化铝粉,充分搅拌混合均匀。称取6.60g碳酸氢钠溶于14mL水中,将溶液均匀加入上述混合物中至完全润湿。浸渍好的样品经冷冻干燥16h,用压片机在10MPa的压力下压片,压片经破碎、筛分后得到10-20目的催化剂颗粒。
实施例7
将6.20g天然磁铁矿粉(铁质量百分含量69%),6.20g褐锰矿粉(锰质量百分含量67%),13.20孔容0.2-0.6cm3/g的氧化铝粉和4.40g g孔容0.8-1.2cm3/g的氧化铝粉,充分搅拌混合均匀。称取3.30g氢氧化钠溶于15mL水中,将溶液均匀加入上述混合物中至完全润湿。浸渍好的样品经冷冻干燥18h,用压片机在10MPa的压力下压片,压片经破碎、筛分后得到10-20目的催化剂颗粒。
对比例1:
将7.05g化学合成的质量百分含量99%的市售四氧化三铁,5.70g化学合成的质量百分含量98%的市售二氧化锰,3.45g孔容0.2-0.6cm3/g的氧化铝粉和13.80g孔容0.8-1.2cm3/g的氧化铝粉,充分搅拌混合均匀。称取4.50g碳酸钾溶于15mL水中,将溶液均匀加入上述混合物中至完全润湿。浸渍好的样品经冷冻干燥18h,用压片机在 10MPa的压力下压片,压片经破碎、筛分后得到10-20目的催化剂颗粒。
对比例2:
将7.30g化学合成的质量百分含量98%的市售三氧化二铁,4.65g化学合成的质量百分含量99%的市售一氧化锰,3.60g孔容0.2-0.6cm3/g的氧化铝粉和14.45g孔容0.8-1.2cm3/g的氧化铝粉,充分搅拌混合均匀。称取4.50g无水碳酸钾溶于15mL水中,将溶液均匀加入上述混合物中至完全润湿。浸渍好的样品经冷冻干燥18h,用压片机在 10MPa的压力下压片,压片经破碎、筛分后得到10-20目的催化剂颗粒。
下表为实施例1-7和对比例1-2制备的20mL催化剂连续运行24h的活性评价结果对比表,包括反应生成的水量以及计算得出的CO2转化率,以及产物中甲烷、一氧化碳、C5 +以上的液体烃收率和C2-C4低碳烃中的烯烷比。可以看出,采用本发明以天然铁矿石粉制备的铁基催化剂具有较好的二氧化碳加氢活性,二氧化碳单程转化率可达 40%以上,产物中甲烷和一氧化碳的选择性均低于10%,低碳烯烃和液体烃的选择性均高于采用化学合成的四氧化三铁或三氧化二铁制备的铁基催化剂。
实施例 | 水(mL/24h) | CO<sub>2</sub>转化率(%) | CH<sub>4</sub>(%) | CO(%) | C<sub>5</sub><sup>+</sup>(%) | C<sub>2</sub>-C<sub>4</sub>烯烷比 |
实施例1 | 50.5 | 43.65 | 9.54 | 3.51 | 53.93 | 3.86 |
实施例2 | 48.5 | 41.92 | 9.01 | 4.36 | 53.89 | 3.88 |
实施例3 | 49.0 | 42.35 | 8.24 | 4.43 | 55.16 | 4.23 |
实施例4 | 47.5 | 41.05 | 8.46 | 4.89 | 54.63 | 3.94 |
实施例5 | 46.5 | 40.19 | 8.63 | 4.92 | 53.87 | 3.91 |
实施例6 | 49.5 | 42.78 | 7.98 | 4.50 | 54.15 | 4.02 |
实施例7 | 46.5 | 40.19 | 7.65 | 5.14 | 54.23 | 4.15 |
对比例1 | 26.0 | 22.47 | 18.87 | 11.75 | 18.76 | 1.46 |
对比例2 | 22.0 | 19.01 | 17.12 | 12.03 | 20.24 | 1.58 |
Claims (5)
1.一种二氧化碳加氢制液体烃联产低碳烯烃的催化剂制备方法,其特征在于,包括如下步骤:
(1)以质量百分含量计,将天然铁矿石粉15%-45%、氧化锰粉0%-30%、氧化铝25%-85%混合均匀。
(2)以质量百分含量计,称取上述混合物质量百分数10%-25%的碱金属的碱性盐或氢氧化物,配制成水溶液加入上述混合物中,水的加入量使混合物可完全均匀润湿。之后将混合物冷冻干燥10-24h,研磨、压片成型并破碎、筛分为10-20目颗粒,得到二氧化碳加氢催化剂。
2.根据权利要求1所述的二氧化碳加氢制液体烃联产低碳烯烃的催化剂制备方法,其特征在于:所述的天然铁矿石为天然磁铁矿、赤铁矿、褐铁矿中的一种或二种以上组合,其中铁的质量百分含量为62-72%,颗粒直径为1-150μm。
3.根据权利要求1所述的二氧化碳加氢制液体烃联产低碳烯烃的催化剂制备方法,其特征在于:所述的氧化锰为天然或化学合成的二氧化锰、三氧化二锰、四氧化三猛、一氧化锰中的一种或二种以上组合,天然的氧化锰包括软锰矿、硬锰矿、水锰矿、黑锰矿、褐锰矿、方锰矿中的一种或二种以上组合,其中锰的质量百分含量为60-77%,颗粒直径为1-150μm。
4.根据权利要求1所述的二氧化碳加氢制液体烃联产低碳烯烃的催化剂制备方法,其特征在于:所述的氧化铝为孔容0.2-0.6cm3/g的氧化铝和孔容0.8-1.2cm3/g的氧化铝中的一种或二种组合,二者质量比优选5:1-1:5。
5.根据权利要求1所述的二氧化碳加氢制液体烃联产低碳烯烃的催化剂制备方法,其特征在于,所述的碱金属的碱性盐或氢氧化物为碳酸钾、碳酸氢钾、氢氧化钾、碳酸钠、碳酸氢钠、氢氧化钠中的一种或二种以上组合。
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