CN111530458A - 一种单原子催化剂及其在二氧化碳加氢反应中的应用 - Google Patents
一种单原子催化剂及其在二氧化碳加氢反应中的应用 Download PDFInfo
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- CN111530458A CN111530458A CN202010411135.2A CN202010411135A CN111530458A CN 111530458 A CN111530458 A CN 111530458A CN 202010411135 A CN202010411135 A CN 202010411135A CN 111530458 A CN111530458 A CN 111530458A
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- catalyst
- carbon dioxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 35
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 30
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 5
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052737 gold Inorganic materials 0.000 claims abstract description 3
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- 239000006185 dispersion Substances 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract 2
- 239000000969 carrier Substances 0.000 abstract 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract 1
- 239000011787 zinc oxide Substances 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 45
- 230000000694 effects Effects 0.000 description 27
- 238000012360 testing method Methods 0.000 description 24
- 238000001179 sorption measurement Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 6
- PYPNFSVOZBISQN-LNTINUHCSA-K cerium acetylacetonate Chemical compound [Ce+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O PYPNFSVOZBISQN-LNTINUHCSA-K 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910019580 Cr Zr Inorganic materials 0.000 description 1
- 229910019817 Cr—Zr Inorganic materials 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- -1 aromatics Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XYYVDQWGDNRQDA-UHFFFAOYSA-K trichlorogold;trihydrate;hydrochloride Chemical compound O.O.O.Cl.Cl[Au](Cl)Cl XYYVDQWGDNRQDA-UHFFFAOYSA-K 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/685—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with chromium
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- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
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- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
- C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明公开了一种单原子催化剂及其在二氧化碳加氢反应中的应用,属于二氧化碳转化技术领域。本发明采用二氧化铈、氧化锌、二氧化锆、三氧化二铬等作为载体,单原子的Pd、In、Cu、Au为活性组分;其中催化剂载体重量占催化剂总重量的95%~99.9%,活性组分重量占催化剂总重量的0.01%‑5%。本发明中的催化剂制备方法简单,通过调整反应条件可以选择性生成甲醇或者一氧化碳,且甲醇或者CO的选择性很高,均能达到90%以上,具有广阔的工业化应用前景。
Description
技术领域
本发明涉及一种单原子催化剂及其在二氧化碳加氢反应中的应用,属于二氧化碳转化技术领域。
背景技术
CO2是重要的温室气体,会引发一系列严峻的环境问题,如气候异常、全球变暖、海洋酸化、冰川消融、生态破坏等。它的减排以及催化转化已经引起全世界的关注,其中利用太阳能等可再生能源通过光催化、光电催化制氢,并将其用于二氧化碳的加氢以合成CO、甲醇等化工原料是二氧化碳利用的有效途径之一。CO是最为常见的碳一基础原料,其加氢可以直接合成烯烃、芳烃、汽油、柴油、航空煤油等基础化学品和燃料。甲醇是重要的基础化工原料,通过甲醇可以制取烯烃、芳烃等大宗化学品以及汽油柴油等,也可以直接用作燃料或燃料添加剂。
目前使用的二氧化碳加氢制甲醇的催化剂主要是在一氧化碳加氢制甲醇催化剂的基础上开发出来的,以Cu-Zn催化剂为主,主要选用载体包括SiO2、Al2O3、TiO2等,制备方法也大都以浸渍法或者共沉淀方法为主,但这类催化剂的催化性能不甚理想,存在CO2转化率低、甲醇选择性不高等问题。除此之外,最近还有一些新型金属氧化物催化剂的报道,比如Zr-Cd、Zr-Ga、Cr-Zn、Cr-Zr复合氧化物催化剂,这类催化剂虽然甲醇选择性比较高,可达80%,但活性不太理想,高活性、高选择性催化剂的开发仍然是目前研究的热点。
单原子催化剂在许多选择性加氢反应中表现出了较高的反应活性,比如肉桂醛上包含C=C双键和C=O双键,使用单原子催化剂可以有效地将不容易加氢的C=O双键加氢,而C=C双键保持不变。此外,在C≡C选择性加氢变为C=C的反应中,单原子催化剂也表现出了优异的选择性。目前并没有单原子催化剂在二氧化碳加氢制甲醇中的应用,在二氧化碳加氢的反应中,加氢产物主要有三种,CO、甲醇和甲烷,高选择性地得到某一种产物是研究的关键所在。
发明内容
针对上述问题,本发明提供了一种单原子催化剂用于二氧化碳加氢反应,通过调节反应条件,能够高选择性地得到甲醇或CO两种产物,且该催化剂的制备方法简单,具有工业化应用前景。
本发明的第一个目的是提供一种单原子催化剂,所述催化剂是由活性组分和载体组成,其中活性组分为Pd、Cu、Au、In中的一种或两种以上;载体为CeO2、ZrO2、ZnO、Cr2O3中的一种或两种以上;
其中,活性组分在载体上呈单原子分散状态,其含量占催化剂总质量的0.01%~5%;载体占催化剂总质量的95%~99.99%。
在本发明的一种实施方式中,活性组分的含量占催化剂总质量的0.1%~1%;载体占催化剂总质量的99%~99.9%。
本发明的第二个目的是提供制备上述单原子催化剂的方法,所述制备方法如下:
将活性组分前驱体和载体前驱体混合后放入球磨机中,设定球磨机转速为200~800rpm,球磨时间5~30h;然后将球磨后得到的固体粉末于200~500℃下焙烧1~15h,得到催化剂。
在本发明的一种实施方式中,所述制备方法中活性组分前驱体和载体前驱体的质量比为1:100~1:1000。
在本发明的一种实施方式中,所述制备方法中活性组分前驱体为含活性组分的乙酰丙酮盐、醋酸盐、柠檬酸盐、硝酸盐、碳酸盐、氯化盐中的一种。
在本发明的一种实施方式中,所述制备方法中载体前驱体为含载体的乙酰丙酮盐、醋酸盐、柠檬酸盐、硝酸盐、碳酸盐、氯化盐中的一种。
本发明的第三个目的是提供一种二氧化碳加氢制甲醇的方法,所述方法中利用了上述单原子催化剂。
本发明的第四个目的是提供一种二氧化碳加氢制CO的方法,所述方法中利用了上述单原子催化剂。
在本发明的一种实施方式中,所述二氧化碳加氢制甲醇或者CO的方法中,单原子催化剂制备好之后不需要还原,直接用于二氧化碳加氢的反应。
在本发明的一种实施方式中,所述二氧化碳加氢制甲醇的反应条件为:CO2/H2=1:1~10,空速为1~20L/gcat/h,反应温度为200℃~300℃,反应压力为0.1~10MPa。
在本发明的一种实施方式中,所述二氧化碳加氢制CO的反应条件为:CO2/H2=1:1~10,空速为1~20L/gcat/h,反应温度为300℃~400℃,反应压力为0.1~10MPa。
本发明的有益效果:
(1)本发明制备的单原子催化剂在二氧化碳加氢反应中时选择性可调,通过调整反应条件可高选择性地得到CO或者甲醇,原因在于:在单原子纳米颗粒上,尤其是单原子的Pd上,甲酸盐中间体稳定,从而有利于形成甲醇。同时,合成甲醇是一种放热反应,高温不利于甲醇的生成,但有利于发生逆水煤气变换反应生成CO,因为逆水煤气变换反应是吸热反应,高温比较有利反应的发生。同时由于催化剂单原子的属性,生成的CO倾向于直接脱附,而不会被深度加氢变成甲烷。因此,本发明中的单原子催化剂在低温下主要产物是甲醇,高温下产物则主要为CO。
(2)本发明中的单原子催化剂制备方法简单,具体地,仅需将活性组分前驱体和载体前驱体混合后放入球磨机中进行球磨,再经过一次煅烧便可得到本发明中的单原子催化剂。此外,本发明提供的制备方法每次制备的催化剂的量较大,相较一些实验室生产产量仅几克的制备规模,本发明提供的制备方法更具有工业化的应用前景。
附图说明
图1为实施例1中制备的催化剂的透射电镜图。
具体实施方式
下面结合具体实施例,进一步阐述本发明,应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。
1、催化剂性能评价:以下实施例中催化二氧化碳加氢的反应是在不锈钢固定床或浆态床反应器中进行的,具体催化性能测试即评价的方法如下:
取1g单原子催化剂与2.0g石英砂混合后置于反应器中,随后CO2/H2以一定流量流过催化剂床层,反应压力逐步升至设定压力,反应温度逐步升至设定温度开始反应。产物经冷阱后常压在线分析,由一台同时配有热导池和氢离子火焰检测器的气相色谱来分析,色谱条件为5A分子筛填充柱和毛细填充柱(50米),程序升温(初温50℃,保持10分钟,随后5℃/min升温至200℃,保持10分钟);冷阱中产物由另一台配有氢离子火焰检测器的气相色谱离线分析,色谱条件为HP-1毛细填充柱(50米),程序升温(初温50℃,保持5分钟,随后5℃/min升温至250℃,保持10分钟)。
CO2转化率=(进口CO2摩尔数–出口CO2摩尔数)/进口CO2摩尔数×100%
产物选择性=出口产物摩尔数×产物分子中碳原子数/(进口CO2摩尔数–出口CO2摩尔数)×100%
2、采用CO脉冲吸附法测定Pd的分散度。具体条件如下:采用BEL-CAT-BInstrument进行CO脉冲吸附。将50mg催化剂置于石英管中,在He气氛围下升温至200℃预处理1h,然后降至室温;切气为5%CO/He进行脉冲吸附,直至催化剂吸附饱和。通过催化剂表面吸附CO的分子数计算Pd的分散度,其中Pd/CO(摩尔比)为1:1。
Pd的平均粒径(d,nm)可根据Pd的分散度(D,%)进行计算,d(nm)=112/D。
实施例1
(1)将1g乙酰丙酮钯和200g乙酰丙酮铈加入球磨机中,500rpm下球磨10h。然后将所得固体在空气氛围下,450℃下焙烧3h,得到Pd含量为0.4%的Pd/CeO2催化剂。
图1为本实施例制备的催化剂的透射电镜图,在此图中没有发现Pd颗粒的存在,只有载体的晶格条纹,说明Pd在催化剂载体上呈现高分散状态。此外,采用CO脉冲吸附法测定Pd的分散度,Pd的分散度高达98.1%,认为此催化剂上Pd是单分散的状态,此催化剂为单原子催化剂。
(2)活性测试:参考前述“催化剂性能评价”在固定床反应器中对所制备催化剂进行催化活性评价,反应条件为:H2/CO2=3.0,温度为220℃,压力为3.0MPa,空速为2L/g/h,活性测试结果见表1。
实施例2
(1)将1g乙酰丙酮钯和400g乙酰丙酮铈加入球磨机中,500rpm下球磨10h。然后将所得固体在空气氛围下,450℃下焙烧3h,得到Pd含量为0.2%的Pd/CeO2催化剂,采用CO脉冲吸附法测定Pd的分散度,测得Pd的分散度为99.3%。
(2)活性测试的反应条件同实施例1,活性测试结果见表1。
实施例3
(1)将1g乙酰丙酮钯和600g乙酰丙酮铈加入球磨机中,500rpm下球磨10h。然后将所得固体在空气氛围下,450℃下焙烧3h,得到Pd含量为0.1%的Pd/CeO2催化剂,采用CO脉冲吸附法测定Pd的分散度,测得Pd的分散度为99.5%。
(2)活性测试的反应条件同实施例1,活性测试结果见表1。
实施例4
(1)将1g乙酰丙酮钯和200g乙酰丙酮铈加入球磨机中,300rpm下球磨15h。然后将所得固体在空气氛围下,450℃下焙烧3h,得到Pd含量为0.4%的Pd/CeO2催化剂,采用CO脉冲吸附法测定Pd的分散度,测得Pd的分散度为94.5%。
(2)活性测试的反应条件同实施例1,活性测试结果见表1。
实施例5
(1)催化剂制备同实施例1。
(2)在固定床反应器中对所制备催化剂进行活性评价,反应条件为:H2/CO2=5.0,温度为220℃,压力为5.0MPa,空速为2L/g/h,活性测试结果见表1。
实施例6
(1)催化剂制备同实施例1。
(2)在固定床反应器中对所制备催化剂进行活性评价,反应条件为:H2/CO2=3.0,温度为350℃,压力为3.0MPa,空速为2L/g/h,活性测试结果见表1。
实施例7
(1)将1g乙酰丙酮钯和200g乙酰丙酮锌加入球磨机中,500rpm下球磨10h。然后将所得固体在空气氛围下,400℃下焙烧3h,得到Pd含量为0.5%的Pd/ZnO催化剂,采用CO脉冲吸附法测定Pd的分散度,测得Pd的分散度为98.2%。
(2)活性测试的反应条件同实施例1,活性测试结果见表1。
实施例8
(1)将1g四氯金酸三水合物和600g氯化铬六水合物加入球磨机中,500rpm下球磨10h。然后将所得固体在空气氛围下,500℃下焙烧3h,得到Au含量为0.3%的Au/Cr2O3催化剂。
(2)活性测试的反应条件同实施例1,活性测试结果见表1。
实施例9
(1)将1g乙酰丙酮钯和200g乙酰丙酮锆加入球磨机中,500rpm下球磨10h。然后将所得固体在空气氛围下,500℃下焙烧3h,得到Pd含量为0.7%的Pd/ZrO2催化剂,采用CO脉冲吸附法测定Pd的分散度,测得Pd的分散度为98.2%。
(2)活性测试的反应条件同实施例6,活性测试结果见表1。
实施例10
(1)将1g乙酰丙酮铜和200g乙酰丙酮铈加入球磨机中,500rpm下球磨10h。然后将所得固体在空气氛围下,350℃下焙烧3h,得到Cu含量为0.3%的Cu/CeO2催化剂。
(2)活性测试的反应条件同实施例1,活性测试结果见表1。
实施例11
(1)将1g硝酸铟和600g硝酸铈加入球磨机中,500rpm下球磨10h。然后将所得固体在空气氛围下,350℃下焙烧3h,得到In含量为0.1%的In/CeO2催化剂。
(2)活性测试的反应条件同实施例6,活性测试结果见表1。
表1实施例中不同催化剂的反应性能
对比例1
(1)采用浸渍法制备Pd含量为0.4%的Pd/CeO2催化剂。具体的制备方法为:将0.043g硝酸钯前驱体溶解在去离去水中并等体积浸渍在5gCeO2载体上,于120℃下干燥过夜后,在450℃下焙烧3h,得到Pd含量为0.4%的Pd/CeO2催化剂,采用CO脉冲吸附法测定Pd的分散度,采用CO脉冲吸附法测定Pd的分散度,测得Pd的分散度为58.2%。
(2)活性测试的反应条件同实施例1,测试结果见表2。
对比例2
(1)采用浸渍法制备Pd含量为0.4%的Pd/CeO2催化剂,同对比例1。
(2)活性测试的反应条件同实施例6,测试结果见表2。
表2对比例中催化剂的反应性能
通过表1和表2中的产物分布结果可以看出,在本发明所制备单原子催化剂,通过改变反应条件,可以选择性的得到甲醇或者CO产物,且甲醇或者CO的选择性很高,均能达到90%以上;而对比例采用常规方法制备的催化剂,虽然Pd的含量和载体与对比例相同,反应条件也相同,但甲醇和CO的产物分布较为平均,没有优势产物,所有产物选择性均不高于60%。可能的原因是对比例中Pd的分散度不高,相应Pd颗粒比较大。
虽然本发明已以较佳实施例公开如上,但其并非用以限定本发明,任何熟悉此技术的人,在不脱离本发明的精神和范围内,都可做各种的改动与修饰,因此本发明的保护范围应该以权利要求书所界定的为准。
Claims (10)
1.一种单原子催化剂,其特征在于,所述催化剂是由活性组分和载体组成,其中活性组分为Pd、Cu、Au、In中的一种或两种以上;载体为CeO2、ZrO2、ZnO、Cr2O3中的一种或两种以上;
其中,活性组分在载体上呈单原子分散状态,其含量占催化剂总质量的0.01%~5%;载体占催化剂总质量的95%~99.99%。
2.根据权利要求1所述的单原子催化剂,其特征在于,活性组分的含量占催化剂总质量的0.1%~1%;载体占催化剂总质量的99%~99.9%。
3.一种制备权利要求1或2中所述单原子催化剂的方法,其特征在于,所述制备方法如下:
将活性组分前驱体和载体前驱体混合后放入球磨机中,设定球磨机转速为200~800rpm,球磨时间5~30h;然后将球磨后得到的固体粉末于200~500℃下焙烧1~15h,得到催化剂。
4.根据权利要求3中所述的方法,其特征在于,所述方法中活性组分前驱体和载体前驱体的质量比为1:100~1:1000。
5.根据权利要求3中所述的方法,其特征在于,所述方法中活性组分前驱体为含活性组分的乙酰丙酮盐、醋酸盐、柠檬酸盐、硝酸盐、碳酸盐、氯化盐中的一种。
6.根据权利要求3中所述的方法,其特征在于,所述方法中载体前驱体为含载体的乙酰丙酮盐、醋酸盐、柠檬酸盐、硝酸盐、碳酸盐、氯化盐中的一种。
7.一种二氧化碳加氢制甲醇的方法,其特征在于,所述方法中利用了权利要求1或2中的单原子催化剂。
8.根据权利要求7所述的二氧化碳加氢制甲醇的方法,其特征在于,所述二氧化碳加氢制甲醇的反应条件为:CO2/H2=1:1~10,空速为1~20L/gcat/h,反应温度为200℃~300℃,反应压力为0.1~10MPa。
9.一种二氧化碳加氢制CO的方法,其特征在于,所述方法中利用了权利要求1或2中的单原子催化剂。
10.根据权利要求9所述的二氧化碳加氢制CO的方法,其特征在于,所述二氧化碳加氢制CO的反应条件为:CO2/H2=1:1~10,空速为1~20L/gcat/h,反应温度为300℃~400℃,反应压力为0.1~10MPa。
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