CN112705191A - Catalyst for preparing carbon monoxide and preparation method and application thereof - Google Patents
Catalyst for preparing carbon monoxide and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 17
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 229910001868 water Inorganic materials 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 230000007547 defect Effects 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000010436 fluorite Substances 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 238000011156 evaluation Methods 0.000 description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 235000012501 ammonium carbonate Nutrition 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000005431 greenhouse gas Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/78—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 alkali- or alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst for preparing carbon monoxide by catalytic conversion of carbon dioxide, which comprises a composite metal oxide, wherein the composite metal oxide comprises Ba element, Zr element and other elements, and the other elements are selected from at least one of Zn, Cu, Fe, Co, Ni and Mn. The invention can obtain high CO at the same time by using the composite metal oxide containing a specific kind of metal elements and having a specific crystal phase structure as a catalyst2Conversion and CO selectivity.
Description
Technical Field
The invention relates to the field of carbon monoxide production, and particularly relates to a catalyst for preparing carbon monoxide through catalytic conversion of carbon dioxide, and a preparation method and application thereof.
Background
The synthesis gas mainly comprises carbon monoxide and hydrogen, and the production process of the synthesis gas mainly comprises the routes of methane steam reforming, methane carbon dioxide reforming, non-catalytic partial oxidation, methane self-heating reforming and the like which take natural gas as a raw material, coal gasification and the like which take coal as a raw material. With the development of coal chemical industry, more attention is paid to coal gasification technology.
Carbon dioxide is a main greenhouse gas, is the main cause of global warming, is a very abundant carbon resource which can be utilized, and has the current utilization rate of only about 1 percent. 2018, global CO2The total emission is 320 hundred million tons, wherein CO in China2The total emission amount reaches 82 hundred million tons, and the emission amount is the first in the world. Development of CO2The technologies of trapping, storage, conversion utilization and the like of the oil-water separation device are to be the targets commonly pursued by the global chemists. With CO2The greenhouse effect caused by large amount of emission is increasingly serious, and CO2Are being studied more and more actively.
The reverse water gas shift Reaction (RWGS) can convert a large amount of greenhouse gases into synthesis gas, and then the synthesis gas is used for preparing series of downstream chemical products with high added values, and the RWGS process and the catalyst technology can be used as a platform technology for key development. Reverse water gas shift reaction (CO)2+H2＝CO+H2O) is an endothermic reaction, with high temperatures favoring the generation of CO, typically in the range of 400-600 ℃. When the temperature is higher than 600 ℃, the energy consumption is very high, and the reaction economy is poor. The reverse water gas shift reaction is an isometric reaction, so the pressure has little influence on the reaction, but in order to increase the reaction rate, a certain pressure is increased appropriately. In order to increase the selectivity of CO, the side reactions are greatly suppressed.
The main side reaction of the reverse water gas shift reaction is CO2Methanation (CO)2+4H2＝CH4+2H2O). CO suppression2The methanation side reaction is mainly started from the following aspects: a) temperature, which is a strongly exothermic reaction, increases the temperature, moving the equilibrium to the left, high temperature being beneficial for CO suppression2Methanation; b) pressure, which is a volume reduction reaction, increasing pressure, balancing right, high pressure favoring CO2Carrying out methanation side reaction; (c) the hydrogen-carbon ratio is reduced, the methane selectivity is reduced, and the inhibition of CO is facilitated2And (4) carrying out methanation reaction.
The catalyst for reverse water gas shift mainly includes copper-base catalyst, nickel-base catalyst, noble metal catalyst, other new catalytic material, etc. Copper-based catalysts are not suitable for high temperature reactions because of their poor thermal stability, tendency to sinter and oxidize [ see appl. Catal. A: Gen.2004,257,97-106]. Since the Ni-based catalyst is usually used as a methanation catalyst, CH as a by-product is easily produced when it is used as a reverse water gas shift catalyst4The use of Ni, a metal element, should be avoided. Noble metal catalysts are expensive and tend to be deactivated by sintering at high temperatures.
CO is converted by Reverse Water Gas Shift (RWGS)2Conversion to CO is a CO with great potential for use2And (5) a conversion and utilization process. Early research reports that Fe-Cr oxide catalyst is used for the reaction, but the disadvantages are that the methanation side reaction is serious, and in addition, the addition of Cr element has negative influence on the environment. WO9606064A1 adopts Zn-Cr/Al2O3Both the catalyst and EP2175986a2, which employ chromium-alumina catalysts, suffer from the disadvantages described above.
US20130150466A1 in its examples, CO at 560 ℃ C2The conversion rate reaches 62.9 percent, but by-product CH is not given4The content of (a).
Ja Hun KWak et Al reported monodisperse Pd/Al2O3Reverse water gas shift catalyst, indicating that the function of Pd is to activate dissociation H2While the carrier alumina is used for activating and adsorbing CO2Can also activate CO by adding La2But the cost is higher because noble metal is adopted as an active component [ see ACS Catal.2013,3,2094-]。
European patents EP742172 and EP737647 propose a process for the preparation of a catalyst containing CO and CO by steam reforming of methane2And H2In the process of the synthesis gas, water generated by the reverse water gas shift reaction is removed by adopting an adsorbent, and the method needs stages of adsorption, pressure reduction, regeneration and the like, and has more complex steps.
Chinese patent CN107552056A proposes that Ti or Zr, alkaline earth metal elements, Fe and other precursor salts are prepared into CO by adopting a coprecipitation method2The highest CO selectivity obtained in the embodiment of the conversion catalyst is 96-98%, and the CO selectivity needs to be further improved by optimizing the active phase of the catalyst.
Chinese patent CN101624186B proposes a two-stage reverse water-gas shift reaction process, which adopts a catalyst loaded with at least two elements of Co, Ni, W and Mo, and CO2The total conversion can reach 80%, but the reaction temperature is higher than 580 ℃, CO selectivity and methane condition are not given, and side reaction leads to H2The consumption is large and the economy is poor.
In view of the above, there is a need to develop a method for increasing CO2Novel catalysts for conversion and CO selectivity.
Disclosure of Invention
In view of the problems in the prior art, the present invention aims to provide a catalyst for preparing carbon monoxide by catalytic conversion of carbon dioxide, a preparation method and an application thereof. By using a composite metal oxide containing a specific kind of metal element and having a specific crystal phase structure as a catalyst, higher CO can be obtained at the same time2Conversion and CO selectivity.
The invention provides a catalyst for preparing carbon monoxide by catalytic conversion of carbon dioxide, which comprises a composite metal oxide, wherein the composite metal oxide comprises Ba element, Zr element and other elements, and the other elements are selected from at least one of Zn, Cu, Fe, Co, Ni and Mn.
The inventors of the present application have found through studies that a composite metal oxide including a Ba element, a Zr element and at least one element selected from Zn, Cu, Fe, Co, Ni, Mn belongs to a Zr composite metal oxide having a typical ABO3Cubic fluorite type perovskite structure, and composite metal oxide is homogeneousAn active phase of one, no other free impurity phase. In addition, in the composite metal oxide, the content of the active phase accounts for 99-100% of the total mass of the composite metal oxide. Because the composite metal oxide contains specific metal elements and has a specific crystal phase structure, when the composite metal oxide is used as a catalyst for preparing carbon monoxide by catalytic conversion of carbon dioxide, higher CO can be obtained simultaneously2Conversion and CO selectivity.
According to the invention, the catalyst is of monolithic type, the higher the proportion of the active phase in the catalyst, the higher the activity of the catalyst, the higher the proportion of the active phase in the catalyst is calculated by XRD spectrum, in particular, by cubic perovskite structure ABO3The main characteristics are the intensity of XRD line and the diffraction peak intensity of XRD line of impurity diffraction peak. The calculation formula of the ratio of the active phase in the catalyst is shown as the formula (1).
In some preferred embodiments of the present invention, the molar content of the Zr element is 0.8 to 0.99 mol, preferably 0.9 to 0.99 mol, and the molar content of the other elements is 0.01 to 0.2 mol, preferably 0.01 to 0.1 mol, based on 1 mol of the Ba element.
In some preferred embodiments of the present invention, the complex metal oxide has ABO3-δThe structure of the cubic fluorite type perovskite structure is shown in the specification, wherein delta refers to the oxygen vacancy defect amount, and the value of delta is preferably 0.01-0.1.
Generally, the oxygen species in the composite oxide are typically active centers for redox reactions, and the composite oxide includes lattice oxygen and surface oxygen. At medium and low temperature reaction conditions, surface oxygen plays a major role. Under medium-high temperature reaction conditions, bulk lattice oxygen plays a major role. According to literature reports, for CO2The activation requires higher activation energy, and a surface or bulk phase doping technology is usually adopted, so that the composite oxide generates certain lattice oxygen defects to promote CO2And (4) activating. Doping of perovskite oxide with ionsMismatch with the charge and radius of the bulk ion, resulting in a certain amount of oxygen vacancies being generated by the perovskite catalyst due to charge balance. Through doping, the crystal lattice is rich in more oxygen vacancies and better oxidation-reduction property, and reduction treatment is carried out before reaction, so that the oxygen migration of crystal lattices can be further improved, and active crystal lattice oxygen vacancies are generated.
In the invention, Raman is adopted to carry out indirect test, the intensity of the generated distortion peak represents the content of oxygen defects, and the stronger the distortion peak is, the more oxygen defects are represented. The oxygen defect content delta is indirectly expressed by the Raman distortion peak intensity at 635 wave number, and the calculation formula is shown as formula (2).
CO2The carbon dioxide is a weak acid molecule, is easily adsorbed by basic ions, is further polarized by adjacent crystal lattice oxygen vacancies, weakens or even breaks C ═ O bonds, is filled into crystal lattice oxygen by dissociative oxygen, and CO is desorbed and diffused into a gas phase body due to weak adsorption. The catalyst used in the invention can be used for converting carbon dioxide into carbon monoxide by hydrogenation, and the reaction equation is shown as formula (3).
CO2+H2+ catalyst → CO + H2O + catalyst type (3)
According to the present invention, in one embodiment of the present invention, the catalyst may be represented by general formula (4):
BaZr1-xMexO3-δformula (4)
In the formula (4), Me represents other elements, and x ranges from 0.01 to 0.2.
In another aspect of the present invention, a preparation method of the catalyst is provided, which includes:
a) providing a salt solution containing said Ba element, Zr element and other elements;
b) gelatinizing the salt solution under the action of a precipitator to generate gel;
c) diluting the gel, and enabling the diluted gel to generate a precipitate under the action of a precipitating agent;
d) and roasting the precipitate to obtain the catalyst.
According to the invention, the precipitant is not particularly limited, and in a specific embodiment of the invention, the precipitant is an ammonium carbonate solution having a mass concentration of 25 wt% to 35 wt%.
According to the invention, in step b), the precipitant is added into the salt solution at a rotation speed of 280-350 rpm and a dropping speed of 1-5 drops/second; in step c), the precipitant is added to the diluted gel at a rotation speed of 350-450 rpm and a dropping speed of 5-15 drops/second.
According to the present invention, the generated precipitate can be separated from the solution by a solid-liquid separation method which is conventional in the art, for example, in a specific embodiment of the present invention, the precipitate is obtained by suction filtration, and after suction filtration, the precipitate is washed and dried for subsequent calcination treatment.
In some preferred embodiments of the present invention, the procedure of the calcination treatment is:
at a first temperature rise rate, raising the temperature from room temperature to a first intermediate temperature, and keeping the temperature at the first intermediate temperature for 1h-5 h;
then, at a second temperature rising rate, raising the temperature from the first intermediate temperature to a second intermediate temperature, and keeping the temperature at the second intermediate temperature for 1h-6 h;
and then raising the temperature from the second intermediate temperature to the target temperature at a third temperature raising rate, and keeping the temperature at the target temperature for 1h-6 h.
In some preferred embodiments of the present invention, the first ramp rate is from 120 ℃/h to 180 ℃/h, and the first intermediate temperature is from 500 ℃ to 600 ℃; and/or
The second heating rate is 60 ℃/h-120 ℃/h, and the second intermediate temperature is 850-1000 ℃; and/or
The third heating rate is 30-60 ℃/h, and the target temperature is 1100-1200 ℃.
In some preferred embodiments of the present invention, the catalyst is subjected to a methanol-hydrothermal treatment under conditions comprising: the temperature of the methanol-water heat treatment is 150-220 ℃, the time is 12-48 h, and the mass ratio of the methanol to the water is 1:9-4: 6.
The invention further provides application of the catalyst or the catalyst prepared by the preparation method in the field of preparing carbon monoxide by catalytic conversion of carbon dioxide.
In another aspect, the present invention provides a method for preparing carbon monoxide by catalytic conversion of carbon dioxide, comprising: a raw material gas containing carbon dioxide and hydrogen is contacted with the above-described catalyst or the catalyst produced according to the above-described production method under reaction conditions to produce carbon monoxide and steam.
According to the invention, the mixed gas of carbon monoxide and water vapor from the outlet of the catalyst bed layer is cooled, so that the water vapor is completely condensed into water, and then the water and the gas carbon monoxide are obtained through a gas-liquid separator.
In some preferred embodiments of the present invention, the volume ratio of carbon dioxide to hydrogen in the feed gas is (1-3): 1.
In some preferred embodiments of the present invention, the reaction conditions include: the reaction temperature is 500-700 ℃, and the reaction pressure is 0.5-3.0 MPa.
The method can fully convert greenhouse gas carbon dioxide into synthesis gas rich in carbon monoxide and hydrogen, and is used for synthesizing carbon-raw material gas of downstream chemical products. In addition, the method of the invention is adopted to prepare carbon monoxide and CO2High conversion rate and high CO selectivity.
Drawings
Fig. 1 is an XRD pattern of the catalysts prepared in example 1, example 3 and comparative example 1.
Fig. 2 is a Raman spectrum of the catalysts prepared in example 1, example 3, example 5 and comparative example 1.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In the present invention, room temperature means 25 ℃ to 40 ℃ unless otherwise specified.
Example 1
386.4g of zirconium nitrate, 281.4g of barium nitrate, 50g of 50 wt% manganese nitrate aqueous solution and 3000mL of water are weighed, dissolved and stirred at the temperature of 55 ℃ and mixed uniformly to form a salt solution. 384g ammonium carbonate was dissolved in 1000mL water to form a homogeneous precipitant.
The precipitant was added dropwise to the above salt solution under the conditions of a stirring speed of 350 rpm and a dropping speed of 3 drops per second. In the dropping process, after the salt solution is gelatinized, 500mL of water is added, the dropping speed is increased to 10 drops per second, and the stirring speed is increased to 400 r/min until the precipitating agent is dropped completely, so that the solution containing the precipitate is obtained.
After which stirring was continued for 8 hours at a temperature of 55 ℃ to age the precipitate. Standing, cooling to room temperature, performing suction filtration for 3 times, washing after suction filtration to obtain a filter cake, and vacuum drying the filter cake at 110 deg.C for 12 hr.
And finally, roasting the dried filter cake to obtain the catalyst powder. The roasting procedure is as follows: raising the temperature from room temperature to 550 ℃ at a temperature raising rate of 127.5 ℃/h, and then staying for 1 h; then the temperature is raised from 550 ℃ to 900 ℃ at the heating rate of 70 ℃/h and then stays for 1 hour, then the temperature is raised from 900 ℃ to 1200 ℃ at the heating rate of 60 ℃/h and stays for 3 hours, and finally the temperature is naturally reduced to the room temperature.
The catalyst powder is placed in an autoclave for methanol-hydrothermal treatment, specifically, the catalyst powder is treated for 12-24 hours at 200 ℃ under autogenous pressure in a methanol-containing water environment (the mass ratio of methanol to water is 1: 9), and then filtered and dried to obtain the catalyst powder. And (3) granulating the powder, specifically, adjusting a tablet machine by adopting a phi 3-phi 5 mould, and tabletting and forming.
[ catalyst characterization ]: the catalyst was sampled and tested on a D8 advanced type polycrystalline powder diffractometer and an Aramis laser Raman spectrometer from Bruker, Germany, and the results are shown in FIG. 1 and FIG. 2, respectively.
[ catalyst evaluation]: loading the catalyst into a fixed bed reactor, the composition of the gas mixture being CO2＝333ml/min,H2667ml/min catalyst bed was operated at 600 ℃ and 0.5MPa, after reaction, water was separated off by cooling. The evaluation results are shown in Table 1.
Example 2
A catalyst was prepared as in example 1 except that a 50 wt% aqueous solution of manganese nitrate was used in an amount of 25 g. The obtained catalyst was evaluated in the catalyst evaluation manner in example 1, and the evaluation results are shown in table 1.
Example 3
A catalyst was prepared as in example 1 except that 32g of a 50 wt% aqueous solution of ferric nitrate was used in place of the aqueous solution of manganese nitrate in example 1. The catalyst obtained was characterized in the manner described in example 1, and the results are shown in FIGS. 1 and 2, respectively. The obtained catalyst was evaluated in the catalyst evaluation manner in example 1, and the evaluation results are shown in table 1.
Example 4
A catalyst was prepared as in example 1 except that 64g of a 50 wt% aqueous solution of ferric nitrate was used in place of the aqueous solution of manganese nitrate in example 1. The obtained catalyst was evaluated in the catalyst evaluation manner in example 1, and the evaluation results are shown in table 1.
Example 5
A catalyst was prepared as in example 1 except that 92g of a 50 wt% aqueous nickel nitrate solution was used in place of the aqueous manganese nitrate solution in example 1. The catalyst obtained was characterized in the manner described in example 1, and the results are shown in FIG. 2. The obtained catalyst was evaluated in the catalyst evaluation manner in example 1, and the evaluation results are shown in table 1.
Example 6
A catalyst was prepared as in example 1 except that 74g of a 50 wt% aqueous solution of copper nitrate was used in place of the aqueous solution of manganese nitrate in example 1. The obtained catalyst was evaluated in the catalyst evaluation manner in example 1, and the evaluation results are shown in table 1.
Comparative example 1
Weighing 429.3 g of zirconium nitrate, 148 g of magnesium nitrate and 4.1 g of ferric nitrate, respectively dissolving in deionized water, and then uniformly mixing to prepare a mixed salt solution; weighing 250 g of ammonium carbonate to prepare a precipitant solution; uniformly dripping the precipitant solution and the salt solution into a three-neck flask, quickly stirring, controlling the temperature of a water bath to be 60 ℃, adjusting the pH value to be 8, stirring for 12 hours, and standing overnight. And filtering and washing the solution after standing overnight, and then placing a filter cake into a hydrothermal kettle for pure water heat treatment at the treatment temperature of 180 ℃ for 24 hours. Then, the precipitate was filtered and washed again, vacuum-dried at 120 ℃ for 12 hours, and calcined at 800 ℃ for 5 hours.
The catalyst obtained was characterized in the manner described in example 1, and the results are shown in FIGS. 1 and 2, respectively. The obtained catalyst was evaluated in the catalyst evaluation manner in example 1, and the evaluation results are shown in table 1.
Comparative example 2
A catalyst was prepared as in example 1 except that zirconium nitrate was not used.
The obtained catalyst was evaluated in the catalyst evaluation manner in example 1, and the evaluation results are shown in table 1.
Comparative example 3
A catalyst was prepared as in example 1 except that barium nitrate was not used.
The obtained catalyst was evaluated in the catalyst evaluation manner in example 1, and the evaluation results are shown in table 1.
Comparative example 4
A catalyst was prepared as in example 1 except that a 50 wt% aqueous solution of manganese nitrate was not used.
The obtained catalyst was evaluated in the catalyst evaluation manner in example 1, and the evaluation results are shown in table 1.
Comparative example 5
A catalyst was prepared as in example 1 except that 13.7g of lanthanum nitrate was used in place of the 50 wt% aqueous manganese nitrate solution in example 1.
The obtained catalyst was evaluated in the catalyst evaluation manner in example 1, and the evaluation results are shown in table 1.
Comparative example 6
A catalyst was prepared as in example 1 except that 7g of palladium chloride was used in place of the 50 wt% aqueous manganese nitrate solution in example 1.
The obtained catalyst was evaluated in the catalyst evaluation manner in example 1, and the evaluation results are shown in table 1.
TABLE 1
Comparing the data in table 1, it can be seen that the catalyst prepared by the technical scheme of the invention can simultaneously have higher CO2Conversion and CO selectivity.
As can be seen from fig. 1, the lattice oxygen defect contents of examples 1 and 3 are greater than those of comparative example 1. As can be seen from fig. 2, example 1, example 3 and example 5 have more lattice defects than comparative example 1.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A catalyst for preparing carbon monoxide by catalytic conversion of carbon dioxide comprises a composite metal oxide, wherein the composite metal oxide comprises Ba element, Zr element and other elements, and the other elements are selected from at least one of Zn, Cu, Fe, Co, Ni and Mn.
2. The catalyst according to claim 1, wherein the molar content of the Zr element is 0.8 to 0.99 mol, preferably 0.9 to 0.99 mol, and the molar content of the other elements is 0.01 to 0.2 mol, preferably 0.01 to 0.1 mol, based on 1 mol of the Ba element.
3. The catalyst according to claim 1 or 2, wherein the composite metal oxide has ABO3-δThe structure of the cubic fluorite type perovskite structure is shown in the specification, wherein delta refers to the oxygen vacancy defect amount, and the value of delta is preferably 0.01-0.1.
4. A method of preparing the catalyst of any one of claims 1-3, comprising:
a) providing a salt solution containing said Ba element, Zr element and other elements;
b) gelatinizing the salt solution under the action of a precipitator to generate gel;
c) diluting the gel, and enabling the diluted gel to generate a precipitate under the action of a precipitating agent; and
d) and roasting the precipitate to obtain the catalyst.
5. The method according to claim 4, wherein the baking treatment is carried out by a procedure comprising:
at a first temperature rise rate, raising the temperature from room temperature to a first intermediate temperature, and keeping the temperature at the first intermediate temperature for 1h-5 h;
then, at a second temperature rising rate, raising the temperature from the first intermediate temperature to a second intermediate temperature, and keeping the temperature at the second intermediate temperature for 1h-6 h;
and then raising the temperature from the second intermediate temperature to the target temperature at a third temperature raising rate, and keeping the temperature at the target temperature for 1h-6 h.
6. The production method according to claim 5,
the first heating rate is 120 ℃/h-180 ℃/h, and the first intermediate temperature is 500-600 ℃; and/or
The second heating rate is 60 ℃/h-120 ℃/h, and the second intermediate temperature is 850-1000 ℃; and/or
The third heating rate is 30-60 ℃/h, and the target temperature is 1100-1200 ℃.
7. The production method according to claim 5 or 6, characterized in that the catalyst is subjected to a methanol-hydrothermal treatment under conditions including: the temperature of the methanol-water heat treatment is 150-220 ℃, the time is 12-48 h, and the mass ratio of the methanol to the water is 1:9-4: 6.
8. Use of a catalyst according to any one of claims 1 to 3 or a catalyst prepared by a method of preparing a catalyst according to any one of claims 4 to 7 in the field of carbon dioxide catalytic conversion to produce carbon monoxide.
9. A process for the preparation of carbon monoxide by catalytic conversion of carbon dioxide comprising: contacting a feed gas comprising carbon dioxide and hydrogen with a catalyst according to any one of claims 1 to 3 or a catalyst prepared according to the method of preparing a catalyst according to any one of claims 4 to 7 under reaction conditions to produce carbon monoxide and water vapour.
10. The method of claim 9, wherein the volume ratio of carbon dioxide to hydrogen in the feed gas is (1-3): 1; preferably, the reaction conditions include: the reaction temperature is 500-700 ℃, and the reaction pressure is 0.5-3.0 MPa.
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