CN117339587A - Sea urchin-shaped ZnZrOx bimetallic oxide solid solution catalyst, and preparation method and application thereof - Google Patents
Sea urchin-shaped ZnZrOx bimetallic oxide solid solution catalyst, and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 239000006104 solid solution Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 51
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000004202 carbamide Substances 0.000 claims abstract description 49
- 238000003756 stirring Methods 0.000 claims abstract description 37
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 27
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 230000032683 aging Effects 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 6
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims description 37
- 239000011259 mixed solution Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 20
- 239000012018 catalyst precursor Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 238000004448 titration Methods 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 7
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 31
- 239000012065 filter cake Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 238000012216 screening Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000446 fuel Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—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
- C07C29/151—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
- 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
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The application discloses a preparation method and application of a double precipitant of a sea urchin-shaped ZnZrOx solid solution catalyst. The preparation of the solid solution catalyst comprises the following specific steps: dissolving zinc nitrate hexahydrate and zirconium nitrate pentahydrate, then dropwise adding two precipitants of ammonium carbonate and urea step by step, continuously stirring after the dropwise adding is finished, and standing at room temperature for ageing; and cooling the aged product, filtering and washing to obtain solid precipitate, and drying and calcining to obtain the catalyst. The catalyst disclosed by the invention is used for the reaction of synthesizing methanol by hydrogenating carbon dioxide, and can improve the carbon dioxide conversion rate and the methanol selectivity.
Description
Technical Field
The invention relates to the technical field of chemical catalysis, in particular to a sea urchin-shaped ZnZrOx bimetallic oxide solid solution catalyst, and a preparation method and application thereof.
Background
Human activity expansion and industrial development to CO in the atmosphere 2 The concentration of (2) is greatly increased. CO in the atmosphere 2 High content of (2)The global warming, the rain acidification and the like are caused to change in a series of climates, and the ecological balance in the natural world is greatly destroyed. CO is processed by 2 Conversion to high value chemicals is the reduction of atmospheric CO 2 Content effective strategy.
Methanol is a basic organic chemical raw material, and is widely applied to the fields of organic synthesis, medicine, formaldehyde, dye and the like, and the yield is inferior to that of synthetic ammonia and ethylene. Meanwhile, methanol is also an important clean fuel, and the methanol and gasoline or other substances can be mixed to prepare industrial or civil novel fuels with different purposes.
For CO 2 The catalyst for synthesizing methanol by hydrogenation is the Cu-based catalyst, most of researches are to synthesize the CuZnAl catalyst by a coprecipitation method, and an auxiliary agent is added into the catalyst for modification, wherein the best auxiliary agent is the Zr or Ti modified CuZnAl catalyst [ petrochemical industry, 2009,38 (5), 482; fuel chemistry journal 2011,39 (12), 912]But the methanol selectivity of Cu-based catalysts is generally not higher than 60%; and CO 2 The hydrogenation methanol preparation is an exothermic reaction, the Cu-based catalyst is easy to sinter, and the sintering of Cu is aggravated by reaction byproduct water.
Chinese patent CN 111841524A discloses a method for preparing mesoporous ZnO-ZrO 2 Method for preparing mesoporous ZnO-ZrO by using CTAB and PEG2000 double template agent assisted co-current coprecipitation method and application thereof 2 However, under the reaction conditions of 250 ℃, 2MPa and 12000 ml/(g h), CO 2 The conversion of (2) is also only 4.2%. Therefore, the preparation method of the ZnZrOx solid solution catalyst also needs to be explored more to improve the reactivity and the methanol selectivity of the ZnZrOx solid solution catalyst under low pressure (less than or equal to 3 MPa).
Therefore, there is a need to develop a ZnZrOx bimetallic oxide solid solution catalyst for preparing methanol by hydrogenation of carbon dioxide, which has better catalytic performance and high cost performance.
Disclosure of Invention
The invention provides a sea urchin-shaped ZnZrOx bimetallic oxide solid solution catalyst, a preparation method and application thereof, and aims to overcome the defects in the prior art. In order to achieve the aim of the invention, the invention is realized by the following technical scheme:
in a first aspect, the present invention provides a method for preparing a sea urchin-shaped ZnZrOx solid solution catalyst by using a double precipitant, comprising the following steps:
step S1, dissolving zinc nitrate hexahydrate and zirconium nitrate pentahydrate by deionized water to obtain a metal nitrate mixed solution;
step S2, firstly adding an ammonium carbonate aqueous solution into the metal nitrate mixed solution, and stirring to obtain a white suspension; adding urea and stirring; then, aging at room temperature;
step S3, cooling, solid-liquid separating, washing and drying the product obtained in the step S2 to obtain a catalyst precursor;
and S4, calcining the catalyst precursor to obtain the sea urchin-shaped ZnZrOx solid solution catalyst.
Preferably, in step S1, the Zn/(Zn+Zr) value is 8 to 20% by mole.
Preferably, in step S2, the ratio of the total moles of ammonium carbonate to urea to the total moles of metal cations is 1-2.5:1.
Preferably, in step S2, the molar ratio of ammonium carbonate to urea is 23:1 to 1:23.
Preferably, in the step S2, an ammonium carbonate aqueous solution is dropwise added into a metal nitrate mixed solution, a white suspension is obtained after the titration is finished, and the mixture is stirred for 10 to 50 minutes at the reaction temperature of 30 to 90 ℃; then adding urea, heating to 90-95 ℃ and stirring for 10-60 min, then stopping stirring, and aging for 3-5 h at room temperature.
Preferably, in step S3, the washing step is to wash the solid precipitate 3 to 5 times with deionized water.
Preferably, in step S3, the drying temperature in the drying step is 60-120 ℃ and the drying time is 12-20 h.
Preferably, in step S3, the roasting step is carried out at 400-600 ℃ in an air atmosphere, the roasting time is 2-8 h, and the heating rate is 2-10 ℃/min.
In a second aspect, the invention also provides the sea urchin-shaped ZnZrOx solid solution catalyst prepared by the method.
In a third aspect, the invention also provides an application of the sea urchin-shaped ZnZrOx solid solution catalyst, which is used as a catalyst for a process of preparing methanol by hydrogenating carbon dioxide.
Therefore, the invention has the following beneficial effects:
(1) The invention researches the structure of the catalyst prepared by different precipitants, and discovers that ammonium carbonate can rapidly perform precipitation reaction with metal ions, the formed crystal grain size is large, the ion reaction speed of urea and the metal ions is slower, and the formed crystal grain size is small. The invention adopts two precipitants, ammonium carbonate is added for precipitation, urea is added for precipitation, and the formed catalyst is that small grains formed by urea precipitation are attached to large grains formed by ammonium carbonate precipitation, and has a sea urchin-shaped structure. Compared with a catalyst prepared by adopting a single precipitant, the catalyst can simultaneously improve CO in the reaction of synthesizing the methanol by hydrogenating the carbon dioxide 2 Conversion and methanol selectivity.
(2) The two precipitants of ammonium carbonate and urea are adopted, so that the use amount of the precipitants is reduced, the catalytic performance is improved, and the catalyst with high performance ratio can be obtained, thereby saving the cost.
Drawings
Fig. 1 is an XRD spectrum of the catalysts prepared in example 2, comparative example 1 and comparative example 2 of the present invention.
FIG. 2a is an SEM image of the catalyst of example 2 of the present invention.
FIG. 2b is an SEM image of the catalyst of comparative example 1 of the present invention.
FIG. 2c is an SEM image of the catalyst of comparative example 2 of the present invention.
FIG. 3 is H of the catalysts of the invention prepared in example 2, comparative example 1, comparative example 2 and comparative example 3 2 -TPR profile.
Detailed Description
The invention is further described below with reference to the drawings and specific examples. Those of ordinary skill in the art will be able to implement the invention based on these descriptions. In addition, the embodiments of the present invention referred to in the following description are typically only some, but not all, embodiments of the present invention. Therefore, all other embodiments, which can be made by one of ordinary skill in the art without undue burden, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
Example 1:
(1) Zn (NO) was weighed out in a molar ratio Zn/(Zn+Zr) =13% 3 ) 2 ·6H 2 O1.64 g (molecular weight 297.51,5.5 mmol) and Zr (NO) 3 ) 4 ·5H 2 15.85g (molecular weight 423.56, 37.4 mmol) of O is dissolved in deionized water to obtain a metal nitrate mixed solution, and the mixed solution is heated, stirred and dissolved at 60 ℃ until the solid is completely dissolved and mixed, wherein the stirring speed is 300r/min;
(2) In a molar ratio (Zn+Zr) ((NH) 4 ) 2 CO 3 +urea) =1:1.94, (NH 4 ) 2 CO 3 Urea=20:4 (NH 4 ) 2 CO 3 6.59g and urea 0.82g, 6.59g (NH 4 ) 2 CO 3 Dissolving in deionized water, and completely dissolving;
(3) Firstly, dropwise adding an ammonium carbonate aqueous solution into a metal nitrate mixed solution, obtaining a white suspension after titration, adding 0.82g of urea, continuously stirring for 30min at 60 ℃, then heating to 90 ℃, stirring for 30min, stopping stirring, and aging for 3h at room temperature;
(4) Cooling and filtering the aged product, washing the obtained filter cake with deionized water for 3 times, and then putting the filter cake into a blast drying oven for drying at 70 ℃ for 16 hours to obtain a catalyst precursor;
(5) And (3) placing the catalyst precursor into a muffle furnace, calcining for 5 hours at 500 ℃ in an atmospheric air atmosphere, heating at a rate of 8 ℃/min to obtain white powder, tabletting, crushing and screening the powder to obtain the required granular catalyst, and marking the catalyst as the catalyst 1.
Example 2:
(1) Zn (NO) was weighed out in a molar ratio Zn/(Zn+Zr) =13% 3 ) 2 ·6H 2 O1.64 g and Zr (NO) 3 ) 4 ·5H 2 15.85g of O is dissolved in deionized water to obtain metal nitrate mixtureHeating, stirring and dissolving the solution at 60 ℃ until the solid is completely dissolved and mixed, wherein the stirring speed is 300r/min;
(2) In a molar ratio (Zn+Zr) ((NH) 4 ) 2 CO 3 +urea) =1:1.94, (NH 4 ) 2 CO 3 Urea=16:8 (NH 4 ) 2 CO 3 5.27g and urea 1.64g, 5.27g (NH 4 ) 2 CO 3 Dissolving in deionized water, and completely dissolving;
(3) Firstly, dropwise adding an ammonium carbonate aqueous solution into a metal nitrate mixed solution, obtaining a white suspension after titration, adding 1.64g of urea, continuously stirring for 30min at 60 ℃, then heating to 90 ℃, stirring for 30min, stopping stirring, and aging for 3h at room temperature;
(4) Cooling and centrifugally separating the aged product, washing the filter cake with deionized water for 3 times, and then putting the filter cake into a blast drying oven for drying at 70 ℃ for 16 hours to obtain a catalyst precursor;
(5) And (3) placing the catalyst precursor into a muffle furnace, calcining for 5 hours at 500 ℃ in an atmospheric air atmosphere, heating at a rate of 8 ℃/min to obtain white powder, tabletting, crushing and screening the powder to obtain the required granular catalyst, and marking the catalyst as the catalyst 2.
Example 3:
(1) Zn (NO) was weighed out in a molar ratio Zn/(Zn+Zr) =16% 3 ) 2 ·6H 2 O2.01 g and Zr (NO) 3 ) 4 ·5H 2 15.30g of O is dissolved in deionized water to obtain a metal nitrate mixed solution, and the mixed solution is heated and stirred at 60 ℃ until the solid is completely dissolved and mixed, wherein the stirring speed is 300r/min;
(2) In a molar ratio (Zn+Zr) ((NH) 4 ) 2 CO 3 +urea) =1:1.94, (NH 4 ) 2 CO 3 Urea=16:8 (NH 4 ) 2 CO 3 5.27g and urea 1.64g, 5.27g (NH 4 ) 2 CO 3 Dissolving in deionized water, and completely dissolving;
(3) Firstly, dropwise adding an ammonium carbonate aqueous solution into a metal nitrate mixed solution, obtaining a white suspension after titration, adding 1.64g of urea, continuously stirring for 30min at 60 ℃, then heating to 90 ℃, stirring for 30min, stopping stirring, and aging for 3h at room temperature;
(4) Cooling and filtering the aged product, washing the obtained filter cake with deionized water for 3 times, and then putting the filter cake into a blast drying oven for drying at 70 ℃ for 16 hours to obtain a catalyst precursor;
(5) And (3) placing the catalyst precursor into a muffle furnace, calcining for 5 hours at 500 ℃ in an atmospheric air atmosphere, heating at a rate of 8 ℃/min to obtain white powder, tabletting, crushing and screening the powder to obtain the required granular catalyst, and marking the catalyst as a catalyst 3.
Comparative example 1:
(1) Zn (NO) was taken at a molar ratio Zn/(Zn+Zr) =13% 3 ) 2 ·6H 2 O1.64 g and Zr (NO) 3 ) 4 ·5H 2 15.85g of O is dissolved in deionized water to obtain a metal nitrate mixed solution, and the mixed solution is heated and stirred at 60 ℃ until the solid is completely dissolved and mixed, wherein the stirring speed is 300r/min;
(2) In a molar ratio (Zn+Zr) ((NH) 4 ) 2 CO 3 +urea) =1:1.94, (NH 4 ) 2 CO 3 Urea=24:0 (NH 4 ) 2 CO 3 7.91g of the solution is dissolved in deionized water to obtain a precipitant solution;
(3) Dropwise adding an ammonium carbonate aqueous solution into the metal nitrate mixed solution, obtaining a white suspension after titration, continuously stirring for 30min at 60 ℃, then heating to 90 ℃, stirring for 30min, stopping stirring, and aging for 3h at room temperature;
(4) Cooling and filtering the aged product, washing the obtained filter cake with deionized water for 3 times, and then putting the filter cake into a blast drying oven for drying at 70 ℃ for 16 hours to obtain a catalyst precursor;
(5) And (3) placing the catalyst precursor into a muffle furnace, calcining for 5 hours at 500 ℃ in an atmospheric air atmosphere, heating at a rate of 8 ℃/min to obtain white powder, tabletting, crushing and screening the powder to obtain the required granular catalyst, and marking the catalyst as a reference catalyst 1.
The difference between the preparation methods of comparative example 1 and example 2 is that a single precipitant, ammonium carbonate, was used without urea addition.
Comparative example 2:
(1) Zn (NO) was weighed out in a molar ratio Zn/(Zn+Zr) =13% 3 ) 2 ·6H 2 O1.64 g and Zr (NO) 3 ) 4 ·5H 2 15.85g of O is dissolved in deionized water to obtain a metal nitrate mixed solution, and the mixed solution is heated and stirred at 60 ℃ until the solid is completely dissolved and mixed, wherein the stirring speed is 300r/min;
(2) In a molar ratio (Zn+Zr) ((NH) 4 ) 2 CO 3 +urea) =1:1.94, (NH 4 ) 2 CO 3 Urea=0:24 urea 4.94g was weighed and dissolved in deionized water;
(3) Dropwise adding the urea aqueous solution into the metal nitrate mixed solution, heating to 90 ℃ after titration, continuously stirring for 2 hours, stopping stirring, and aging for 3 hours at room temperature;
(4) Cooling the aged product, filtering, washing the filter cake with deionized water for 3 times, and then putting the filter cake into a blast drying oven for drying at 70 ℃ for 16 hours to obtain a catalyst precursor;
(5) And (3) placing the catalyst precursor into a muffle furnace, calcining for 5 hours at 500 ℃ in an atmospheric air atmosphere, heating at a rate of 8 ℃/min to obtain white powder, tabletting, crushing and screening the powder to obtain the required granular catalyst, and marking the catalyst as a reference catalyst 2.
Comparative example 2 differs from the preparation of example 2 in that urea, a single precipitant, was used, without the addition of ammonium carbonate.
Comparative example 3:
(1) Zn (NO) was weighed out in a molar ratio Zn/(Zn+Zr) =13% 3 ) 2 ·6H 2 O1.64 g and Zr (NO) 3 ) 4 ·5H 2 15.85g of O is dissolved in deionized water to obtain a metal nitrate mixed solution, and the mixed solution is heated and stirred at 60 ℃ until the solid is completely dissolved and mixed, wherein the stirring speed is 300r/min;
(2) In a molar ratio (Zn+Zr) ((NH) 4 ) 2 CO 3 +urea) =1:1.94, (NH 4 ) 2 CO 3 Urea=16:8 is weighed separately(NH 4 ) 2 CO 3 5.27g and 1.64g of urea, firstly adding 1.64g of urea into the metal nitrate mixed solution, stirring at 90 ℃ for 2 hours, and then cooling to 60 ℃;
(3) 5.27g (NH) 4 ) 2 CO 3 Dissolving in deionized water, dripping into the mixed solution after completely dissolving, obtaining white suspension after titration, continuously stirring for 1h at 60 ℃, stopping stirring, and aging for 3h at room temperature;
(4) Cooling and filtering the aged product, washing the obtained filter cake with deionized water for 3 times, and then putting the filter cake into a blast drying oven for drying at 70 ℃ for 16 hours to obtain a catalyst precursor;
(5) And (3) placing the catalyst precursor into a muffle furnace, calcining for 5 hours at 500 ℃ in an atmospheric air atmosphere, heating at a rate of 8 ℃/min to obtain white powder, tabletting, crushing and screening the powder to obtain the required granular catalyst, and marking the catalyst as a reference catalyst 3.
Comparative example 3 differs from the preparation method of example 2 in that the order of addition of the two precipitants is different.
Comparative example 4:
(1) Zn (NO) was weighed out in a molar ratio Zn/(Zn+Zr) =16% 3 ) 2 ·6H 2 O2.01 g and Zr (NO) 3 ) 4 ·5H 2 15.30g of O is dissolved in deionized water to obtain a metal nitrate mixed solution, and the mixed solution is heated and stirred at 60 ℃ until the solid is completely dissolved and mixed, wherein the stirring speed is 300r/min;
(2) In a molar ratio (Zn+Zr) ((NH) 4 ) 2 CO 3 +urea) =1:1.94, (NH 4 ) 2 CO 3 Urea=24:0 (NH 4 ) 2 CO 3 7.91g of the solution is dissolved in deionized water to obtain a precipitant solution;
(3) Dropwise adding an ammonium carbonate aqueous solution into the metal nitrate mixed solution, obtaining a white suspension after titration, continuously stirring at 60 ℃ for 1h, stopping stirring, and aging at room temperature for 3h;
(4) Cooling and filtering the aged product, washing the obtained filter cake with deionized water for 3 times, and then putting the filter cake into a blast drying oven for drying at 70 ℃ for 16 hours to obtain a catalyst precursor;
(5) And (3) placing the catalyst precursor into a muffle furnace, calcining for 5 hours at 500 ℃ in an atmospheric air atmosphere, heating at a rate of 8 ℃/min to obtain white powder, tabletting, crushing and screening the powder to obtain the required granular catalyst, and marking the catalyst as a reference catalyst 4.
Comparative example 4 differs from the preparation of example 3 in that a single precipitant, ammonium carbonate, was used, without the addition of urea.
The catalyst 1, the catalyst 2, the catalyst 3, the reference catalyst 1, the reference catalyst 2, the reference catalyst 3 and the reference catalyst 4 are all subjected to CO under the same reaction condition 2 The hydrogenation reaction performance test comprises the following specific reaction conditions: mixing 0.3g of catalyst and 1.2g of quartz sand, loading into a fixed bed reactor, and firstly, at 400 ℃ and normal pressure H 2 Reducing in gas for 5h, and CO at 320 deg.C, 3.0MPa, 40mL/min 2 :N 2 :H 2 Sample analysis after 24 hours of reaction in a mixture of =23:8:69 (volume ratio), and the results of the reaction performance test of the catalyst are shown in table 1.
Comparative example 1 and comparative example 2 differ from the preparation method of example 2 in that a single precipitant is used. As can be seen from the data in Table 1, when the same Zn/(Zn+Zr), (Zn+Zr): precipitants were used, (NH) was used as compared with the single precipitant samples (comparative examples 1 and 2) 4 ) 2 CO 3 And the catalyst prepared by the urea double precipitant has better CO 2 The conversion rate and the methanol selectivity of the catalyst are improved, and the methanol yield is increased.
Comparative example 4 differs from the preparation of example 3 in that a single precipitant is used. As can be seen from the data in Table 1, when the same Zn/(Zn+Zr), (Zn+Zr) precipitants were used, as compared with the single precipitant sample (comparative example 4), the (NH) 4 ) 2 CO 3 And the catalyst prepared by the urea double precipitant has better CO 2 Conversion rate and methanol selectivity of (C) are improvedMethanol yield.
Comparative example 3 and example 2 both employed dual precipitants, but the order of addition of the two precipitants was different. As can be seen from the data in Table 1, the (NH 4 ) 2 CO 3 The use sequence of the post urea is beneficial to improving the reaction performance of the catalyst.
Figure 1 is an XRD spectrum of the catalysts of the examples and comparative examples. As can be seen from the figure, no phase state of ZnO was detected in the samples, indicating that ZnO was in ZrO 2 The inside is highly dispersed, and the prepared catalyst has a solid solution structure. According to the aspect ratio of diffraction peaks, the grain size in the catalyst in which the precipitant is urea is small (comparative example 2), and the grain size in the catalyst in which the precipitant is ammonium carbonate is large (comparative example 1).
Fig. 2a, 2b and 2c are SEM spectra of the catalysts prepared in example 2 and comparative examples 1 and 2. It can be seen from the figure that at the same magnification, the particles of the catalyst prepared with ammonium carbonate as single precipitant (comparative example 1) spread over the whole SEM field of view, the particles of the catalyst prepared with urea as single precipitant (comparative example 2) were very small, with a diameter of about 1.5um, and the catalyst with ammonium carbonate and urea as precipitant (example 2) combined in a structure of large and small grains to form particles (example 2).
FIG. 3 is a schematic representation of H for the catalysts of the examples and comparative examples 2 -TPR profile. As can be seen from the figure, the catalyst prepared from urea as a single precipitant (comparative example 2) is most easily reduced, the catalyst prepared from ammonium carbonate as a single precipitant (comparative example 1) is more difficult to reduce, and the catalyst prepared from ammonium carbonate and urea as a precipitant (example 2) is reduced to the greatest extent, forms more active centers, and thus has higher catalytic reaction performance. The catalyst (comparative example 3) in which the precipitant is urea and ammonium carbonate is reduced with greater difficulty.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core concept, and it should be pointed out that it is possible for a person skilled in the art to make several improvements and modifications without departing from the principle of the invention, which also falls within the scope of protection of the claims of the present invention.
Claims (10)
1. The method for preparing the sea urchin-shaped ZnZrOx solid solution catalyst by adopting the double precipitants is characterized by comprising the following steps of:
step S1, dissolving zinc nitrate hexahydrate and zirconium nitrate pentahydrate by deionized water to obtain a metal nitrate mixed solution;
step S2, firstly adding an ammonium carbonate aqueous solution into the metal nitrate mixed solution, and stirring to obtain a white suspension; adding urea and stirring; then, the mixture was aged at room temperature,
step S3, cooling, solid-liquid separating, washing and drying the product obtained in the step S2 to obtain a catalyst precursor;
and S4, calcining the catalyst precursor to obtain the sea urchin-shaped ZnZrOx solid solution catalyst.
2. The method for preparing a sea urchin-like ZnZrOx solid solution catalyst according to claim 1, wherein in step S1, the Zn/(zn+zr) value is 8 to 20% on a molar basis.
3. The method for preparing the sea urchin-shaped ZnZrOx solid solution catalyst by adopting the double precipitants according to claim 1, which is characterized in that: in the step S2, the ratio of the total mole number of the ammonium carbonate to the urea to the total mole number of the metal cations is 1-2.5:1.
4. A method for preparing a sea urchin-like ZnZrOx solid solution catalyst using a dual precipitant according to claim 3, wherein: in the step S2, the molar ratio of the ammonium carbonate to the urea is 23:1-1:23.
5. The method for preparing the sea urchin-shaped ZnZrOx solid solution catalyst by adopting the double precipitants according to claim 1, which is characterized in that: in the step S2, dropwise adding an ammonium carbonate aqueous solution into a metal nitrate mixed solution, obtaining a white suspension after titration, and stirring for 10-50 min at a reaction temperature of 30-90 ℃; then adding urea, heating to 90-95 ℃ and stirring for 10-60 min, then stopping stirring, and aging for 3-5 h at room temperature.
6. The method for preparing the sea urchin-shaped ZnZrOx solid solution catalyst by adopting the double precipitants according to claim 1, which is characterized in that: in the step S3, the washing step is to wash the solid precipitate 3-5 times with deionized water.
7. The method for preparing the sea urchin-shaped ZnZrOx solid solution catalyst by adopting the double precipitants according to claim 1, which is characterized in that: in the step S3, the drying temperature in the drying step is 60-120 ℃ and the drying time is 12-20 h.
8. The method for preparing the sea urchin-shaped ZnZrOx solid solution catalyst by adopting the double precipitants according to claim 1, which is characterized in that: in the step S3, the roasting step is carried out at 400-600 ℃ in air atmosphere, the roasting time is 2-8 h, and the heating rate is 2-10 ℃/min.
9. A sea urchin-like ZnZrOx solid solution catalyst prepared by the method of any one of claims 1-8.
10. The use of the sea urchin-like ZnZrOx solid solution catalyst according to claim 9, as a catalyst in a process for preparing methanol by hydrogenation of carbon dioxide.
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