CN110586064B - Lithium-doped zirconium oxide loaded indium oxide catalyst and preparation method and application thereof - Google Patents
Lithium-doped zirconium oxide loaded indium oxide catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of supported oxide catalysts, and discloses a lithium-doped zirconia supported indium oxide catalyst, a preparation method and application thereof, wherein the catalyst is prepared by bulk phase doping of zirconia by lithium atoms through a coprecipitation method to obtain a carrier, and indium oxide particles are uniformly loaded on a lithium-doped monoclinic zirconia carrier; during preparation, firstly, adding lithium and zirconium precursors by a coprecipitation method, and precipitating, drying and roasting to obtain a lithium-doped monoclinic zirconia carrier; and then loading indium oxide on the carrier by a wet impregnation method, and drying and roasting again to obtain the final catalyst. The catalyst prepared by the invention is suitable for the reaction of preparing methanol by hydrogenating carbon dioxide, the lithium-doped zirconium oxide is used as a carrier, and the indium oxide is used as an active component, so that the conversion rate of carbon dioxide of more than 10 percent and the selectivity of methanol of about 90 percent are realized, and the catalyst has the characteristics of simple structure, convenient preparation and low operation pressure, and simultaneously, the series of catalysts also keep long-term stability.
Description
Technical Field
The invention belongs to the technical field of supported oxide catalysts, and particularly relates to a lithium-doped zirconia supported indium oxide catalyst, a preparation method thereof and application of the catalyst in efficiently generating methanol in carbon dioxide hydrogenation.
Background
At present, a large amount of carbon dioxide discharged due to industrial production causes serious global greenhouse effect, and damages the global environment and sustainable development of human beings, so that the research on carbon dioxide emission reduction and conversion utilization technology becomes a problem to be solved urgently. The carbon dioxide hydrogenation technology developed by utilizing solar energy to hydrolyze water to produce hydrogen is beneficial to reducing the concentration of carbon dioxide in the atmosphere, can also generate high-efficiency fuels such as carbon monoxide, methane, methanol, dimethyl ether, ethanol, hydrocarbons and the like, and is convenient to store and transport. Wherein, the generated methanol is easier in thermodynamics and kinetics, and the methanol is used for preparing gasoline and diesel oil and C by preparing olefin from methanol 2 -C 4 The raw material of high-grade olefin is also an important raw material for preparing various fine chemicals such as medicines, cosmetics, polyesters and the like; in addition, methanol is a clean and efficient high-heat fuel,can be used as a gasoline additive, and therefore the catalytic conversion of carbon dioxide to a methanol product is of more interest.
Due to CO 2 The conversion rate of the reaction is generally low due to stable chemical properties and difficult activation, while the generation of methanol is an exothermic reaction, and the low temperature in thermodynamics is favorable for methanol production but not favorable for carbon dioxide activation, so that a proper reaction temperature needs to be selected and a high-efficiency catalyst needs to be designed; on the other hand, carbon monoxide and methanol are two concomitant products in the carbon dioxide hydrogenation reaction, the two products have similar intermediates, and the reaction is carried out on the same catalytic site, so that the selectivity of the two products is not high; how to design high-efficiency catalyst for kinetic control to promote CO 2 Activating conversion and regulating product selectivity, so as to efficiently obtain methanol is a problem to be solved.
At present, the widely researched methanol synthesis catalyst is a copper-zinc-aluminum catalyst, the conversion rate of carbon dioxide of the catalyst is high, but the selectivity of methanol is only about 60%, and the cost of the subsequent separation step is high; in addition, metallic copper is easily sintered and deactivated under high temperature reaction conditions, and reaction stability is lowered. Meanwhile, an oxide catalyst represented by indium oxide can realize 90% of methanol selectivity, can reduce the cost of a subsequent separation process, and has a stable high-temperature structure and low probability of deactivation, so that the oxide catalyst is more and more attracted by people. It is reported that a generally accepted increase in CO 2 The yield of the hydrogenated methanol has the following regulation paths. Firstly, adjusting the particle size of oxide particles on a supported oxide catalyst; secondly, the electronic property and the adsorption property of the carbon dioxide at the interface of the active oxide and the carrier are adjusted by changing the carrier species, thereby achieving the purpose of changing the product distribution. The above two methods have complex preparation method and are not easy to repeat due to the complex structure of the catalyst and undefined reaction sites, and are easy to be interfered by environmental factors. Indium oxide based catalysts are widely used in carbon dioxide hydrogenation reactions. How to further improve the catalyst to have stronger CO 2 The activation capacity and the stability over a longer period of time, in particular the higher methanol selectivity being CO 2 The research of hydrogenation is focused.
Disclosure of Invention
The invention aims to solve the technical problems of poor selectivity (< 60%) of single products such as methanol and the like and poor catalytic stability of a traditional copper-based catalyst in a carbon dioxide hydrogenation reaction, and provides a lithium-doped zirconia-supported indium oxide catalyst, a preparation method thereof and application thereof in carbon dioxide hydrogenation.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a lithium doped zirconia supported indium oxide catalyst comprising lithium doped monoclinic zirconia (xLi-ZrO) 2 ) The lithium-doped monoclinic zirconia (xLi-ZrO) 2 ) The lithium-doped monoclinic zirconia is prepared by bulk phase doping of zirconia by lithium atoms through a coprecipitation method, wherein the molar doping amount x of lithium ions in the lithium-doped monoclinic zirconia is =5-10%; indium oxide particles are uniformly loaded on the lithium-doped monoclinic zirconia, and the mass percentage of the indium oxide in the lithium-doped monoclinic zirconia is 6-10%.
Further, the lithium-doped monoclinic zirconia is used as a carrier, and the indium oxide is used as a catalytic active component.
Further, the particle size range of the lithium-doped monoclinic zirconia is 50-100 nanometers.
Further, the indium oxide particles have a particle size in the range of 8 to 15 nm.
A preparation method of the lithium-doped zirconia supported indium oxide catalyst comprises the following steps:
(1) Zirconium oxychloride octahydrate (ZrOCl) 2 ·8H 2 O) and lithium nitrate (LiNO) 3 ) Dissolving in deionized water at a certain ratio to form a mixed solution with a concentration of 0.2-1M/L, and heating the mixed solutionTo 50-90 ℃;
(2) Continuously stirring the mixed solution obtained in the step (1), and dropwise adding strong ammonia water (NH) into the mixed solution 3 ·H 2 O, the mass concentration is 22-25%), until the pH value of the mixed solution reaches 8-10;
(3) Aging the mixed solution obtained in the step (2) at 50-90 ℃ for 1-3h, centrifuging and washing the obtained suspension, and drying in vacuum; then roasting for 2-6h at 300-500 ℃ to obtain xLi-ZrO 2 A support, x =5-10%, wherein x represents the molar doping amount of lithium ions in the lithium-doped monoclinic zirconia;
(4) Mixing indium nitrate (In (NO) hydrate 3 ) 3 ·H 2 O) is dissolved in deionized water to form a solution with the concentration of 0.4-1M/L, and the solution is dripped into the prepared xLi-ZrO 2 On the carrier, ensuring the mass fraction of the loaded indium oxide to be 6-10%; performing ultrasonic treatment, drying, and roasting at 300-500 deg.C for 4-6h to obtain In 2 O 3 /xLi-ZrO 2 Catalyst, x =5-10%.
Further, the speed of dripping the concentrated ammonia water in the step (2) is 20-50 drops/min.
Further, the temperature of vacuum drying in the step (3) is 80-100 ℃, and the time is 8-12h.
Further, the ultrasonic treatment time in the step (4) is 1-3h, the vacuum drying temperature is 80-100 ℃, and the time is 8-12h.
An application of the lithium-doped zirconia supported indium oxide catalyst is used for preparing methanol by carbon dioxide hydrogenation.
Further, the method comprises the following steps:
(1) Tabletting and granulating the lithium-doped zirconium oxide loaded indium oxide catalyst;
(2) The granular catalyst prepared by the method is subjected to high-pressure continuous reaction in reaction gas at the reaction temperature of 250-350 ℃.
The beneficial effects of the invention are:
the invention takes zirconia loaded with indium oxide as a main component, and can prepare a series of zirconia loaded indium oxide-based catalysts with different crystal forms by changing the doping amount of lithium element (Li).
In one aspect, a small amount of Li-doped zirconia-supported ZrO 2 (Li: zr =5: 95-10) exhibits a particle structure, zirconia being mainly monoclinic; the monoclinic zirconium oxide and the indium oxide are matched in energy band structure, and have strong electronic interaction, namely, the zirconium oxide can transfer electrons to the indium oxide, and the electron-rich indium oxide is beneficial to activation of carbon dioxide and bond breaking of carbon-oxygen bonds. Thus, catalysts obtained after loading indium oxide on monoclinic zirconia, e.g. In 2 O 3 /5Li-ZrO 2 The catalyst has good effect on the carbon dioxide hydrogenation reaction, the carbon dioxide conversion rate is higher than 10%, the methanol selectivity reaches 88%, and the catalyst has good stability.
On the other hand, after studying the structure and catalytic performance of the catalyst outside the optimum Li-doping range, it was also found that ZrO was a zirconia support without Li-doping 2 With excess Li (Li: zr)>20: 40Li-ZrO 2 (Li: zr = 40) has a particle structure, but its crystal structure is mainly tetragonal, and tetragonal zirconia and indium oxide do not have an electronic interaction because of the mismatch of band structures, so that In obtained after the indium oxide is loaded on the carrier is In 2 O 3 /ZrO 2 And In 2 O 3 /40Li-ZrO 2 The catalyst has only a common effect on the carbon dioxide hydrogenation reaction under the low pressure condition, particularly the methanol selectivity is only about 60 percent and is far lower than that of an indium oxide catalyst loaded by monoclinic zirconia, which further proves that the monoclinic zirconia carrier is the key for improving the methanol selectivity.
It can be seen that the crystal form of zirconia is transformed from tetragonal form to monoclinic form with the addition of Li, but when the doping amount of Li is excessive, the crystal form of zirconia is transformed into tetragonal form again. The indium oxide catalysts loaded by the zirconium oxides with different crystal forms have different catalytic performances in the carbon dioxide hydrogenation reaction due to different interactions among the oxides, wherein the indium oxide loaded by the monoclinic zirconium oxide is obviously stronger than the indium oxide loaded by the tetragonal zirconium oxide no matter the conversion rate of carbon dioxide or the selectivity of methanol, and the yield of the methanol and the proportion of the monoclinic zirconium oxide in the catalyst carrier present a positive correlation relationship in the carbon dioxide hydrogenation reaction process, so that the interaction between the monoclinic zirconium oxide and the indium oxide really promotes the activation of the carbon dioxide in the reaction process and is beneficial to the generation of the methanol. Meanwhile, the method has a certain industrial significance because the indium oxide is low in using amount and toxicity, and the methanol can be produced by the hydrogenation of carbon dioxide through a simple method under relatively low pressure.
Drawings
FIG. 1 shows In prepared In example 1 2 O 3 /5Li-ZrO 2 The distribution of products obtained by the catalyst catalytic carbon dioxide hydrogenation and the carbon dioxide conversion rate are shown as time-dependent graphs (280 ℃,30bar, space velocity =3 h) -1 ，CO 2 /N 2 /H 2 ＝1/1/3)；
FIG. 2 is a graph of methanol selectivity and carbon dioxide conversion as a function of reaction temperature (225-350 deg.C, 30bar, space velocity =3 h) in the hydrogenation of carbon dioxide catalyzed by the indium oxide-based catalysts prepared in examples 1, 26, 29, 30 -1 ，CO 2 /N 2 /H 2 ＝1/1/3)；
FIG. 3 is a graph of methanol yield as a function of reaction temperature for the catalytic hydrogenation of carbon dioxide with indium oxide based catalysts prepared in examples 1, 26, 29, and 30 (225-350 deg.C, 30bar, space velocity =3 h) -1 ，CO 2 /N 2 /H 2 ＝1/1/3)；
FIG. 4 is an X-ray diffraction pattern of the indium oxide-based catalysts prepared in examples 1, 26, 29 and 30;
fig. 5 shows surface raman spectra of the indium oxide-based catalysts prepared in examples 1, 26, 29 and 30.
Detailed Description
The present invention is further described in detail below by way of specific examples, which will enable one skilled in the art to more fully understand the present invention, but which are not intended to limit the invention in any way.
Example 1
(1) 3.0g of zirconium oxychloride octahydrate (ZrOCl) is taken 2 ·8H 2 O) and 0.03g of lithium nitrate (LiNO) 3 ) Adding into 50ml deionized water (the mol doping amount of lithium is 5%), the concentration of the formed solution is 0.2M/L, heating the solution to 80 ℃, standing and stirring;
(2) Adding strong ammonia water (NH) 3 ·H 2 O, the concentration is 22-25%) is added into the mixed solution of zirconium oxychloride and lithium nitrate in the step (1) drop by drop at the dropping speed of 20 drops/minute, and the dropping is stopped under the condition of continuously stirring until the pH value of the mixed solution reaches 9;
(3) Standing at 80 ℃ for aging reaction for 2h, centrifuging the obtained suspension, and washing with deionized water for four times; drying the obtained solid in an oven at 80 ℃ for 12h; roasting the dried solid in air at 300 ℃ for 4h to obtain 5Li-ZrO 2 A zirconia support.
(4) 0.21g of indium nitrate hydrate (In (NO) 3 ) 3 ·H 2 O) was dissolved in deionized water to form a solution having a concentration of 0.7M/L, and the solution was added dropwise to 1g of the 5Li-ZrO obtained in (3) 2 And (4) carrying out ultrasonic treatment for 2h on a zirconium oxide carrier (the mass fraction of the loaded indium oxide is 8%).
(5) Drying the solid obtained In the step (4) In a vacuum oven at 80 ℃ for 12h, and then roasting In air at 300 ℃ for 4h to obtain a series of In 2 O 3 /5Li-ZrO 2 A catalyst.
(6) Tabletting the powder catalyst into 20-40 mesh granular catalyst;
(7) The tabletted catalyst in 0.2g was loaded into a fixed bed reactor and N was added 2 Stamping to 30bar, and switching to reaction gas when the reaction temperature reaches 280 ℃, wherein the molar ratio of carbon dioxide to hydrogen is 3 2 ＝10ml/min,H 2 ＝30mL/min，N 2 =10 mL/min), the space velocity of the reaction based on carbon dioxide is 3h -1 。
The catalyst activity is expressed in terms of methanol produced (mL/min) and selectivity, the product selectivity being calculated as follows:
conversion rate:
and (3) selectivity:
wherein, F CO2,in Represents the volumetric flow rate of carbon dioxide at the inlet of the reactor, F CO2,out Representing the gas volumetric flow rate of carbon dioxide at the outlet of the reactor, i representing the reaction product, including CH 4 And CO, n represents the number of carbons contained in these substances.
The reaction products were analyzed on-line using a gas chromatograph, and the product rates and selectivities were related to time as shown in table 1 and fig. 1.
TABLE 1 product Selectivity at different reaction times
As can be seen from Table 1 and FIG. 1, in 2 O 3 /5Li-ZrO 2 The catalyst has high activity and good stability, and the reaction data is basically unchanged after 5 hours of reaction.
Example 2:
the reaction was carried out by the method of example 1 except that the concentration of the mixed solution in the step (1) was 0.5M/L.
Example 3:
the reaction was carried out by the method of example 1 except that the concentration of the mixed solution in the step (1) was 1M/L.
Example 4:
the reaction was carried out by the method of example 1, except that the heating temperature of the mixed solution in step (1) and the aging temperature in step (3) were 50 ℃.
Example 5:
the reaction was carried out by the method of example 1, except that the heating temperature of the mixed solution in step (1) and the aging temperature in step (3) were 90 ℃.
Example 6:
the reaction was carried out by the method of example 1 except that the pH of the mixed solution in the step (2) finally reached 8.
Example 7:
the reaction was carried out by the method of example 1 except that the pH of the mixed solution in the step (2) finally reached 10.
Example 8:
the reaction was carried out by the method of example 1, except that the aging time of the mixed solution in the step (3)) was 1 hour.
Example 9:
the reaction was carried out by the method of example 1 except that the aging time of the mixed solution in step (3) was 3 hours.
Example 10:
the reaction was carried out by the method of example 1, except that the dropping rate of the concentrated aqueous ammonia of step (2) was 30 drops/min.
Example 11:
the reaction was carried out by the method of example 1, except that the dropping rate of the concentrated aqueous ammonia of step (2) was 50 drops/min.
Example 12:
the reaction was carried out by the method of example 1, except that the drying temperatures of the step (3) and the step (5) were both 90 ℃.
Example 13:
the reaction was carried out by the method of example 1, except that the drying temperatures of the step (3) and the step (5) were 100 ℃.
Example 14:
the reaction was carried out by the method of example 1, except that the drying time of step (3) and step (5) was 8 hours.
Example 15:
the reaction was carried out by the method of example 1, except that the drying time of step (3) and step (5) was 10 hours.
Example 16:
the reaction was carried out by the method of example 1 except that the calcination temperatures of step (3) and step (5) were 400 ℃.
Example 17:
the reaction was carried out by the method of example 1 except that the calcination temperatures of step (3) and step (5) were 500 ℃.
Example 18:
the reaction was carried out by the method of example 1, except that the calcination time in step (3) was 2 hours.
Example 19:
the reaction was carried out by the method of example 1, except that the calcination time in step (3) was 6 hours.
Example 20:
the reaction was carried out by the method of example 1 except that the concentration of the indium nitrate solution of step (4) was 0.4M/L.
Example 21:
the reaction was carried out by the method of example 1 except that the concentration of the indium nitrate solution of step (4) was 1M/L.
Example 22:
the reaction was carried out by the method of example 1, differing only In the indium nitrate (In (NO) used In step (4) 3 ) 3 ·H 2 O) was 0.16g, and the mass fraction of the supported indium oxide was 6%.
Example 23:
the reaction was carried out by the method of example 1, differing only In the indium nitrate (In (NO) used In step (4) 3 ) 3 ·H 2 O) was 0.26g, and the mass fraction of the supported indium oxide was 10%.
Example 24:
the reaction was carried out by the method of example 1, except that the sonication time for step (4) was 1h.
Example 25:
the reaction was carried out by the method of example 1, except that the sonication time for step (4) was 3 hours.
Example 26:
the reaction was carried out by the method of example 1, except that only 3.2g of zirconium oxychloride (ZrOCl) was taken in step (1) 2 ·8H 2 O) was dissolved in 50ml of deionized water.
Example 27:
the reaction was carried out by the method of example 1, except that 2.9g of zirconium oxychloride (ZrOCl) was taken in step (1) 2 ·8H 2 O) and 0.04g of lithium nitrate (LiNO) 3 ) 50ml of deionized water (molar doping of lithium 7.5%) were added.
Example 28:
the reaction was carried out by the method of example 1, except that 2.8g of zirconium oxychloride (ZrOCl) was taken in step (1) 2 ·8H 2 O) and 0.06g of lithium nitrate (LiNO) 3 ) 50ml of deionized water (molar doping of lithium: 10%) are added.
Example 29:
the reaction was carried out by the method of example 1, except that 2.5g of zirconium oxychloride (ZrOCl) was taken in step (1) 2 ·8H 2 O) and 0.12g of lithium nitrate (LiNO) 3 ) 50ml of deionized water (20% molar doping of lithium) are added.
Example 30:
the reaction was carried out by the method of example 1, except that 1.9g of zirconium oxychloride (ZrOCl) was taken in step (1) 2 ·8H 2 O) and 0.24g of lithium nitrate (LiNO) 3 ) 50ml of deionized water (40% molar doping of lithium) are added.
Example 31:
the reaction was carried out by the method of example 1, except that the calcination time in step (5) was 5 hours.
Example 32:
the reaction was carried out by the method of example 1 except that the calcination time in step (5) was 6 hours.
Example 33:
the reaction was carried out by the method of example 1, except that the reaction temperature in step (7) was 225 ℃.
Example 34:
the reaction was carried out by the method of example 1, except that the reaction temperature in step (7) was 250 ℃.
Example 35:
the reaction was carried out by the method of example 1, except that the reaction temperature in step (7) was 300 ℃.
Example 36:
the reaction was carried out by the method of example 1, except that the reaction temperature in the step (7) was 350 ℃.
Example 37:
the reaction was carried out by the method of example 26 except that the reaction temperature in step (7) was 225 ℃.
Example 38:
the reaction was carried out by the method of example 26 except that the reaction temperature in step (7) was 250 ℃.
Example 39:
the reaction was carried out by the method of example 26 except that the reaction temperature in step (7) was 300 ℃.
Example 40:
the reaction was carried out by the method of example 26 except that the reaction temperature in step (7) was 350 ℃.
Example 41:
the reaction was carried out by the method of example 29 except that the reaction temperature in step (7) was 225 ℃.
Example 42:
the reaction was carried out by the method of example 29 except that the reaction temperature in step (7) was 250 ℃.
Example 43:
the reaction was carried out by the method of example 29 except that the reaction temperature in step (7) was 300 ℃.
Example 44:
the reaction was carried out by the method of example 29 except that the reaction temperature in step (7) was 350 ℃.
Example 45:
the reaction was carried out by the method of example 30 except that the reaction temperature in step (7) was 225 ℃.
Example 46:
the reaction was carried out by the method of example 30 except that the reaction temperature in step (7) was 250 ℃.
Example 47:
the reaction was carried out by the method of example 30 except that the reaction temperature in step (7) was 300 ℃.
Example 48:
the reaction was carried out by the method of example 30 except that the reaction temperature in step (7) was 350 ℃.
Example 49:
the reaction was carried out by the method of example 1, except that the space velocity of carbon dioxide in step (7) was 1 hour -1 。
Example 50:
the reaction was carried out by the method of example 1, except that the space velocity of carbon dioxide volume in step (7) was 5 hours -1 。
Example 51:
the reaction was carried out by the method of example 1, except that the space velocity of carbon dioxide in volume in step (7) was 10 hours -1 。
Example 52:
the reaction was carried out by the method of example 1, except that 3.2g of zirconium oxychloride (ZrOCl) was taken in step (1) 2 ·8H 2 O) is added into 50ml of deionized water, and the space velocity of the volume of the carbon dioxide in the step (7) is 1h -1 。
Example 53:
the reaction was carried out by the method of example 1, except that 3.2g of zirconium oxychloride (ZrOCl) was taken in step (1) 2 ·8H 2 O) is added into 50ml of deionized water, and the space velocity of the volume of the carbon dioxide in the step (7) is 5h -1 。
Example 54:
the reaction was carried out by the method of example 1, except that 3.2g of zirconium oxychloride (ZrOCl) was taken in step (1) 2 ·8H 2 O) is added into 50ml of deionized water, and the space velocity of the volume of the carbon dioxide in the step (7) is 10h -1 。
Example 55:
the reaction was carried out by the method of example 1, except that 1.9g of zirconium oxychloride (ZrOCl) was taken in step (1) 2 ·8H 2 O) and 0.24g of lithium nitrate (LiNO) 3 ) Adding 50ml of deionized water, wherein the volume space velocity of the carbon dioxide in the step (7) is 1h -1 。
Example 56:
the reaction was carried out by the method of example 1, except that 1.9g of zirconium oxychloride (ZrOCl) was taken in step (1) 2 ·8H 2 O) and 0.24g of lithium nitrate (LiNO) 3 ) Adding 50ml of deionized water, wherein the volume space velocity of the carbon dioxide in the step (7) is 5h -1 。
Example 57:
the reaction was carried out by the method of example 1, except that 1.9g of zirconium oxychloride (ZrOCl) was taken in step (1) 2 ·8H 2 O) and 0.24g of lithium nitrate (LiNO) 3 ) Adding 50ml of deionized water, wherein the volume space velocity of the carbon dioxide in the step (7) is 10h -1 。
For the results and data of the above examples, the activity data at 4h of reaction were compared to examine the effect of different parameters on the catalyst reactivity. With the exception of the conditions specified below, changes in the above conditions allowed the preparation of our catalyst and exhibited similar performance in the carbon dioxide hydrogenation reaction.
The effect of the molar doping amount of (I) lithium on the catalyst reactivity, see Table 2. The reaction conditions were the same as in examples 1, 26, 27, 28, 29 and 30.
TABLE 2 influence of different Li-doping amounts on the hydrogenation activity of carbon dioxide
| Li：Zr | CO 2 Conversion (%) | Methanol selectivity (%) |
| 0 | 5.2 | 72 |
| 5:95 | 12 | 88 |
| 7.5:92.5 | 12 | 88 |
| 10:90 | 11 | 86 |
| 20:80 | 8.5 | 77.4 |
| 40:60 | 6.3 | 61.6 |
As can be seen from table 2, the series of lithium-doped zirconia-supported indium oxide catalysts all showed better carbon dioxide hydrogenation activity and methanol selectivity when the molar doping amount of lithium ions x =5-10%, i.e., the molar doping amount of lithium ions x =5-10% was the optimum doping amount.
The influence of the molar doping amount of lithium (II) on the catalyst reactivity and the crystal form of zirconia can be seen in the attached figures 2, 3, 4 and 5 of the table. The reaction conditions were the same as in examples 1, 26, 29 and 30.
As can be seen from fig. 2 and 3, in the range of the carbon dioxide hydrogenation reaction temperature of 225 to 350 ℃, as the mol doping amount of Li increases (5 to 40%), the carbon dioxide conversion rate, the methanol selectivity and the methanol yield are gradually reduced, and the carbon monoxide selectivity is gradually increased; at an optimal reaction temperature of 280 DEG CMethanol selectivity from In 2 O 3 /5Li-ZrO 2 86% to In 2 O 3 /40Li-ZrO 2 61% of (1), carbon monoxide selectivity from In 2 O 3 /5Li-ZrO 2 12% to In 2 O 3 /40Li-ZrO 2 39% of the total. The reactivity of all samples was maintained for at least 5 hours without degradation, indicating good stability of the catalyst.
It is worth noting that the zirconia without doping Li is still in a tetragonal crystal form, and the conversion rate of carbon dioxide and the selectivity of methanol are not high; and a small amount of doped Li (the molar doping amount is 5-10%) can change the crystal form of the zirconium oxide to a monoclinic crystal form, and the catalytic performance (methanol selectivity) is obviously improved. As shown in fig. 4, when the molar doping amount of lithium in the zirconia support was 5%, the lithium-doped zirconia bulk phase completely exhibited a monoclinic crystal form. As shown in fig. 5, when the molar doping amount of lithium in the zirconia support is 5%, the surface of the lithium-doped zirconia completely shows a monoclinic crystal form. It can be seen that, as the doping amount of Li is continuously increased (the mol doping amount is 10-40%), the bulk crystal form of zirconia is transformed from a monoclinic crystal form to a tetragonal crystal form, and meanwhile, the surface crystal form also shows the same change trend.
(III) carbon dioxide hydrogenation reaction temperature vs. In 2 O 3 /5Li-ZrO 2 The effect of catalytic activity, see table 3. The reaction conditions were the same as in examples 1, 33, 34, 35 and 36.
TABLE 3 influence of reaction temperature on the hydrogenation activity of carbon dioxide
| Reaction temperature (. Degree.C.) | CO 2 Conversion (%) | Methanol selectivity (%) |
| 225 | 4 | 99.3 |
| 250 | 5 | 95 |
| 280 | 12 | 86 |
| 300 | 16 | 46.8 |
| 350 | 26 | 19.2 |
As can be seen from table 3, the conversion rate of carbon dioxide hydrogenation increases significantly, i.e. the reaction activity increases gradually, with the increase of the reaction temperature; for In 2 O 3 /5Li-ZrO 2 The selectivity of the catalyst and the product is very sensitive to the change of the reaction temperature, the selectivity of methanol is gradually reduced along with the increase of the reaction temperature, and the selectivity of carbon monoxide is gradually increased; referring to fig. 3, the methanol yield reaches a maximum value when the reaction temperature is 280 ℃.
(IV) carbon dioxide hydrogenation reaction temperature vs. In 2 O 3 /ZrO 2 See table 4 for the effect of catalytic activity. The reaction conditions were the same as in examples 26, 37, 38, 39 and 40.
TABLE 4 influence of reaction temperature on the hydrogenation activity of carbon dioxide
| Reaction temperature (. Degree.C.) | CO 2 Conversion (%) | Methanol selectivity (%) |
| 225 | 2 | 100 |
| 250 | 3.7 | 83 |
| 280 | 5.2 | 72 |
| 300 | 10.9 | 34 |
| 350 | 22 | 3 |
As can be seen from table 4, the conversion rate of carbon dioxide hydrogenation increases significantly, i.e. the reaction activity increases gradually, with the increase of the reaction temperature; for In 2 O 3 /ZrO 2 The catalyst has the product selectivity which is very sensitive to the change of the reaction temperature, the methanol selectivity is gradually reduced along with the increase of the reaction temperature, the carbon monoxide selectivity is gradually increased, when the reaction temperature is 280 ℃, the methanol yield reaches the maximum value, but a certain amount of carbon monoxide is still generated at the moment; at any reaction temperature, in 2 O 3 /ZrO 2 All methane selectivities are lower than In 2 O 3 /5Li-ZrO 2 。
(V) carbon dioxide hydrogenation reaction temperature vs. In 2 O 3 /20Li-ZrO 2 See table 5 for the effect of catalytic activity. The reaction conditions were the same as in examples 29, 41, 42, 43 and 44.
TABLE 5 influence of reaction temperature on carbon dioxide hydrogenation Activity
| Reaction temperature (. Degree.C.) | CO 2 Conversion (%) | Methanol selectivity (%) |
| 225 | 3.8 | 100 |
| 250 | 4.6 | 87.9 |
| 280 | 8.1 | 77.4 |
| 300 | 12.1 | 42 |
| 350 | 25 | 12 |
As can be seen from table 5, the conversion rate of carbon dioxide hydrogenation increases significantly, i.e. the reactivity increases gradually, with the increase of the reaction temperature; for In 2 O 3 /20Li-ZrO 2 The catalyst gradually reduces the selectivity of methanol and gradually increases the selectivity of carbon monoxide with the increase of the reaction temperature; referring to FIG. 3, when the reaction temperature is 280 deg.C, the methanol yield reaches a maximum, and In is present at any reaction temperature 2 O 3 /20Li-ZrO 2 All methane selectivities are lower than In 2 O 3 /5Li-ZrO 2 。
(VI) temperature of carbon dioxide hydrogenation reaction to In 2 O 3 /40Li-ZrO 2 See table 6 for the effect of catalytic activity. The reaction conditions were the same as in examples 30, 45, 46, 47 and 48.
TABLE 6 influence of reaction temperature on carbon dioxide hydrogenation Activity
| Reaction temperature (. Degree.C.) | CO 2 Conversion (%) | Methanol selectivity (%) |
| 225 | 2.3 | 92 |
| 250 | 3.4 | 80.4 |
| 280 | 6.3 | 61.6 |
| 300 | 10.9 | 30.8 |
| 350 | 22.9 | 6 |
As can be seen from the table, with the increase of the reaction temperature, the conversion rate of the carbon dioxide hydrogenation is obviously increased, namely the reaction activity is gradually increased; for In 2 O 3 /40Li-ZrO 2 The catalyst gradually reduces the selectivity of methanol and gradually increases the selectivity of carbon monoxide with the increase of the reaction temperature; referring to FIG. 3, the methanol yield reaches a maximum when the reaction temperature is 280 ℃, in at any reaction temperature 2 O 3 /40Li-ZrO 2 All methane selectivities are lower than In 2 O 3 /5Li-ZrO 2 。
As shown in fig. 2, the conversion rate of the three samples is consistent with the trend of the product distribution along with the change of the reaction temperature, but the difference of the product selectivity among the three samples is very obvious, and the difference along with the change of the temperature is ubiquitous and does not change.
(VII) influence of the carbon dioxide volumetric space velocity on the catalytic activity of the catalyst, see Table 7. The reaction conditions were the same as in examples 1 and 49 to 57.
TABLE 7 influence of the space velocity of carbon dioxide on the catalytic Activity
As can be seen from the table, the carbon dioxide conversion rate is continuously reduced with the increase of the volume space velocity of the carbon dioxide, but the selectivity of the methane and the carbon monoxide is basically unchanged, and the space velocity is 1h -1 And 3h -1 The difference is not large, so it is bestThe volume space velocity of the carbon dioxide is 3h -1 。
(eight) influence of calcination temperature in step (3) and step (5) on catalytic activity of the catalyst. The reaction conditions were the same as in examples 1, 16 and 17.
In when the calcination temperature is 300-400 DEG C 2 O 3 /5Li-ZrO 2 While the crystal form is still monoclinic, but at the roasting temperature>5Li-ZrO at 400 DEG C 2 The monoclinic structure of the zirconia carrier can be destroyed, and the corresponding catalyst In 2 O 3 /5Li-ZrO 2 The carbon dioxide conversion and methanol selectivity also decrease dramatically.
(nine) the effect of other factors on the catalytic activity of the catalyst.
Tests prove that under the experimental conditions, the zirconium oxychloride octahydrate (ZrOCl) 2 ·8H 2 O) and lithium nitrate (LiNO) 3 ) The concentration of the mixed solution is 0.2-1M/L, the heating temperature and the aging temperature of the mixed solution are kept between 50 and 100 ℃, and concentrated ammonia water is dripped until the pH value of the mixed solution reaches the range of 8 to 10; aging for 1-3h and roasting for 2-6h to obtain the xLi-ZrO 2 The carriers have no obvious difference in crystal form, particle size, surface structure and the like;
in addition, different indium nitrate hydrates (In (NO) 3 ) 3 ·H 2 O) (0.4-1M/L) and the mass fraction (6-10%) of the supported indium oxide; the time of ultrasonic treatment (1-3 h), drying temperature and time and the like are adjusted to obtain In 2 O 3 /xLi-ZrO 2 The structure and catalytic performance of the catalyst are not obviously influenced.
Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are merely illustrative and not restrictive, and those skilled in the art can make various changes and modifications within the spirit and scope of the present invention without departing from the spirit and scope of the appended claims.
Claims (8)
1. A lithium-doped zirconia supported indium oxide catalyst is characterized by being used for preparing methanol by carbon dioxide hydrogenation; the lithium-doped monoclinic zirconia is prepared by bulk phase doping of zirconia by lithium atoms through a coprecipitation method, and the molar doping amount x of lithium ions in the lithium-doped monoclinic zirconia is =5-10%; indium oxide particles are uniformly loaded on the lithium-doped monoclinic zirconia, and the mass percent of the indium oxide in the lithium-doped monoclinic zirconia is 6-10%;
the particle size range of the lithium-doped monoclinic zirconia is 50-100 nanometers; the particle size range of the indium oxide particles is 8-15 nanometers; and is obtained by the following method:
(1) Dissolving zirconium oxychloride octahydrate and lithium nitrate in deionized water according to the value of x in proportion to form a mixed solution with the concentration of 0.2-1M/L, and heating the mixed solution to 50-90 ℃;
(2) Continuously stirring the mixed solution obtained in the step (1), and dropwise adding strong ammonia water into the mixed solution until the pH value of the mixed solution reaches 8-10;
(3) Aging the mixed solution obtained in the step (2) at 50-90 ℃ for 1-3h, centrifuging and washing the obtained suspension, and drying in vacuum; then roasting for 2-6h at 300-400 ℃ to obtain xLi-ZrO 2 A support, x =5-10%, wherein x represents the molar doping amount of lithium ions in the lithium-doped monoclinic zirconia;
(4) Dissolving indium nitrate hydrate in deionized water to form a solution with the concentration of 0.4-1M/L, and dropwise adding the solution to the prepared xLi-ZrO 2 On the carrier, ensuring the mass fraction of the loaded indium oxide to be 6-10%; performing ultrasonic treatment, drying, and roasting at 300-500 deg.C for 4-6h to obtain In 2 O 3 /xLi-ZrO 2 Catalyst, x =5-10%.
2. The lithium-doped zirconia supported indium oxide catalyst according to claim 1, wherein the lithium-doped monoclinic zirconia is a support and the indium oxide is a catalytically active component.
3. A method for preparing the lithium doped zirconia supported indium oxide catalyst according to any of claims 1 to 2, wherein the method is carried out according to the following steps:
(1) Dissolving zirconium oxychloride octahydrate and lithium nitrate in deionized water according to the value of x in proportion to form a mixed solution with the concentration of 0.2-1M/L, and heating the mixed solution to 50-90 ℃;
(2) Continuously stirring the mixed solution obtained in the step (1), and dropwise adding strong ammonia water into the mixed solution until the pH value of the mixed solution reaches 8-10;
(3) Aging the mixed solution obtained in the step (2) at 50-90 ℃ for 1-3h, centrifuging and washing the obtained suspension, and drying in vacuum; then roasting for 2-6h at 300-400 ℃ to obtain xLi-ZrO 2 A support, x =5-10%, wherein x represents the molar doping amount of lithium ions in the lithium-doped monoclinic zirconia;
(4) Dissolving indium nitrate hydrate in deionized water to form a solution with the concentration of 0.4-1M/L, and dropwise adding the solution to the prepared xLi-ZrO 2 On the carrier, ensuring the mass fraction of the loaded indium oxide to be 6-10%; performing ultrasonic treatment, drying, and roasting at 300-500 deg.C for 4-6h to obtain In 2 O 3 /xLi-ZrO 2 Catalyst, x =5-10%.
4. The method for preparing a lithium-doped zirconia-supported indium oxide catalyst according to claim 3, wherein the dropping rate of the concentrated ammonia water in the step (2) is 20 to 50 drops/min.
5. The method for preparing the lithium-doped zirconium oxide supported indium oxide catalyst according to claim 3, wherein the temperature of the vacuum drying in the step (3) is 80-100 ℃ and the time is 8-12h.
6. The preparation method of the lithium-doped zirconium oxide supported indium oxide catalyst according to claim 3, wherein the ultrasonic treatment time in the step (4) is 1-3h, the vacuum drying temperature is 80-100 ℃, and the vacuum drying time is 8-12h.
7. Use of the lithium doped zirconia supported indium oxide catalyst according to any of claims 1 to 2 for the preparation of methanol by hydrogenation of carbon dioxide.
8. The use of the lithium doped zirconia supported indium oxide catalyst according to claim 7, wherein the following steps are performed:
(1) Tabletting and granulating the lithium-doped zirconium oxide loaded indium oxide catalyst;
(2) The granular catalyst prepared by the method is subjected to high-pressure continuous reaction in reaction gas at the reaction temperature of 250-350 ℃.
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