WO2017193696A1 - 一种催化剂、其制备方法及其在合成气制备中的应用 - Google Patents
一种催化剂、其制备方法及其在合成气制备中的应用 Download PDFInfo
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- WO2017193696A1 WO2017193696A1 PCT/CN2017/076793 CN2017076793W WO2017193696A1 WO 2017193696 A1 WO2017193696 A1 WO 2017193696A1 CN 2017076793 W CN2017076793 W CN 2017076793W WO 2017193696 A1 WO2017193696 A1 WO 2017193696A1
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Definitions
- the present application relates to a catalyst, a preparation method thereof and application thereof in carbon dioxide methane reforming reaction, and belongs to the field of chemical industry.
- Coal, oil and natural gas are the three fossil energy resources.
- China's coal resources are abundant, but in recent years, the pollution of the atmosphere, soil and groundwater in the process of coal mining and utilization has become more and more serious, which limits its large-scale use.
- China's oil reserves are small and must rely on imports, resulting in high oil use costs.
- China's shale gas reserves have leapt to the forefront of the world, the development and utilization of natural gas has received more and more attention.
- the state has introduced relevant policies to encourage the comprehensive and efficient use of natural gas, and the efficient use of natural gas has risen to the national strategic level.
- natural gas can be efficiently converted into high-value-added chemical products via synthesis gas, such as ammonia and methanol for large-tonnage demand, as well as intermediates for liquid fuels such as olefins and aromatics.
- synthesis gas such as ammonia and methanol for large-tonnage demand
- intermediates for liquid fuels such as olefins and aromatics.
- synthesis gas mainly uses natural gas as a raw material method, mainly including natural gas partial oxidation method and steam conversion method. Partial oxidation of natural gas is a relatively energy-intensive method that requires the consumption of large amounts of oxygen or air as feed gas. If no catalyst is used, the reaction temperature is as high as 1300 to 1400 °C. Even if a catalyst is used, the temperature of the catalytic bed is about 900 to 1000 ° C, and the reaction needs to be carried out at a high pressure (3.0 MPa), which is demanding for high temperature and high pressure resistance of the equipment. The maximum temperature of the reaction process in the natural gas batch conversion steam process is as high as 1300 ° C, and the process is very energy intensive.
- methane carbon dioxide reforming is a recent synthetic gas production technology approach that has received increasing attention.
- the advantages of the methane carbon dioxide reforming route are as follows: (1) Methane carbon dioxide dry reforming process does not require oxygen and water, and requires less equipment. (2) The H 2 / CO ratio is adjustable, which is more suitable for the proportion of the subsequent Fischer-Tropsch synthesis materials; the reaction can be carried out above 650 ° C, and the energy consumption is relatively low. (3) The raw material has a wide range of carbon dioxide sources and is cheaper than oxygen. The process achieves carbon dioxide emission reduction while efficiently utilizing methane, and has significant economic and environmental benefits. Carbon dioxide is the final product of the efficient use of coal and its downstream products.
- a catalyst for solving the problem that existing supported metal catalysts are inactivated by sintering and carbon deposition in a high temperature reaction acts as a high-temperature stable catalyst for carbon dioxide reforming methane reaction, and can produce syngas to achieve carbon dioxide emission reduction and recycling.
- the multi-stage pore-supporting metal catalyst exhibits excellent comprehensive catalytic performance.
- the catalyst has very good stability and has both anti-sintering and anti-coking properties. .
- the catalyst comprises a carrier and an active component dispersed on a carrier, wherein the carrier is selected from at least one of inorganic oxides, the carrier comprising macropores and mesopores;
- the active component contains an active element, and the active element includes an iron-based element selected from at least one of iron, cobalt, and nickel.
- the active element contains nickel.
- the macropores have an average pore diameter of greater than 50 nm, and the mesopores have an average pore diameter of from 1 nm to 50 nm.
- the macropores have an average pore diameter of from 1 ⁇ m to 2 ⁇ m.
- the mesopores have an average pore diameter of 5 nm to 15 nm.
- the carrier has a specific surface area of from 100 m 2 /g to 350 m 2 /g.
- the carrier cooperates with the active component to uniformly disperse and firmly support the active component on the carrier, thereby avoiding sintering of the active component metal particles during the catalytic reaction and preventing carbon deposition. Formed to extend catalyst life.
- the inorganic oxide having the above macropores and mesopores can be used as a carrier in the catalyst of the present application to solve the problem of high temperature sintering and carbon deposition and prolong the life of the catalyst.
- the support is at least one selected from the group consisting of alumina, silica, titania, and zirconia.
- the active element includes a precious metal element.
- the noble metal element is at least one selected from the group consisting of gold, silver, ruthenium, rhodium, palladium, osmium, iridium, and platinum. Further preferably, the noble metal element is at least one of platinum, rhodium, gold, and iridium.
- the noble metal cooperates with a non-noble metal (iron-based metal) to make the catalyst containing both the noble metal and the iron-based metal more excellent in overall catalytic performance than the catalyst containing only the iron-based metal.
- a non-noble metal iron-based metal
- the introduction of the precious metal active component facilitates better dispersion of the non-precious metal component in the carrier, further reduces the size of the active metal component particles, increases the number of active sites, and thereby increases the catalytic conversion rate.
- the size of the active metal particles is decreased, the metal-support interaction is increased, and the high temperature stability of the catalyst is improved.
- the active component is present in the catalyst in an amount of from 1% to 15% by mass; the mass percent of the active component in the catalyst is based on the active element contained in the catalyst. Further preferably, the active component is present in the catalyst in an amount of from 3.5% to 9% by mass; the mass percent of the active component in the catalyst is based on the active element contained in the catalyst.
- the lower limit of the mass percentage of the iron-based element in the catalyst in the active element is selected from the group consisting of 1.0%, 1.5%, 1.76%, 2.0%, 2.76%, 3.0%, 3.5%, 3.84%, 4.0%, 4.09%. , 4.05%, 4.12%, 4.16%, 4.18%, 4.5%, 4.74%, 4.8% or 4.9%, the upper limit is selected from 5.0%, 5.1%, 5.41%, 5.45%, 6.24%, 6.49%, 7.0%, 8.0 %, 9.0% or 10%; the mass percentage of the iron-based element in the catalyst is calculated as the sum of the mass percentages of all the iron-based elements contained in the catalyst.
- the iron element in the active element is contained in the catalyst in an amount of from 1% to 10% by mass. Still more preferably, the iron element in the active element is contained in the catalyst in an amount of from 3% to 6% by mass.
- the lower limit of the mass percentage of the precious metal element in the active element in the active element is selected from the group consisting of 0.1%, 0.2%, 0.24%, 0.29%, 0.3%, 0.31%, 0.33%, 0.35%, 0.37%, 0.38%. , 0.39%, 0.40%, 0.42%, 0.43%, 0.45%, 0.5%, 0.54%, 0.55%, 0.6%, 0.7%, 0.8% or 0.9%, the upper limit is selected from 1.0%, 1.07%, 1.5%, 2.0 %, 2.5%, 2.93%, 3.0%, 3.5%, 4.0%, 4.5% or 5.0%; the mass percentage of the precious metal element in the catalyst is calculated as the sum of the mass percentages of all precious metal elements contained in the catalyst . Further preferably, the content of the precious metal element in the active element in the catalyst is from 0.1% to 5% by mass. Still more preferably, the content of the precious metal element in the active element in the catalyst is from 0.5% to 3% by mass.
- the catalyst contains a modifying component dispersed on a carrier; the modifying component contains a modifying element selected from the group consisting of an alkali metal element, an alkaline earth metal element, and a rare earth metal element. At least one of them.
- the lower limit of the mass percentage of the modifying element in the catalyst is selected from the group consisting of 0.1%, 0.2%, 0.3%, 0.36%, 0.4%, 0.5%, 0.6%, 0.7%, 0.77%, and 0.8. %, 0.85%, 0.87%, 0.9%, 0.95% or 1%
- the upper limit is selected from 1.28%, 1.32%, 1.5%, 2.0%, 2.07%, 2.11%, 2.5%, 2.65%, 2.8%, 3%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 5.87%, 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, 8.5% or 9.0%; the quality of the modified element in the catalyst The fraction is based on the sum of the mass percentages of all the modifying elements contained in the catalyst.
- the alkali metal element is present in the catalyst in an amount of from 0.1% to 10% by mass.
- the lower limit of the mass percentage of the alkali metal element in the catalyst is selected from 0.1%, 0.5%, 0.87%, 0.97% or 1.0%, and the upper limit is selected from 1.32%, 1.5%, 2.0%, 2.11%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 4.85% or 5.0%.
- the alkali metal element is present in the catalyst in an amount of from 0.1% to 5% by mass.
- the alkaline earth metal element is present in the catalyst in an amount of from 0.1% to 10% by mass.
- the lower limit of the mass percentage of the alkaline earth metal element in the catalyst is selected from 0.1%, 0.5%, 0.82%, 0.95% or 1%
- the upper limit is selected from the group consisting of 2.0%, 2.11%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 4.77%, 4.82% or 5.0%.
- the alkaline earth metal element is present in the catalyst in an amount of from 0.1% to 5% by mass.
- the rare earth metal element is present in the catalyst in an amount of from 0.1% to 10% by mass.
- the lower limit of the mass percentage of the rare earth metal element in the catalyst is selected from 0.1%, 0.2%, 0.3%, 0.36%, 0.5%, 0.6%, 0.8% or 1.0%
- the upper limit is selected from the group consisting of 1.26% and 1.38. %, 1.39%, 1.4%, 1.5%, 2.0%, 2.11%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.07% or 5.87%.
- the rare earth metal element is present in the catalyst in an amount of from 0.1% to 6% by mass.
- the active component is present on the support in the form of a compound of a zero valent metal and/or an active metal element of the active metal element.
- the active component is present on the support in the form of a zero valent metal of the active metal element.
- the modifying component is present on the support in the form of a modifying elemental compound or a zerovalent metal.
- the modifying component is present as a modifying elemental compound on the support.
- the active component and the modified component have a narrow particle size distribution and are highly dispersedly distributed in the multistage pore carrier.
- the active component dispersed on the carrier has a particle size distribution between 1 nm and 50 nm.
- the upper limit of the particle size range of the active component dispersed on the carrier is selected from the group consisting of 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, and the lower limit is selected from 1 nm, 5 nm, 10 nm.
- the active component dispersed on the carrier has a particle size distribution between 1 nm and 15 nm.
- the modified component dispersed on the carrier has a particle size distribution between 1 nm and 50 nm.
- the upper limit of the particle size range of the modified component dispersed on the carrier is selected from the group consisting of 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, and the lower limit is selected from 1 nm, 5 nm, and 10 nm.
- the modified component dispersed on the carrier has a particle size distribution between 1 nm and 15 nm.
- a rare earth element is contained in the modifying element.
- the active element includes a noble metal element
- the modified element contains a rare earth element
- the active element is nickel and the modifying element is a rare earth element.
- the active element is composed of platinum and nickel, and the modifying element is composed of lanthanum and potassium;
- step b) After the solid obtained in step a) is separated, dried, calcined in air and reduced by hydrogen, the catalyst is obtained.
- the impregnation in step a) is ultrasonic impregnation
- the total immersion time is from 24 hours to 96 hours
- the ultrasonic accumulation time is from 2 hours to 10 hours.
- the ultrasonic immersion in step a) is intermittent ultrasonic, the total immersion time is 36 hours to 60 hours, and the ultrasonic accumulation time is 2 hours to 6 hours.
- the drying temperature of step b) is from 60 ° C to 200 ° C.
- the drying in step b) is vacuum drying at 60 ° C to 100 ° C for 8 hours to 10 hours.
- the air calcination in step b) is carried out at a temperature increase rate of 1 ° C / min to 10 ° C / min from room temperature to a temperature between 300 ° C and 800 ° C, and calcined for not less than 1 hour.
- the air calcination in step b) is carried out at a temperature increase rate of 1 ° C / min to 5 ° C / min from room temperature to a temperature between 500 ° C and 700 ° C, and calcined for 2 hours to 4 hours.
- the hydrogen reduction in step b) is carried out at a temperature increase rate of 5 ° C / min to 20 ° C / min from room temperature to a temperature between 600 ° C and 1000 ° C, in hydrogen or hydrogen and inactive
- the mixture of gases is reduced for not less than one hour; the flow rate of hydrogen or a mixture of hydrogen and an inert gas is from 20 mL/min to 80 mL/min.
- the hydrogen reduction in step b) is carried out at a temperature increase rate of 5 ° C / min to 15 ° C / min from room temperature to a temperature between 800 ° C and 1000 ° C, and the reduction in hydrogen is not less than 1 hour to 2 hours; the flow rate of hydrogen is 20 mL/min to 40 mL/min.
- the inert gas is selected from at least one of nitrogen gas and inert gas. Further preferably, the inert gas is at least one selected from the group consisting of nitrogen, helium, and argon.
- a method for producing a synthesis gas by carbon dioxide methane reforming reaction wherein the raw material containing methane and carbon dioxide is contacted with a catalyst to prepare a synthesis gas; and the catalyst is selected from any one of the above At least one of a catalyst, a catalyst prepared according to any of the above methods.
- the raw material containing methane and carbon dioxide is contacted with the catalyst at a reaction temperature of 600 ° C to 900 ° C and a reaction pressure of 0.1 MPa to 0.5 MPa to prepare a synthesis gas;
- the molar ratio of carbon dioxide to methane in the feed gas is:
- Carbon dioxide: methane 0.5 to 2.
- the catalyst provided by the present application when the rare earth element is added for modification, the addition of the rare earth element-modified component effectively enhances the activity of the catalyst; even in the case of a lower active component loading, the rare earth The modified catalyst exhibits a higher catalytic conversion.
- the catalyst provided by the present application when containing a noble metal, incorporates a noble metal as a second active component in addition to an iron-based metal (at least one of iron, cobalt, and nickel) as the first active component.
- the noble metal synergizes with the non-noble metal, so that the catalyst containing both the noble metal and the iron-based metal has superior comprehensive catalytic performance than the catalyst containing only the iron-based metal.
- the introduction of the precious metal active component facilitates better dispersion of the non-precious metal component in the carrier, further reduces the size of the active metal component particles, and obtains more active sites to increase the catalytic conversion rate.
- a relatively strong metal-support interaction between the small-sized metal active component particles and the carrier can effectively improve the high-temperature stability of the catalyst.
- a catalyst containing both an iron-based metal and a noble metal reduces the amount of the precious metal by introducing a non-precious metal, so that the catalyst cost is lowered.
- the catalyst containing both iron-based metals and noble metals has a good cost performance and has a good application prospect.
- the catalyst provided in the present application can introduce a modifying component (alkali metal salt, alkaline earth metal salt or rare earth metal salt) to further improve the overall performance of the catalyst.
- the catalyst provided in the present application can be used as a high-temperature stable catalyst for carbon dioxide reforming methane reaction to produce a synthesis gas to achieve carbon dioxide emission reduction and recycling. Under normal pressure and 800 °C reaction conditions, it exhibits excellent comprehensive catalytic performance (activity, selectivity and stability), and is cost-effective, and has a good application prospect.
- 1 is a scanning electron micrograph of a cross-section of a carrier multi-stage alumina microsphere I; (a) is a scanning electron micrograph at a magnification of 1100 times; (b) is a scanning electron microscope image magnified 35,000 times.
- Figure 2 is a chromatographic test result of the sample CAT-I-1 for carbon dioxide reforming methane reaction product; (a) is the result of the thermal conductivity detector TCD; (b) is the flame ionization detector FID result.
- Figure 3 is a graph showing the stability test results of the sample CAT-I-1.
- Figure 4 is a transmission electron micrograph of the sample before and after the reaction of CAT-I-1; (a) is a transmission electron micrograph of the sample CAT-I-1 before the reaction; (b) is a sample of the sample CAT-I-1 after reacting at 800 ° C for 102 hours. Transmission electron micrograph.
- Figure 5 is a graph comparing the catalytic activities of samples CAT-II-1 and DCAT-II-1; (a) is the carbon dioxide conversion rate; and (b) is the methane conversion rate.
- Figure 6 is a chromatographic test result of the sample CAT-II-1 for carbon dioxide reforming methane reaction product; (a) is the result of the thermal conductivity detector TCD; (b) is the result of the flame ionization detector FID.
- Figure 7 shows the stability test results of the sample CAT-II-1.
- Figure 8 is a transmission electron micrograph of the sample before and after the reaction of CAT-II-1; (a) is a transmission electron micrograph of the sample CAT-II-1 before the reaction; (b) is a sample of the sample CAT-II-1 after reacting at 800 ° C for 102 hours. Transmission electron micrograph.
- Figure 9 is a comparison of the stability of the samples CAT-III-1, CAT-III-2 and CAT-III-17; wherein: (a) is the relationship of carbon dioxide conversion with time; (b) is the conversion of methane The relationship of time changes.
- Figure 10 is a transmission electron micrograph of sample CAT-III-1, samples CAT-III-17 and CAT-III-18; (a) is a transmission electron micrograph of sample CAT-III-1, and (b) is sample CAT-III The transmission electron micrograph of -17, (c) is the transmission electron micrograph of CAT-III-18.
- the scanning electron micrograph of the sample was taken using a Japanese Hitachi S4800 scanning electron microscope; the transmission electron micrograph of the sample was collected on a F20 type transmission electron microscope of FEI.
- the ultrasonic instrument used in the ultrasonic immersion is KQ300ED type produced by Kunshan Ultrasonic Instrument Co., Ltd.
- the loading amounts of iron-based elements, noble metal elements, alkali metal elements, alkaline earth metal elements, and rare earth elements on the catalyst were analyzed by plasma emission spectroscopy (ICP) on a Ultima type 2 instrument of HORIBA JY, France.
- reaction product of the carbon dioxide methane reforming reaction to syngas was detected on a Shimadzu GC-2014 chromatograph (TDX-01 column).
- the multi-stage pore alumina microsphere I has a specific surface area of 197.91 m 2 /g, a large pore average pore diameter of 1.52 ⁇ m, a mesoporous average pore diameter of 9.80 nm, and a specific surface area of the multistage pore alumina microsphere II.
- the average pore diameter of the macropores is 1.61 ⁇ m; the average pore diameter of the mesopores is 10.23 nm; the specific surface area of the multi-stage pore alumina microspheres III is 213.09 m 2 /g; the average pore diameter of the macropores is 1.57 ⁇ m; mesopores The average pore diameter was 11.08 nm.
- a certain amount of the active component metal salt and/or the modified component metal salt is dissolved in 10 mL of water to form a solution, 5 g of the carrier is added, and after ultrasonic immersion for a while, the solvent and excess unabsorbed metal salt are removed by filtration.
- the carrier to which the metal ions were adsorbed was vacuum dried at 80 ° C for 8 hours, then calcined in an air atmosphere, and finally hydrogen was reduced to obtain the catalyst.
- Example 2 sample characterization
- the carrier multi-stage pore alumina microsphere I, multi-stage pore alumina microsphere II and multi-stage pore alumina microsphere III were characterized by scanning electron microscopy.
- the carrier multi-stage pore alumina microsphere I is typical, and its cross-sectional scanning electron micrograph is shown in Fig. 1. It can be seen that it has micropores and nanopores.
- a cross-sectional scanning electron micrograph of the multi-stage porous alumina microsphere II and the multi-stage porous alumina microsphere III is similar to that of FIG.
- the particle size range of the active component and the modified component rare earth particles on the catalyst sample was observed by transmission scanning electron microscopy. The results are shown in Table 1.
- the mass percentage of iron, precious metal, alkali metal, alkaline earth metal and rare earth metal elements in the sample was determined by ICP. The results are shown in Table 1.
- 0.2 g of the catalyst sample CAT-I-1 was placed in a fixed bed reactor having an inner diameter of 1 cm, and after hydrogen reduction was carried out, the temperature was adjusted to the reaction temperature.
- the gas was switched to a mixture of CO 2 and CH 4 with N 2 as an internal standard. After the reaction, the gas was cooled and then subjected to gas chromatography to determine the concentration of each substance, and the conversion rates of CO 2 and CH 4 were calculated.
- the reaction condition is A
- the chromatographic detection result of the reaction tail gas is shown in Fig. 2.
- the catalyst sample provided by the present application has good selectivity, and the product is basically the main component of the synthesis gas: hydrogen and carbon monoxide.
- F CO2,in and F CO2,out are the volume fraction of CO 2 in the feed gas and reaction off-gas
- F CH4,in and F CH4,out are the volume fraction of CH 4 in the reactants and products, respectively.
- reaction results of the catalyst samples CAT-I-2 ⁇ CAT-I-11 are similar to those of CAT-I-1.
- the conversion of CO 2 and CH 4 is within ⁇ 10% depending on the preparation method of the catalyst. Variety.
- CAT-I-1 0.2 g of the catalyst sample CAT-I-1 was placed in a fixed bed reactor having an inner diameter of 1 cm, and the catalyst stability evaluation was carried out under the reaction condition A of Example 3, and the results are shown in Fig. 3. It can be seen from Fig. 3 that CAT-I-1 has excellent stability under normal pressure and 800 ° C reaction conditions, and the conversion rates of carbon dioxide and methane remain substantially unchanged within 100 hours of reaction time.
- Fig. 4(a) is a transmission electron micrograph of the sample CAT-I-1 before the reaction
- Fig. 4(b) is a transmission electron micrograph of the sample CAT-I-1 after reacting at 800 ° C for 102 hours.
- Figure 4 It can be seen that the active component nickel particles on the catalyst sample did not substantially change before and after the reaction, and no sintering occurred; and no carbon formation occurred in the reaction catalyst for 102 hours.
- the catalyst stability evaluation results of the catalyst samples CAT-I-2 ⁇ CAT-I-11 were similar to those of CAT-I-1.
- the conversion rates of carbon dioxide and methane remained basically unchanged within 100 hours of the reaction time.
- the transmission electron micrographs of the samples CAT-I-2 ⁇ CAT-I-11 after reacting at 800 °C for 102 hours were compared with those before the reaction. Similar to CAT-I-1, the nickel particles did not sinter and there was no carbon formation in the catalyst. .
- the mass percentage of nickel in CAT-II-1 was 3.82%; the mass percentage of nickel in DCAT-II-1 was 4.25%. It can be seen from Fig. 5 that the conversion of CAT-II-1, carbon dioxide and methane with modified rare earth elements and low active component content is higher than that of DCAT-II-1 with higher active components.
- the reaction condition is A
- the chromatographic detection result of the reaction tail gas is shown in Fig. 6.
- the catalyst provided by the present application has good selectivity, and the product is basically the main component of the synthesis gas: hydrogen and carbon monoxide.
- F CO2,in and F CO2,out are the volume fraction of CO 2 in the feed gas and reaction off-gas
- F CH4,in and F CH4,out are the volume fraction of CH 4 in the reactants and products, respectively.
- reaction results of the catalyst samples CAT-II-2 ⁇ CAT-II-15 are similar to those of CAT-II-1.
- the conversion of CO 2 and CH 4 is within ⁇ 10% depending on the preparation method of the catalyst. Variety.
- 0.2 g of the catalyst sample CAT-II-1 was placed in a fixed bed reactor having an inner diameter of 1 cm, and the catalyst stability evaluation was carried out under the reaction condition A of Example 7, and the results are shown in Fig. 7. It can be seen from Fig. 7 that the catalyst provided by the present application has excellent stability under normal pressure and 800 ° C reaction conditions, and the conversion rates of carbon dioxide and methane remain substantially unchanged within 100 hours of the reaction time.
- FIG. 8(a) is a transmission electron micrograph of the sample CAT-II-1 before the reaction
- Fig. 8(b) is a transmission electron micrograph of the sample CAT-II-1 after reacting at 800 ° C for 102 hours.
- the particles of the active component and the modified component on the catalyst sample did not substantially change before and after the reaction, and no sintering occurred; and no carbon formation occurred in the reaction catalyst for 102 hours.
- F CO2,in and F CO2,out are the volume fraction of CO 2 in the feed gas and reaction off-gas
- F CH4,in and F CH4,out are the volume fraction of CH 4 in the reactants and products, respectively.
- reaction results of catalyst samples CAT-III-2 to CAT-III-29 are similar to those of CAT-III-1.
- the conversion of CO 2 and CH 4 is within ⁇ 20% depending on the preparation method of the catalyst. Variety.
- Fig. 9(a) and Fig. 9(b) The stability test results of the catalysts CAT-III-1, CAT-III-2 and CAT-III-17 are shown in Fig. 9(a) and Fig. 9(b). It can be seen from Fig. 9 that the active elements contain precious metals and iron-based catalysts CAT-III-1 and CAT-III-2, under normal pressure, 800 ° C reaction conditions, within 200 hours of reaction time, carbon dioxide and methane The conversion rate maintains good stability. If the noble metal element is not contained in the active element, the catalyst stability is slightly lower. Catalyst stability: CAT-III-2>CAT-III-1>CAT-III-17, indicating that the addition of precious metals improves the stability of the catalyst.
- Figure 9(a) The data in Figure 9(b) also shows that after the introduction of precious metals in the catalyst, in addition to the improved stability, the conversion of carbon dioxide and methane is also significantly improved. After further adding a small amount of rare earth salt to modify, the conversion rate is slightly increased.
- the sample CAT-III-1 is typical, and its transmission electron micrograph is shown in Fig. 10(a). It can be seen from Fig. 10 that the particle size of the metal particles is uniform on the catalyst containing noble metal, and the particle size ranges from 5 nm. Between ⁇ 15 nm, and the metal particles are uniformly dispersed on the carrier.
- Fig. 10(b) and Fig. 10(c) are transmission electron micrographs of samples CAT-III-17 and CAT-III-18, respectively. Comparing Fig. 10(a) to Fig. 10(c), it can be seen that after adding rare earth elements to the non-precious metal catalyst, the active metal particles become smaller; while the addition of the noble metal, the particle size becomes smaller than that of the rare earth salt. .
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Abstract
一种多级孔负载型催化剂、制备方法及其在二氧化碳甲烷重整反应中的应用。催化剂包括载体和分散在载体上的活性组分,载体选自无机氧化物中的至少一种,所述载体包含平均孔径大于50nm的大孔和平均孔径为1nm~50nm介孔;所述活性组分含有活性元素,活性元素包括铁系元素。催化剂在二氧化碳甲烷重整反应中表现出优异的催化性能,耐烧结和抗积炭性能。
Description
本申请涉及一种催化剂、制备方法及其在二氧化碳甲烷重整反应中的应用,属于化工领域。
煤炭、石油和天然气是三大化石能源资源。我国煤炭资源丰富,但近些年煤炭开采和利用过程中对大气、土壤和地下水的污染越来越严重,限制了其大量使用。而我国石油储量少,必须依靠进口,导致石油使用成本偏高。近几年,随着我国页岩气矿储量跃居世界前列,天然气的开发利用越来越受重视,国家出台了相关政策鼓励天然气的综合高效利用,天然气的高效利用上升到国家战略层次。天然气除了可以直接作为燃料外,其主要成分甲烷可以经由合成气高效转化为具有高附加值的化工产品,如生产大吨位需求的氨、甲醇,也可生产烯烃、芳烃等液体燃料的中间体。
目前工业上生产合成气主要采用天然气为原料的方法,主要包括天然气部分氧化法和蒸汽转化法。天然气部分氧化法是一种比较耗能的方法,需要消耗大量氧气或空气作为原料气。如果不使用催化剂,反应温度高达1300~1400℃。即使使用催化剂,催化床层温度高约900~1000℃、而且反应需要在高压(3.0MPa)进行,对设备的耐高温耐高压要求苛刻。天然气间歇转化蒸汽法中反应过程最高温度高达1300℃,过程非常耗能。连续蒸汽转化虽然能耗比较低,但仍然对设备耐高温高压的要求较高。而且不管是间歇转化还是连续转化,原料气水蒸汽在高温条件下对设备的腐蚀会影响到设备的使用寿命,增加工艺成本。这些技术工艺路线普遍存在反应温度高、耗能高、对设备的耐高温耐高压耐水蒸气腐蚀要求苛刻等技术问题。因此,开发无水无氧工艺生产对合成气的工业生产具有重要的意义。
除了甲烷水蒸汽重整、甲烷部分氧化外,甲烷二氧化碳重整是近些来逐渐受到关注的合成气生产技术途径。甲烷二氧化碳重整路线的优势如下:(1)甲烷二氧化碳干重整过程无需氧气和水,对设备要求较低。(2)H2/CO比值可调,更适合后续费托合成原料比例;反应可在650℃以上进行,能耗相对较低。(3)原料二氧化碳来源广泛,相比氧气廉价。该工艺过程在高效利用甲烷的同时实现了二氧化碳减排,具有显著的经济效益和环保效益。二氧化碳是煤炭及其下游产品高效利用的最终产物,如何实现二氧化碳的再生利用,变废为宝是煤炭清洁高效利用中非常重要的内容之一。该工艺有利于减少大气中二氧化碳的总量,缓解温室气体造成的环境压力,为我国减排提供了一种有效的方法。
要使惰性的甲烷和二氧化碳分子活化并进行定向转化,开发具有高活性、高选择性、高稳定性的低成本催化剂是关键。
发明内容
根据本申请的一个方面,提供一种催化剂,以解决现有负载型金属催化剂在高温反应中易烧结和积炭而失活的问题。该催化剂作为二氧化碳重整甲烷反应的高温稳定催化剂,可制造合成气,实现二氧化碳减排和再生利用。在常压、800℃反应条件下,多级孔负载型金属催化剂表现出优异的综合催化性能,除了活性高、选择性好外,该催化剂稳定性非常好,兼具抗烧结和抗积炭性能。
所述催化剂包括载体和分散在载体上的活性组分,其特征在于,所述载体选自无机氧化物中的至少一种,所述载体包含大孔和介孔;
所述活性组分含有活性元素,所述活性元素包括铁系元素,所述铁系元素选自铁、钴、镍中的至少一种。
优选地,所述活性元素中含有镍。
优选地,所述大孔的平均孔径大于50nm,所述介孔的平均孔径为1nm~50nm。
优选地,所述大孔的平均孔径为1μm~2μm。
优选地,所述介孔的平均孔径为5nm~15nm。
优选地,所述载体的比表面积为100m2/g~350m2/g。
相比传统介孔载体,所述载体与活性组分协调作用,使活性组分均匀分散、牢固负载于载体上,避免了活性组分金属颗粒在催化反应过程中发生烧结,阻止了积炭的形成,延长了催化剂寿命。具备上述大孔和介孔的无机氧化物,均可以作为本申请所述催化剂中的载体,达到解决高温烧结和积炭问题,延长催化剂寿命的效果。优选地,所述载体选自氧化铝、氧化硅、氧化钛、氧化锆中的至少一种。
作为一种优选的实施方式,所述活性元素中包括贵金属元素。所述贵金属元素选自金、银、钌、铑、钯、锇、铱、铂中的至少一种。进一步优选地,所述贵金属元素为铂、钌、金、铑中的至少一种。
贵金属与非贵金属(铁系金属)协同作用,使得同时包含贵金属和铁系金属的催化剂比仅包含铁系金属的催化剂具有更优异的综合催化性能。一方面,引入贵金属活性组分,有利于非贵金属组分在载体中更好地分散,进一步降低活性金属组分颗粒的尺寸,增加活性位点数量,从而提高催化转化率。另一方面,活性金属颗粒的尺寸下降,增加了金属-载体相互作用,提升了催化剂的高温稳定性。
所述活性组分在催化剂中的质量百分含量为1%~15%;所述活性组分在催化剂中的质量百分含量以催化剂中含有的活性元素计。进一步优选地,所述活性组分在催化剂中的质量百分含量为3.5%~9%;所述活性组分在催化剂中的质量百分含量以催化剂中含有的活性元素计。
优选地,所述活性元素中铁系元素在催化剂中的质量百分含量下限选自1.0%、1.5%、1.76%、2.0%、2.76%、3.0%、3.5%、3.84%、4.0%、4.09%、4.05%、4.12%、4.16%、4.18%、4.5%、4.74%、4.8%或4.9%,上限选自5.0%、5.1%、5.41%、5.45%、6.24%、6.49%、7.0%、8.0%、9.0%或10%;所述铁系元素在催化剂中的质量百分含量以催化剂中含有的所有铁系元素的质量百分含量之和计。进一步优选地,所述活性元素中铁系元素在催化剂中的质量百分含量为1%~10%。更进一步优选地,所述活性元素中铁系元素在催化剂中的质量百分含量为3%~6%。
优选地,所述活性元素中贵金属元素在催化剂中的质量百分含量下限选自0.1%、0.2%、0.24%、0.29%、0.3%、0.31%、0.33%、0.35%、0.37%、0.38%、0.39%、0.40%、0.42%、0.43%、0.45%、0.5%、0.54%、0.55%、0.6%、0.7%、0.8%或0.9%,上限选自1.0%、1.07%、1.5%、2.0%、2.5%、2.93%、3.0%、3.5%、4.0%、4.5%或5.0%;所述贵金属元素在催化剂中的质量百分含量以催化剂中含有的所有贵金属元素质量百分含量之和计。进一步优选地,所述活性元素中贵金属元素在催化剂中的质量百分含量为0.1%~5%。更进一步优选地,所述活性元素中贵金属元素在催化剂中的质量百分含量为0.5%~3%。
作为一种实施方式,所述催化剂含有分散在载体上的改性组分;所述改性组分含有改性元素,所述改性元素选自碱金属元素、碱土金属元素、稀土金属元素中的至少一种。
作为一种实施方式,所述改性元素在催化剂中的质量百分含量下限选自0.1%、0.2%、0.3%、0.36%、0.4%、0.5%、0.6%、0.7%、0.77%、0.8%、0.85%、0.87%、0.9%、0.95%或1%,上限选自1.28%、1.32%、1.5%、2.0%、2.07%、2.11%、2.5%、2.65%、2.8%、3%、3.5%、4.0%、4.5%、5.0%、5.5%、5.87%、6.0%、6.5%、7.0%、7.5%、8.0%、8.5%或9.0%;所述改性元素在催化剂中的质量百分含量以催化剂中含有的所有改性元素的质量百分含量之和计。
优选地,所述碱金属元素在催化剂中的质量百分含量为0.1%~10%。进一步优选地,所述碱金属元素在催化剂中的质量百分含量下限选自0.1%、0.5%、0.87%、0.97%或1.0%,上限选自1.32%、1.5%、2.0%、2.11%、2.5%、3.0%、3.5%、4.0%、4.5%、4.85%或5.0%。更进一步优选地,所述碱金属元素在催化剂中的质量百分含量为0.1%~5%。
优选地,所述碱土金属元素在催化剂中的质量百分含量为0.1%~10%。进一步优选地,所述碱土金属元素在催化剂中的质量百分含量下限选自0.1%、0.5%、0.82%、0.95%或1%,上限选自2.0%、2.11%、2.5%、3.0%、3.5%、4.0%、4.5%、4.77%、4.82%或5.0%。更进一步优选地,所述碱土金属元素在催化剂中的质量百分含量为0.1%~5%。
优选地,所述稀土金属元素在催化剂中的质量百分含量为0.1%~10%。优选地,所述稀土金属元素在催化剂中的质量百分含量下限选自0.1%、0.2%、0.3%、0.36%、0.5%、0.6%、0.8%或1.0%,上限选自1.26%、1.38%、1.39%、1.4%、1.5%、2.0%、2.11%、2.5%、3.0%、3.5%、4.0%、4.5%、5.0%、5.07%或5.87%。更进一步优选地,所述稀土金属元素在催化剂中的质量百分含量为0.1%~6%。
所述活性组分在载体上以活性金属元素的零价金属和/或活性金属元素的化合物形式存在。优选地,所述活性组分在载体上以活性金属元素的零价金属形式存在。
所述改性组分在载体上以改性元素化合物或零价金属的形式存在,优选地,所述改性组分在载体上以改性元素化合物形式存在。
所述活性组分和改性组分的粒径分布窄,高度分散地分布在多级孔载体中。
优选地,所述分散在载体上的活性组分的粒径分布在1nm~50nm之间。进一步优选地,所述分散在载体上的活性组分的粒径范围上限选自15nm、20nm、25nm、30nm、35nm、40nm、45nm、50nm,下限选自1nm、5nm、10nm。更进一步优选地,所述分散在载体上的活性组分的粒径分布在1nm~15nm之间。
优选地,所述分散在载体上的改性组分的粒径分布在1nm~50nm之间。进一步优选地,所述分散在载体上的改性组分的粒径范围上限选自15nm、20nm、25nm、30nm、35nm、40nm、45nm、50nm,下限选自1nm、5nm、10nm。更进一步优选地,所述分散在载体上的改性组分的粒径分布在1nm~15nm之间。
作为一种优选的实施方式,所述催化剂中,改性元素中包含稀土元素。
作为一种优选的实施方式,所述催化剂中,活性元素包括贵金属元素,改性元素中包含稀土元素。
作为一种更优选的实施方式,所述催化剂中,活性元素为镍,改性元素为稀土元素。
作为一种进一步优选的实施方式,所述催化剂中,所述活性元素由铂和镍组成,所述改性元素由铒和钾组成;
其中,以元素的摩尔数计,铂、钴、铒和钾的摩尔比为
铂:钴:铒:钾=0.1%~5%:1%~10%:0.3%~5%:0.2%~5%。
根据本申请的又一方面,提供上述任一催化剂的制备方法,至少包括以下步骤:
a)将载体置于含有活性组分元素的溶液中,或者将载体置于含有活性组分元素和改性元素的溶液中,进行浸渍;
b)步骤a)所得固体经分离、干燥、空气中焙烧和氢气还原后,即得所述催化剂。
优选地,步骤a)中所述浸渍为超声浸渍,总浸渍时间为24小时~96小时,超声累计时间为2小时~10小时。
优选地,步骤a)中所述超声浸渍是间歇式超声,总浸渍时间为36小时~60小时,超声累计时间为2小时~6小时。
优选地,步骤b)所述干燥温度为60℃~200℃。
优选地,步骤b)所述干燥是在60℃~100℃下真空干燥8小时~10小时。
优选地,步骤b)所述空气中焙烧是以1℃/min~10℃/min的升温速率将温度从室温升至300℃~800℃间的某一温度,焙烧不少于1小时。
优选地,步骤b)所述空气中焙烧是以1℃/min~5℃/min的升温速率将温度从室温升至500℃~700℃间的某一温度,焙烧2小时~4小时。
优选地,步骤b)中所述氢气还原是以5℃/min~20℃/min的升温速率将温度从室温升至600℃~1000℃间的某一温度,在氢气或氢气与非活性气体的混合物中还原不少于1小时;氢气或氢气与非活性气体的混合物的流速为20mL/min~80mL/min。
优选地,步骤b)中所述氢气还原是以5℃/min~15℃/min的升温速率将温度从室温升至800℃~1000℃间的某一温度,在氢气中还原不少于1小时~2小时;氢气的流速为20mL/min~40mL/min。
优选地,所述非活性气体选自氮气、惰性气体中的至少一种。进一步优选地,所述非活性气体选自氮气、氦气、氩气中的至少一种。
根据本申请的又一方面,提供一种二氧化碳甲烷重整反应制合成气的方法,其特征在于,所述含有甲烷和二氧化碳的原料与催化剂接触,制备合成气;所述催化剂选自上述任一催化剂、根据上述任一方法制备得到的催化剂中的至少一种。
优选地,其特征在于,所述含有甲烷和二氧化碳的原料在反应温度600℃~900℃、反应压力0.1MPa~0.5MPa的条件下与所述催化剂接触,制备合成气;
所述原料气中二氧化碳和甲烷的摩尔比例为:
二氧化碳:甲烷=0.5~2。
本发明的有益效果包括但不限于:
(1)本申请所提供的催化剂,采用具有多级孔道的载体;多级孔载体引入了大孔孔道,增加了介质的扩散和传质速率,多级孔与活性组分的协同效应使得本申请所述催化剂在高温催化反应中同时具有良好的抗烧结和抗积炭性能。
(2)本申请所提供的催化剂,当加入稀土元素进行改性时,稀土元素改性组分的加入,有效地增强了催化剂的活性;甚至在更低活性组分负载量的情况下,稀土改性的催化剂表现出更高的催化转化率。
(3)本申请所提供的催化剂,当含有贵金属时,除了采用铁系金属(铁、钴、镍中的至少一种)作为第一活性组分外,还引入贵金属作为第二活性组分。贵金属与非贵金属协同作用,使得同时包含贵金属与铁系金属的催化剂比仅包含铁系金属的催化剂具有更优异的综合催化性能。一方面,引入贵金属活性组分,有利于非贵金属组分在载体中更好地分散,进一步降低活性金属组分颗粒的尺寸,获得更多的活性位点从而提高催化转化率。另一方面,小尺寸的金属活性组分颗粒与载体之间具有更强的金属-载体相互作用,可以有效地提高催化剂的高温稳定性。此外,与单纯的贵金属催化剂相比,同时包含铁系金属和贵金属的催化剂通过引入非贵金属,减少了贵金属用量,使得催化剂成本下降。总之,同时包含铁系金属和贵金属的催化剂具有较好的性价比,具有很好的应用前景。本申请所提供的催化剂,可引入改性组分(碱金属盐、碱土金属盐或稀土金属盐),进一步提升催化剂综合性能。
(4)本申请提供的催化剂,作为二氧化碳重整甲烷反应的高温稳定催化剂,可制造合成气,实现二氧化碳减排和再生利用。在常压、800℃反应条件下,表现出优异的综合催化性能(活性、选择性和稳定性),且性价比高,具有很好的应用前景。
图1是载体多级孔氧化铝微球I断面的扫描电镜照片;(a)是放大1100倍的扫描电镜照片;(b)是放大35000倍的扫描电镜图。
图2是样品CAT-I-1用于二氧化碳重整甲烷反应产物的色谱检测结果;(a)是热导检测器TCD的结果;(b)是火焰离子化检测器FID结果。
图3是样品CAT-I-1的稳定性测试结果。
图4是样品CAT-I-1反应前后的透射电镜照片;(a)是反应前样品CAT-I-1的透射电镜照片;(b)是样品CAT-I-1在800℃反应102小时后的透射电镜照片。
图5是样品CAT-II-1和DCAT-II-1的催化活性比较图;(a)是二氧化碳转化率;(b)是甲烷转化率。
图6是样品CAT-II-1用于二氧化碳重整甲烷反应产物的色谱检测结果;(a)是热导检测器TCD的结果;(b)是火焰离子化检测器FID结果。
图7样品CAT-II-1的稳定性测试结果。
图8是样品CAT-II-1反应前后的透射电镜照片;(a)是反应前样品CAT-II-1的透射电镜照片;(b)是样品CAT-II-1在800℃反应102小时后的透射电镜照片。
图9是样品CAT-III-1、CAT-III-2和CAT-III-17催化剂稳定性比较图;其中:(a)是二氧化碳转化率随时间的变化关系;(b)是甲烷转化率随时间的变化关系。
图10是样品CAT-III-1、样品CAT-III-17和CAT-III-18的透射电镜图;(a)是样品CAT-III-1的透射电镜图,(b)是样品CAT-III-17的透射电镜图,(c)是CAT-III-18的透射电镜图。
下面结合实施例详述本发明,但本发明并不局限于这些实施例。同时实施例只是给出实现制备催化剂的部分条件,但并不意味着必须满足这些条件才可以达到此目的。
如无特别说明,实施例中所采用原料均来自商业购买,仪器设备采用厂家推荐的参数设置。
实施例中,样品的扫描电镜照片采用日本日立S4800型扫描电子显微镜采集;样品的透射电镜照片在FEI公司的F20型透射电镜上采集。
实施例中,超声浸渍中采用的超声仪是昆山市超声仪器有限公司生产的KQ300ED型。
实施例中,催化剂上铁系元素、贵金属元素、碱金属元素、碱土金属元素和稀土元素的负载量采用等离子体发射光谱(ICP)在法国HORIBA JY公司的Ultima 2型仪器上分析测定。
实施例中,二氧化碳甲烷重整反应制合成气的反应产物检测在岛津GC-2014型色谱仪(TDX-01柱)上进行。
实施例中,多级孔氧化铝微球I的比表面积为197.91m2/g,大孔平均孔径为1.52μm,介孔平均孔径为9.80nm;多级孔氧化铝微球II的比表面积为200.45m2/g;大孔平均孔径为1.61μm;介孔平均孔径为10.23nm;多级孔氧化铝微球III的比表面积为213.09m2/g;大孔平均孔径为1.57μm;介孔平均孔径为11.08nm。
实施例1催化剂样品的制备及表征
取一定量的活性组分金属盐和/或改性组分金属盐溶于10mL水中配成溶液,加入5g载体,超声浸渍一段时间后,过滤除去溶剂和多余未被吸收的金属盐。将吸附了金属离子的载体在80℃真空干燥8h后,空气氛中焙烧,最后氢气还原,获得所述催化剂。
样品编号与具体实验条件、载体、原料的关系详见表1。
表1
实施例2样品表征
采用扫描电镜照片对载体多级孔氧化铝微球I、多级孔氧化铝微球II和多级孔氧化铝微球III进行了表征。以载体多级孔氧化铝微球I为典型代表,其断面扫描电镜照片如图1所示,可以看出其具有微米级的大孔和纳米孔。多级孔氧化铝微球II和多级孔氧化铝微球III的断面扫描电镜照片与图1类似。
采用透射扫描电镜观察催化剂样品上的活性组分和改性组分稀土颗粒的粒径范围,结果详见表1。
采用ICP测定催化剂样品上铁系元素、贵金属元素、碱金属元素、碱土金属元素和稀土金属元素在样品中的质量百分含量,结果详见表1。
实施例3样品CAT-I-1~CAT-I-11的催化性能
取0.2g催化剂样品CAT-I-1置于内径1cm的固定床反应器中,进行氢气在线还原后,将温度调至反应温度。将气体切换为CO2和CH4混合气,N2为内标。反应后气体经冷却后进入气相色谱检测各物质浓度,计算CO2和CH4的转化率。
反应条件与CO2和CH4转化率的关系如表2所示。
反应条件为A时,反应尾气的色谱检测结果如图2所示。由图2可以看出,本申请所提供的催化剂样品具有良好的选择性,产物中基本为合成气的主要成分:氢气和一氧化碳。
表2
CO2和CH4的转化率分别使用下列公式计算:
式中FCO2,in和FCO2,out是原料气和反应尾气中CO2的体积分流量;FCH4,in和FCH4,out分别是反应物和产物中CH4的体积分流量。
相同反应条件下,催化剂样品CAT-I-2~CAT-I-11的反应结果与CAT-I-1类似,根据催化剂制备方法的不同,CO2和CH4的转化率在±10%范围内变化。
实施例4样品CAT-I-1~CAT-I-11的催化剂稳定性评价
取0.2g催化剂样品CAT-I-1置于内径1cm的固定床反应器中,在实施例3的反应条件A下,进行催化剂稳定性评价,结果如图3所示。由图3可以看出,CAT-I-1在常压、800℃反应条件下,具有优异的稳定性,反应时间100小时内,二氧化碳和甲烷的转化率基本维持不变。
催化剂样品CAT-I-1反应前后的透射电镜照片如图4所示。图4(a)是反应前样品CAT-I-1的透射电镜照片;图4(b)是样品CAT-I-1在800℃反应102小时后的透射电镜照片。由图
4可以看出,催化剂样品上的活性组分镍颗粒在反应前后基本没有变化,没有发生烧结;而且在102小时反应催化剂内无积炭形成。
相同反应条件下,催化剂样品CAT-I-2~CAT-I-11的催化剂稳定性评价结果与CAT-I-1类似,反应时间100小时内,二氧化碳和甲烷的转化率基本维持不变。样品CAT-I-2~CAT-I-11在800℃反应102小时后的透射电镜照片与反应前的对比结果,与CAT-I-1类似,镍颗粒没有发生烧结,催化剂内无积炭形成。
实施例5催化剂样品DCAT-II-1的制备
取5mmol乙酸镍溶于10ml水中配成溶液,加入5g多级孔氧化铝微球II,浸渍48h(其中间歇超声4h),过滤除去水和多余未被吸收的乙酸镍。将吸附了镍离子的氧化铝在80℃真空干燥8h后,600℃空气氛中焙烧4h(升温速率为1℃/min),最后用高纯氢在900℃还原4h(升温速率为10℃/min),获得样品记为催化剂样品DCAT-II-1。DCAT-II-1中镍的质量百分含量为4.25%。
实施例6样品CAT-II-1与DCAT-II-1的活性比较
分别取0.2g催化剂样品CAT-II-1、DCAT-II-1置于内径1cm的固定床反应器中,持续通入15mL/min的高纯H2,以10℃/min的升温速率升至800℃还原1h,进行催化剂的氢气在线还原。通入30mL/min原料气(CO2:CH4:N2的摩尔比=47:47:6),保持0.1MPa的反应压力,将温度调至600℃,以10℃/min的升温速率,将反应温度逐渐升至850℃。催化剂样品CAT-II-1、DCAT-II-1上不同反应温度的二氧化碳和甲烷转化率对比如图5所示。
CAT-II-1中镍的质量百分含量为3.82%;DCAT-II-1中镍的质量百分含量为4.25%。由图5可以看出,催化剂中引入改性稀土元素,活性组分含量较低的CAT-II-1,二氧化碳和甲烷的转化率高于活性组分含量较高的DCAT-II-1。
实施例7样品CAT-II-1~CAT-II-15的催化反应性能评价
取0.2g催化剂样品CAT-II-1置于内径1cm固定床反应器中,进行氢气在线还原后,将温度调至反应温度。将气体切换为CO2和CH4混合气,N2为内标。反应后气体经冷却后进入气相色谱检测各物质浓度,计算CO2和CH4的转化率。
反应条件与CO2和CH4转化率的关系如表3所示。
反应条件为A时,反应尾气的色谱检测结果如图6所示。由图6可以看出,本申请所提供的催化剂具有良好的选择性,产物中基本为合成气的主要成分:氢气和一氧化碳。
表3
CO2和CH4的转化率分别使用下列公式计算:
式中FCO2,in和FCO2,out是原料气和反应尾气中CO2的体积分流量;FCH4,in和FCH4,out分别是反应物和产物中CH4的体积分流量。
相同反应条件下,催化剂样品CAT-II-2~CAT-II-15的反应结果与CAT-II-1类似,根据催化剂制备方法的不同,CO2和CH4的转化率在±10%范围内变化。
实施例8CAT-II-1~CAT-II-15稳定性评价
取0.2g催化剂样品CAT-II-1置于内径1cm的固定床反应器中,在实施例7的反应条件A下,进行催化剂稳定性评价,结果如图7所示。由图7可以看出,本申请所提供的催化剂,在常压、800℃反应条件下,具有优异的稳定性,反应时间100小时内,二氧化碳和甲烷的转化率基本维持不变。
催化剂样品CAT-II-1反应前后的透射电镜照片如图8所示。图8(a)是反应前样品CAT-II-1的透射电镜照片;图8(b)是样品CAT-II-1在800℃反应102小时后的透射电镜照片。由图8可以看出,催化剂样品上的活性组分和改性组分的颗粒在反应前后基本没有变化,没有发生烧结;而且在102小时反应催化剂内无积炭形成。
相同反应条件下,催化剂样品CAT-II-2~CAT-II-15的催化剂稳定性评价结果与CAT-II-1类似,反应时间100小时内,二氧化碳和甲烷的转化率基本维持不变。样品CAT-II-2~CAT-II-15在800℃反应102小时后的透射电镜照片与反应前的对比结果,与CAT-II-1类似,催化剂样品上的活性组分和改性组分的颗粒没有发生烧结,催化剂内无积炭形成。
实施例9样品CAT-III-1~CAT-III-2的催化反应性能评价
取0.2g催化剂样品CAT-III-1置于内径1cm固定床反应器中,进行氢气在线还原后,将温度调至反应温度。将气体切换为CO2和CH4混合气,N2为内标。反应后气体经冷却后进入气相色谱检测各物质浓度,计算CO2和CH4的转化率。
反应条件与CO2和CH4转化率的关系如表4所示。
表4
CO2和CH4的转化率分别使用下列公式计算:
式中FCO2,in和FCO2,out是原料气和反应尾气中CO2的体积分流量;FCH4,in和FCH4,out分别是反应物和产物中CH4的体积分流量。
相同反应条件下,催化剂样品CAT-III-2~CAT-III-29的反应结果与CAT-III-1类似,根据催化剂制备方法的不同,CO2和CH4的转化率在±20%范围内变化。
实施例10样品CAT-III-1~CAT-III-2的催化剂稳定性评价
分别取0.2g催化剂样品CAT-III-1、CAT-III-2和CAT-III-17置于内径1cm的固定床反应器中,在实施例9的反应条件A下,进行催化剂稳定性评价。
催化剂CAT-III-1、CAT-III-2和CAT-III-17的稳定性测试结果如图9(a)和图9(b)所示。由图9可以看出,活性元素中包含贵金属和铁系元素的催化剂CAT-III-1和CAT-III-2,在常压、800℃反应条件下,在反应时间204小时内,二氧化碳和甲烷的转化率维持较好的稳定性。活性元素中未包含贵金属元素的,催化剂稳定性略低。催化剂稳定性:CAT-III-2>CAT-III-1>CAT-III-17,表明添加贵金属提高了催化剂的稳定性。同时,图9(a)
和图9(b)中的数据也表明催化剂中引入贵金属后,除了稳定性得以提高外,二氧化碳和甲烷的转化率也显著提高了。进一步再加入少量稀土盐改性后,转化率又略微提高一点。
实施例11贵金属加入对样品的影响
以样品CAT-III-1为典型代表,其透射电镜图如图10(a)所示,由图10可以看出,在含有贵金属的催化剂上,金属颗粒的粒径均匀,粒径范围在5nm~15nm之间,且金属颗粒在载体上分散均匀。图10(b)和图10(c)分别为样品CAT-III-17和CAT-III-18的透射电镜图。对比图10(a)~图10(c)可以看出,在非贵金属催化剂中加入稀土元素后,活性金属颗粒变小;而加入贵金属后颗粒尺寸变小的程度要明显大于添加稀土盐的情况。这很好地解释了包含贵金属的催化剂样品具有更高的二氧化碳和甲烷转化率的原因。同时,小尺寸的金属活性组分颗粒与载体之间具有更强的相互作用,有利于提高催化剂的高温稳定性。与添加改性组分(比如稀土元素)相比,添加贵金属活性组分对铁系催化剂综合性能的改善程度要明显大得多。
以上所述,仅是本发明的几个实施例,并非对本发明做任何形式的限制,虽然本发明以较佳实施例揭示如上,然而并非用以限制本发明,任何熟悉本专业的技术人员,在不脱离本发明技术方案的范围内,利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例,均属于本发明技术方案范围内。
Claims (13)
- 一种催化剂,包括载体和分散在载体上的活性组分,其特征在于,所述载体选自无机氧化物中的至少一种,所述载体包含大孔和介孔;所述活性组分含有活性元素,所述活性元素包括铁系元素,所述铁系元素选自铁、钴、镍中的至少一种。
- 根据权利要求1所述的催化剂,其特征在于,所述大孔的平均孔径大于50nm,所述介孔的平均孔径为1nm~50nm;优选地,所述大孔的平均孔径为1μm~2μm;优选地,所述介孔的平均孔径为5nm~15nm。优选地,所述载体的比表面积为100m2/g~350m2/g。
- 根据权利要求1所述的催化剂,其特征在于,所述活性元素中包括贵金属元素;优选地,所述贵金属元素选自金、银、钌、铑、钯、锇、铱、铂中的至少一种。
- 根据权利要求1或3所述的催化剂,其特征在于,所述活性元素中铁系元素在催化剂中的质量百分含量为1%~10%;优选地,所述活性元素中铁系元素在催化剂中的质量百分含量为3%~6%;优选地,所述活性元素中贵金属元素在催化剂中的质量百分含量为0.1%~5%;进一步优选地,所述活性元素中贵金属元素在催化剂中的质量百分含量为0.5%~3%。
- 根据权利要求1所述的催化剂,其特征在于,所述催化剂含有分散在载体上的改性组分;所述改性组分含有改性元素,所述改性元素选自碱金属元素、碱土金属元素、稀土金属元素中的至少一种;优选地,所述碱金属元素在催化剂中的质量百分含量为0.1%~10%;进一步优选地,所述碱金属元素在催化剂中的质量百分含量为0.1%~5%;优选地,所述碱土金属元素在催化剂中的质量百分含量为0.1%~10%;进一步优选地,所述碱土金属元素在催化剂中的质量百分含量为0.1%~5%;优选地,所述稀土金属元素在催化剂中的质量百分含量为0.1%~10%;进一步优选地,所述稀土金属元素在催化剂中的质量百分含量为0.1%~6%。
- 根据权利要求1或5所述的催化剂,其特征在于,所述分散在载体上的活性组分的粒径分布在1nm~50nm之间;优选地,所述分散在载体上的活性组分的粒径分布在1nm~15nm之间;优选地,所述分散在载体上的改性组分的粒径分布在1nm~50nm之间;进一步优选地,所述分散在载体上的改性组分的粒径分布在1nm~15nm之间。
- 根据权利要求5所述的催化剂,其特征在于,所述活性元素由铂和镍组成,所述改性元素由铒和钾组成;其中,以元素的摩尔数计,铂、钴、铒和钾的摩尔比为铂:钴:铒:钾=0.1%~5%:1%~10%:0.3%~5%:0.2%~5%。
- 权利要求1至7任一项所述催化剂的制备方法,其特征在于,至少包括以下步骤:a)将载体置于含有活性组分元素的溶液中,或者将载体置于含有活性组分元素和改性元素的溶液中,进行浸渍;b)步骤a)所得固体经分离、干燥、空气中焙烧和氢气还原后,即得所述催化剂。
- 根据权利要求8所述的方法,其特征在于,步骤a)中所述浸渍为超声浸渍,总浸渍时间为24小时~96小时,超声累计时间为2小时~10小时;优选地,步骤a)中所述超声浸渍是间歇式超声,总浸渍时间为36小时~60小时,超声累计时间为2小时~6小时。
- 根据权利要求8所述的方法,其特征在于,步骤b)所述干燥温度为60℃~200℃;优选地,步骤b)所述干燥是在60℃~100℃下真空干燥8小时~10小时;进一步优选地,步骤b)所述空气中焙烧是以1℃/min~10℃/min的升温速率将温度从室温升至300℃~800℃间的某一温度,焙烧不少于1小时;更进一步优选地,步骤b)所述空气中焙烧是以1℃/min~5℃/min的升温速率将温度从室温升至500℃~700℃间的某一温度,焙烧2小时~4小时;优选地,步骤b)中所述氢气还原是以5℃/min~20℃/min的升温速率将温度从室温升至600℃~1000℃间的某一温度,在氢气或氢气与非活性气体的混合物中还原不少于1小时;氢气或氢气与非活性气体的混合物的流速为20mL/min~80mL/min;进一步优选地,步骤b)中所述氢气还原是以5℃/min~15℃/min的升温速率将温度从室温升至800℃~1000℃间的某一温度,在氢气中还原不少于1小时~2小时;氢气的流速为20mL/min~40mL/min。
- 根据权利要求10所述的方法,其特征在于,所述非活性气体选自氮气、惰性气体中的至少一种。
- 二氧化碳甲烷重整反应制合成气的方法,其特征在于,所述含有甲烷和二氧化碳的原料与催化剂接触,制备合成气;所述催化剂选自权利要求1至7任一项所述的催化剂、根据权利要求8至11任一项所述方法制备得到的催化剂中的至少一种。
- 根据权利要求12所述的方法,其特征在于,所述含有甲烷和二氧化碳的原料在反应温度600℃~900℃、反应压力0.1MPa~0.5MPa的条件下与所述催化剂接触,制备合成气;所述原料气中二氧化碳和甲烷的摩尔比例为:二氧化碳:甲烷=0.5~2。
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