CN106607033A - Supported catalyst, preparation method and application thereof and method for preparing synthetic gas through methane dry reforming - Google Patents

Abstract

The invention provides a supported catalyst, wherein the catalyst contains a carrier and an active metal component and an auxiliary agent loaded on the carrier, wherein the active metal component is a Ni component and/or a Co component, The dispersion degree of the active metal component is 6-15%. The invention also provides a preparation method and application of the supported catalyst and a method for producing synthesis gas by dry reforming methane. The supported catalyst provided by the invention can obtain significantly improved dispersion of active metal components and smaller grain size of active metal, and has higher catalytic activity, stability and anti-coking performance.

Description

A supported catalyst, its preparation method and application, and a method for producing synthesis gas from methane dry reforming

technical field

The present invention relates to the research field of supported catalysts, in particular to a supported catalyst, a method for preparing a supported catalyst, a supported catalyst prepared by the method, and the supported catalyst used in methane dry reforming reaction The application in and the method of dry reforming of methane to synthesis gas.

Background technique

The methane dry reforming reaction uses the greenhouse gases CH ₄ and CO ₂ as raw materials to produce synthesis gas with a lower H ₂ /CO ratio, which is very suitable as Fischer-Tropsch synthesis for long-chain hydrocarbons, ammonia synthesis, alkylation reaction, methanol synthesis Raw materials for industrial processes. This process can not only realize the resource utilization of _CO2 , but also provides an effective way for the efficient utilization of methane. Therefore, if the commercial application of this process can be realized, it will not only have great practical significance for alleviating the energy crisis and changing the production process and raw material route of some chemical products, but also for reducing the emission of greenhouse gases and alleviating the damage caused by the "greenhouse effect". The destruction of the global ecological environment has far-reaching historical significance. Ni-based catalysts show activity comparable to that of noble metals in methane dry reforming reactions, but the catalysts have serious problems of rapid deactivation due to carbon deposition and sintering, especially during high-temperature reactions. It will continue to migrate and aggregate and grow up, resulting in a continuous decrease in catalyst activity and aggravating the occurrence of carbon deposition. Therefore, how to keep the active metal in the catalyst stable and prevent it from migrating and aggregating during the high-temperature reaction process and causing the size of the metal particles to grow is the key to the preparation of high-activity and high-stability Ni-based catalysts.

In order to prepare a Ni-based catalyst with a stable structure, people usually use the co-precipitation method to prepare the catalyst (Journal of Catalysis, 249 (2007) 300); Catalysis Today, 45 (1998) 35), which can make the active metal Ni in the whole catalyst The bulk phase space is evenly distributed, and other components are used as space barriers to prevent the migration and aggregation of active metals during the high-temperature reaction process. However, the co-precipitation method has lengthy operation steps, many process variables, and it is difficult to guarantee the repeatability of the catalyst. In comparison, the impregnation method is a relatively simple catalyst preparation method, and it is also the most widely used catalyst preparation method in industry. However, the catalysts prepared by the traditional impregnation method have low dispersion of active metals, large metal grain size, low catalyst activity and poor stability. Therefore, it is imperative to develop an efficient and easy-to-use catalyst.

Contents of the invention

The purpose of the present invention is to overcome the defects of low activity stability and poor anti-coking performance of methane dry reforming catalysts in the prior art, and provide a new load with high activity and stability and good anti-coking performance Type catalyst, its preparation method and application, and the method of methane dry reforming to synthesis gas.

Specifically, the present invention provides a supported catalyst, wherein the catalyst contains a carrier and an active metal component and an auxiliary agent loaded on the carrier, wherein the active metal component is a Ni component and/or a Co component, the dispersion of the active metal component is 6-15%.

The present invention also provides a method for preparing a supported catalyst, the method comprising, in the presence of a surfactant, contacting an impregnating solution with a carrier, followed by drying and calcining, wherein the impregnating solution contains an active metal component Soluble compounds and soluble compounds of adjuvants.

The present invention also provides the supported catalyst prepared by the above method.

The invention also provides the application of the supported catalyst in methane dry reforming reaction.

The present invention also provides a method for producing synthesis gas by dry reforming of methane, the method comprising contacting methane and carbon dioxide with a catalyst under the condition of dry reforming of methane for producing synthesis gas, wherein the catalyst is the above-mentioned supported catalyst.

The supported catalyst provided by the invention and the supported catalyst prepared by the preparation method provided by the invention can obtain significantly improved dispersion of active metal components and a smaller active metal grain size, thereby greatly improving catalytic activity and stability performance and anti-coking properties. The reason why the catalyst in the present invention has good performance may be that in the catalyst preparation process, the active metal and the auxiliary agent are simultaneously loaded on the carrier in the form of co-impregnation, and the two are formed into a new composite metal oxide phase by high temperature treatment. structure, so that the prepared catalyst has high dispersion of active metals and small grain size, and due to the steric barrier effect of additives, it can effectively prevent the migration and aggregation of active metal components during high temperature reaction; thus maintaining its stability , high catalytic activity and anti-coking performance. As can be seen from the reaction performance comparison charts of the catalysts of Example 1 and Comparative Example 1, the catalyst provided by the present invention can operate continuously and stably with high activity for more than 1500 hours at an ultra-high space velocity (120000ml g ^-1 h ^-1 ) Not deactivated.

Other features and advantages of the present invention will be described in detail in the detailed description that follows.

Description of drawings

The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the description, together with the following specific embodiments, are used to explain the present invention, but do not constitute a limitation to the present invention. In the attached picture:

Fig. 1 is the reaction performance of the catalyst catalytic methane dry reforming reaction of embodiment 1 gained;

Fig. 2 is the reaction performance of the catalyst catalytic methane dry reforming reaction obtained in comparative example 1;

Fig. 3 is the reaction performance of the catalyst obtained in Comparative Example 2 to catalyze the methane dry reforming reaction.

detailed description

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, not to limit the present invention.

The invention provides a supported catalyst, wherein the catalyst contains a carrier and an active metal component and an auxiliary agent loaded on the carrier, wherein the active metal component is a Ni component and/or a Co component, The dispersion degree of the active metal component is 6-15%. In order to obtain better catalytic activity and anti-coke performance, preferably, the dispersion of the active metal component is 10-14%.

In the present invention, the average particle diameter of the active metal component may be 2-50 nm, preferably 2-10 nm.

According to the supported catalyst provided by the present invention, the content of the active metal component can be determined with reference to the prior art. For example, based on the total weight of the catalyst, the content of the active metal component may be 2-20% by weight, preferably 3-15% by weight, more preferably 4-10% by weight, based on the metal element. It should be noted that since the active metal components actually exist in the form of oxides, and the above-mentioned active metal components are calculated by the content of metal elements, the content of the active metal components is smaller than the actual content. Obviously, when the catalyst only contains the above-mentioned active metal components, additives and supports, the content of the active metal components, additives and supports in terms of oxide must satisfy 100%.

In the present invention, the content of the active metal component is measured by the ICP method.

In the present invention, in terms of metal atoms, the molar ratio of the auxiliary agent to the active metal component may be 0.01-5:1, preferably 0.1-2:1.

In the present invention, the type of the auxiliary agent is a conventional choice in the field. For example, the additives can be metal oxide additives, preferably alkaline earth and/or rare earth metal oxide additives; more preferably MgO, CaO, BaO, La ₂ O ₃ , CeO ₂ , Sm ₂ O ₃ , ZrO ₂ and at least one of Y ₂ O ₃ .

According to the present invention, the type of the carrier is not particularly limited, and can be a conventional choice in the art. For example, the support may be a one-component oxide support or a two-component or three-component composite oxide support. Preferably, the carrier is selected from SiO ₂ , TiO ₂ , MgO, Al ₂ O ₃ , ZrO ₂ , CeO ₂ , La ₂ O ₃ , SiO ₂ -Al ₂ O ₃ , TiO ₂ -SiO ₂ , Al ₂ O One or more of ₃ -MgO and TiO ₂ -SiO ₂ -Al ₂ O ₃ .

In the present invention, the shape of the carrier is a conventional choice in the art. For example, the shape of the carrier may be at least one of cylinder, sphere, clover, four-leaf clover, disc and Raschig ring, preferably four-leaf clover and/or Raschig ring.

The present invention also provides a method for preparing a supported catalyst, the method comprising, in the presence of a surfactant, contacting an impregnating solution with a carrier, followed by drying and calcining, wherein the impregnating solution contains an active metal component Soluble compounds and soluble compounds of adjuvants.

In the present invention, the amount of the surfactant used is not particularly limited. But in order to form the catalyst with higher activity and better stability, the mol ratio of the consumption of the soluble compound of the surfactant and the active metal component in terms of metal atoms can be 0.001-2:1, preferably 0.001-1: 1, more preferably 0.01-0.8:1.

In the present invention, the type of the surfactant can be conventionally selected in the art. For example, the surfactant can be selected from at least one of anionic surfactants, amphoteric surfactants and nonionic surfactants; preferably stearic acid, oleic acid, lauric acid, lecithin, lauryl At least one of alkylalanine, alkyl dimethyl betaine, fatty acid glycerides, polyols, Tween 60 and P123; more preferably at least one of P123, oleic acid and Tween 60.

In the present invention, the amount of the soluble compound of the active metal component is not particularly limited, and may be a conventional choice in the art. For example, in order to make the obtained catalyst, based on the total weight of the catalyst, the content of the active metal component is 2-20% by weight, preferably 3-15% by weight, more preferably 4% by weight, based on the metal element. -10% by weight, relative to 100 parts by weight of the carrier, the amount of the soluble compound of the active metal component may be 10-100 parts by weight, preferably 15-75 parts by weight, more preferably 20-50 parts by weight.

According to the present invention, the type of the soluble compound of the active metal component is well known to those skilled in the art and can be a conventional choice in the art. For example, the soluble compound of the active metal component may be selected from Ni(NO ₃ ) ₂ ·6H ₂ O, Co(NO ₃ ) ₂ ·6H ₂ O, Ni(acac) ₂ , Co(acac) ₃ , Ni( At least one of CH ₃ COO) ₂ ·6H ₂ O and Co(CH ₃ COO) ₂ ·6H ₂ O, preferably Ni(NO ₃ ) ₂ ·6H ₂ O and/or Co(NO ₃ ) ₂ ·6H ₂ O.

According to the present invention, the support may be a single-component oxide support or a two-component or three-component composite oxide support. Preferably, the carrier is selected from SiO ₂ , TiO ₂ , MgO, Al ₂ O ₃ , ZrO ₂ , CeO ₂ , La ₂ O ₃ , SiO ₂ -Al ₂ O ₃ , TiO ₂ -SiO ₂ , Al ₂ O One or more of ₃ -MgO and TiO ₂ -SiO ₂ -Al ₂ O ₃ .

According to the present invention, in the impregnating solution, in terms of metal elements, the total concentration of the soluble compounds of the active metal component and the soluble compounds of the auxiliary agent can be 21.8-162.8 g/liter, and the amount of the carrier is such that the obtained catalyst contains catalyst Based on the total weight of the active metal component, the content of the active metal component in terms of metal elements is 2-20% by weight, preferably 3-15% by weight, more preferably 4-10% by weight.

In the present invention, the amount of the auxiliary agent is not particularly limited. For example, in terms of metal atoms, the molar ratio of the soluble compound of the additive to the soluble compound of the active metal component may be 0.01-5:1, preferably 0.1-2:1.

In the present invention, the type of the soluble compound of the auxiliary agent is a conventional choice in the art. For example, the soluble compound of the auxiliary agent can be selected from alkaline earth and/or rare earth metal soluble compounds; preferably, the soluble compound of the auxiliary agent is selected from magnesium salt, calcium salt, strontium salt, barium salt, cerium salt, lanthanum salt , at least one of zirconium salt and yttrium salt; more preferably, the soluble compound of the auxiliary agent is selected from at least one of magnesium salt, barium salt, lanthanum salt and yttrium salt, more preferably lanthanum salt and/or Magnesium salt.

According to the present invention, the conditions for contacting the impregnating solution with the carrier are not particularly limited. For example, the conditions for contacting the impregnation solution with the carrier include: the temperature may be 10-50° C., preferably 15-30° C.; the time may be 0.5-10 hours, preferably 2-5 hours.

The method of contacting the impregnating solution with the support is not particularly limited in the present invention. For example, the surfactant can be mixed with an impregnation solution containing a soluble compound of the active metal component prior to contacting the support.

In the present invention, the contact product of the impregnating solution and the carrier is dried and calcined, wherein the conditions of drying and calcined are well known to those skilled in the art. For example, the drying conditions include: the temperature may be 80-140°C, preferably 100-120°C; the time may be 1-10 hours, preferably 5-10 hours. The temperature of the calcination can be 400-1000°C, preferably 500-800°C; the time can be 1-10 hours, preferably 2-6 hours.

The present invention also provides the supported catalyst prepared by the above method.

The invention also provides the application of the supported catalyst in preparing synthesis gas by dry reforming of methane.

When the catalyst prepared by the method provided by the present invention is used for methane dry reforming reaction, the active metal needs to be reduced and activated in the presence of hydrogen before the reaction. Wherein, the conditions for reduction activation include: the reduction temperature can be 300-800°C, preferably 400-750°C, the reduction time can be 0.5-10 hours, preferably 1-5 hours; the reduction activation can be carried out in pure hydrogen , can also be carried out in the mixed gas of hydrogen and inert gas, if it is carried out in the mixed gas of hydrogen and nitrogen and/or argon, the reduction pressure can be 0-2MPa, preferably 0-1MPa. In the present invention, the pressure is gauge pressure.

The present invention also provides a method for producing synthesis gas by dry reforming of methane, the method comprising contacting methane and carbon dioxide with a catalyst under the condition of dry reforming of methane for producing synthesis gas, wherein the catalyst is the above-mentioned supported catalyst of the present invention catalyst.

Wherein, the method that methane and carbon dioxide contact with described catalyst is not particularly limited, can be the routine selection of this field, for example, can send methane and carbon dioxide respectively into the reactor and contact with catalyst simultaneously, also can form methane and carbon dioxide The mixture is then contacted with the catalyst, preferably a mixture of methane and carbon dioxide is then contacted with the catalyst.

When the catalyst prepared according to the carrier provided by the present invention is used to catalyze the reaction of methane and _CO2 to prepare synthesis gas, a fixed-bed reactor or a fluidized-bed reactor is used. The conditions for dry reforming of methane to synthesis gas include: the molar ratio of methane and carbon dioxide can be 0.7-1.1:1, preferably 0.8-1:1; the reaction temperature can be 550-850°C, preferably 600-800°C The pressure can be 0-3MPa, preferably 0-1MPa; the total space velocity of the feed gas can be 2000-120000ml·g ^-1 ·h ^-1 , preferably 60000-120000ml·g ^-1 ·h ^-1 .

The present invention will be described in detail below by way of examples.

In the following examples, the performance test of the product is carried out by the following methods:

1) The metal dispersion is measured by the hydrogen chemisorption method using a Micromeritics (ASAP-2010C) chemisorption instrument. Specifically, 0.2 g of the sample was degassed at 300°C for 1 hour, then heated to 700°C for 2 hours, and then cooled to 40°C for hydrogen chemical adsorption. Calculate the dispersion degree of active metal component and the average particle diameter of metal particles according to the amount of chemically adsorbed hydrogen by the following formula afterwards;

Active metal dispersion D:

Average particle size d of active metal particles:

Among them, V _ad refers to the monolayer adsorption amount of hydrogen under standard state, in mL; W _s is the sample mass, in g; FW _Me is the molar mass of metal _{Me in g/mol; F Me is} the The loading capacity of the metal, the unit is %; V _m is the molar gas volume in the index state, the unit is mL/mol; SA _Me is the specific surface area of the metal, the unit is m ² /g; ρ _Me is the density of the metal, the unit is kg/m ³ ;

2) Utilize gas chromatography on-line sampling analysis to calculate the tail gas composition;

3) The content of active metal components is measured by ICP method.

Example 1

This embodiment is used to illustrate the preparation method and application of the catalyst provided by the invention and the catalyst.

(1) Catalyst preparation

Dissolve 1.765g of Ni(NO ₃ ) ₂ 6H ₂ O and 1.167g of Mg(NO ₃ ) ₂ 6H ₂ O in 8.4ml of deionized water and stir to dissolve, then add 0.61g of P123 and mix well to obtain an impregnation solution . Take 4g of _SiO2 carrier and disperse it into the impregnating solution, let it stand at 25°C for 2 hours, evaporate the water to dryness, and then place it in an oven for 10 hours at 120°C. The dried sample was calcined in a muffle furnace at 600°C for 3 hours, and the obtained catalyst was recorded as 6Mg-Ni/SiO ₂ . In terms of metal atoms, the molar ratio of the additive to the active metal component is 0.75:1, and the content of Ni in the active metal component in terms of metal elements is 8% by weight. The dispersion degree of the active metal component in the catalyst is 12.7%, and the average particle diameter of the active metal component is 5.4nm.

(2) Catalyst evaluation

Weigh 0.1g of the above-mentioned 6Mg-Ni/ _SiO2 catalyst, dilute it to 2ml with 40-60 mesh quartz sand, put it into a quartz tube reactor with an inner diameter of 8mm, and activate it by reducing at 700°C for 3 hours under normal pressure in a pure hydrogen atmosphere . After the reduction, the temperature was raised to 750°C under a hydrogen atmosphere, and the raw material gas (CH ₄ /CO ₂ =1/1) was switched for reaction. The reaction space velocity was 120000ml·g ^-1 ·h ^-1 , and the reaction pressure was normal pressure. After the reaction was carried out stably for 80 hours, online sampling was performed by gas chromatography and the composition of the tail gas was analyzed. Calculated: X _CH4 = 62.9%, X _CO2 = 61.5%, H ₂ /CO = 0.96.

The stability evaluation results of the catalyst obtained in Example 1 are shown in FIG. 1 , specifically the methane and carbon dioxide conversion rates in the methane dry reforming reaction catalyzed by the catalyst with a reaction time of 0-1700 hours.

Example 2

This embodiment is used to illustrate the preparation method and application of the catalyst provided by the invention and the catalyst.

(1) Catalyst preparation

Dissolve 0.873 g of Ni(NO ₃ ) ₂ 6H ₂ O, 0.872 g of Co(NO ₃ ) ₂ 6H ₂ O and 1.955 g of La(NO ₃ ) ₃ 6H ₂ O in 8.4 ml of deionized water and stir Dissolve, then add 1.57g of Tween 60, mix evenly to obtain an impregnating solution. Take 4g of _SiO2 carrier and disperse it into the impregnating solution, let it stand at 30°C for 2 hours, evaporate the water to dryness, and then place it in an oven for 7 hours at 100°C. The dried sample was calcined in a muffle furnace at 800°C for 2 hours, and the obtained catalyst was recorded as 4La-Ni-Co/SiO ₂ . In terms of metal atoms, the molar ratio of the additive to the active metal component is 0.75:1, and the total content of the active metal Ni and Co in terms of metal elements is 8% by weight. The dispersion degree of the active metal Ni component in the catalyst is 10.9%, and the average particle diameter of the active metal component is 9.1 nm.

(2) Catalyst evaluation

The catalyst was activated under the same conditions as in Example 1 and the methane dry reforming reaction was carried out. After the reaction was carried out stably for 80 hours, online sampling was performed by gas chromatography and the composition of the tail gas was analyzed. Calculated: X _CH4 = 65.4%, X _CO2 = 66.7%, H ₂ /CO = 1.02.

Example 3

This embodiment is used to illustrate the preparation method and application of the catalyst provided by the invention and the catalyst.

(1) Catalyst preparation

Dissolve 2.81g of Ni(NO ₃ ) ₂ 6H ₂ O and 0.31g of Mg(NO ₃ ) ₂ 6H ₂ O in 8.4ml of deionized water and stir to dissolve, then add 1.36g of oleic acid, mix well to obtain impregnation solution. Take 4g of _SiO2 carrier and disperse it into the impregnating solution, let it stand at 15°C for 5 hours, evaporate the water to dryness, and then place it in an oven for 5 hours at 110°C. The dried sample was calcined in a muffle furnace at 500°C for 6 hours, and the obtained catalyst was recorded as 1Mg-Ni/SiO ₂ . In terms of metal atoms, the molar ratio of the additive to the active metal component is 0.125:1, and the content of the active metal Ni in terms of metal elements is 12% by weight. The dispersion degree of the active metal component in the catalyst is 12.4%, and the average particle diameter of the active metal component is 6.1 nm.

(2) Catalyst evaluation

The catalyst was activated under the same conditions as in Example 1 and the methane dry reforming reaction was carried out. After the reaction was carried out stably for 80 hours, online sampling was performed by gas chromatography and the composition of the tail gas was analyzed. Calculated: X _CH4 = 58.6%, X _CO2 = 59.7%, H ₂ /CO = 1.01.

Example 4

This embodiment is used to illustrate the preparation method and application of the catalyst provided by the invention and the catalyst.

(1) Catalyst preparation

The catalyst was prepared according to the method in Example 1, except that the amount of P123 used was 0.348 g, and the obtained catalyst was recorded as 6Mg-Ni/SiO ₂ -2. The dispersion degree of the active metal component in the catalyst is 11.6%, and the average particle diameter of the active metal component is 5.8nm.

(2) Catalyst evaluation

The catalyst was activated under the same conditions as in Example 1 and the methane dry reforming reaction was carried out. After the reaction was carried out stably for 80 hours, online sampling was performed by gas chromatography and the composition of the tail gas was analyzed. Calculated: X _CH4 = 59.3%, X _CO2 = 60.4%, H ₂ /CO = 1.02.

Example 5

This embodiment is used to illustrate the preparation method and application of the catalyst provided by the invention and the catalyst.

(1) Catalyst preparation

The catalyst was prepared according to the method in Example 1, except that the amount of Mg(NO ₃ ) ₂ ·6H ₂ O was 3.08 g, and the obtained catalyst was recorded as 10Mg-Ni/SiO ₂ -3. In terms of metal atoms, the molar ratio of the auxiliary agent to the active metal component is 2:1, and the content of Ni in the active metal component in terms of metal elements is 7.4% by weight. The dispersion degree of the active metal component in the catalyst is 13.5%, and the average particle diameter of the active metal component is 4.7nm.

(2) Catalyst evaluation

The catalyst was activated under the same conditions as in Example 1 and the methane dry reforming reaction was carried out. After the reaction was carried out stably for 80 hours, online sampling was performed by gas chromatography and the composition of the tail gas was analyzed. Calculated: X _CH4 = 64.6%, X _CO2 = 62.9%, H ₂ /CO = 1.01.

Example 6

This embodiment is used to illustrate the preparation method and application of the catalyst provided by the invention and the catalyst.

(1) Catalyst preparation

The catalyst was prepared according to the method in Example 1, except that magnesium oxide was used as the carrier, and the obtained catalyst was denoted as 6Mg-Ni/MgO. The dispersion degree of the active metal component in the catalyst is 13.1%, and the average particle diameter of the active metal component is 4.9nm.

(2) Catalyst evaluation

The catalyst was activated under the same conditions as in Example 1 and the methane dry reforming reaction was carried out. After the reaction was carried out stably for 80 hours, online sampling was performed by gas chromatography and the composition of the tail gas was analyzed. Calculated: X _CH4 = 63.7%, X _CO2 = 61.9%, H ₂ /CO = 1.0.

Example 7

This embodiment is used to illustrate the preparation method and application of the catalyst provided by the invention and the catalyst.

(1) Catalyst preparation

The catalyst was prepared according to the method in Example 1, except that the support was Al ₂ O ₃ -MgO composite support, and the obtained catalyst was recorded as 6Mg-Ni/Al ₂ O ₃ -MgO. The dispersion degree of the active metal component in the catalyst is 13.9%, and the average particle diameter of the active metal component is 4.2nm.

(2) Catalyst evaluation

The catalyst was activated under the same conditions as in Example 1 and the methane dry reforming reaction was carried out. After the reaction was carried out stably for 80 hours, online sampling was performed by gas chromatography and the composition of the tail gas was analyzed. Calculated: X _CH4 = 66.7%, X _CO2 = 65.1%, H ₂ /CO = 1.01.

Comparative example 1

This comparative example is used to illustrate the reference catalyst and the preparation method of the catalyst and its application.

(1) Catalyst preparation

The catalyst was prepared according to the method in Example 1, except that the surfactant P123 was not used, and the obtained catalyst was designated as 6Mg-Ni/SiO ₂ -D1. The dispersion degree of the active metal component in the catalyst is 2.3%, and the average particle diameter of the active metal component is 44.1nm.

(2) Catalyst evaluation

The catalyst was activated under the same conditions as in Example 1 and the methane dry reforming reaction was carried out. After the reaction was carried out stably for 28 hours, online sampling was performed by gas chromatography and the composition of the tail gas was analyzed. Calculated: X _CH4 = 16.3%, X _CO2 = 21.1%, H ₂ /CO = 0.98.

The reaction performance of the catalyst obtained in Comparative Example 1 is shown in FIG. 2 , specifically the conversion rate of methane and carbon dioxide in the methane dry reforming reaction catalyzed by the catalyst with a reaction time of 0-30 hours.

Comparative example 2

This comparative example is used to illustrate the reference catalyst and the preparation method of the catalyst and its application.

(1) Catalyst preparation

The catalyst was prepared according to the method in Example 1, except that no auxiliary agent was used, and the obtained catalyst was recorded as Ni/SiO ₂ . The dispersion degree of the active metal component in the catalyst is 5.4%, and the average particle diameter of the active metal component is 18.7nm.

(2) Catalyst evaluation

The catalyst was activated under the same conditions as in Example 1 and the methane dry reforming reaction was carried out. After the reaction was carried out stably for 80 hours, online sampling was performed by gas chromatography and the composition of the tail gas was analyzed. Calculated: X _CH4 = 32.2%, X _CO2 = 21.0%, H ₂ /CO = 1.02.

The reaction performance of the catalyst obtained in Comparative Example 2 is shown in FIG. 3 , specifically the conversion rate of methane and carbon dioxide in the methane dry reforming reaction catalyzed by the catalyst with a reaction time of 0-100 hours.

As can be seen from the above results, using the preparation method of the catalyst provided by the present invention and the prepared catalyst can continuously and efficiently run stably for more than 1500 hours, and can also obtain relatively high space velocity at a high space velocity of 120000ml·g ^-1 ·h ^-1 High conversion of methane and carbon dioxide. This shows that the catalyst of the present invention has better reactivity, stability and anti-coking performance.

As can be seen from the results of Examples 1-5, even if the silica carrier with lower reactivity, after using the method of the present invention to make a catalyst, the dispersion degree of the active metal component can be obtained to be 6-15%, The catalyst has better reactivity, stability and anti-coking performance, and can run continuously, efficiently and stably for more than 1500 hours.

From the results of Example 1 and Comparative Example 1 and Comparative Example 2, it can be seen that the preparation method of the catalyst provided by the present invention and the prepared catalyst have better reactivity and stability and anti-coking performance, and can be continuously and efficiently Stable operation for more than 1500 hours. However, the catalysts of Comparative Example 1 and Comparative Example 2 that did not adopt the method of the present invention had low reactivity and poor stability, and their activity dropped significantly after 30 hours of operation.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

In addition, it should be noted that the various specific technical features described in the above specific implementation manners may be combined in any suitable manner if there is no contradiction. In order to avoid unnecessary repetition, various possible combinations are not further described in the present invention.

In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (16)

1. a kind of loaded catalyst, it is characterised in that the catalyst contains carrier and is supported on Active metal component and auxiliary agent on carrier, wherein, the active metal component is Ni components and/or Co Component, the dispersion of the active metal component is 6-15%.

2. catalyst according to claim 1, wherein, the granule of the active metal component is put down Particle diameter is 2-50nm, preferably 2-10nm.

3. catalyst according to claim 1 and 2, wherein, with the gross weight of the catalyst On the basis of, with elemental metal, the content of the active metal component is 2-20 weight %, preferably 3-15 weight %, more preferably 4-10 weight %.

4. the catalyst according to any one in claim 1-3, wherein, with metal atoms, The auxiliary agent is 0.01-5 with the mol ratio of the active metal component：1, preferably 0.1-2:1.

5. the catalyst according to any one in claim 1-4, wherein, the auxiliary agent is gold Category oxides additive, preferably alkaline earth and/or rare-earth oxide auxiliary agent；More preferably MgO、CaO、BaO、La₂O₃、CeO₂、Sm₂O₃、ZrO₂And Y₂O₃In at least one.

6. the catalyst according to any one in claim 1-5, wherein, the carrier is single Component oxide carrier or bi-component or three component composite oxide carriers；Preferably, the carrier Selected from SiO₂、TiO₂、MgO、Al₂O₃、ZrO₂、CeO₂、La₂O₃、SiO₂-Al₂O₃、 TiO₂-SiO₂、Al₂O₃- MgO and TiO₂-SiO₂-Al₂O₃In one or more.

7. a kind of preparation method of loaded catalyst, the method include existing in surfactant Under, dipping solution is contacted with carrier, is then dried and roasting, wherein, in the dipping solution The soluble compound of the soluble compound containing active metal component and auxiliary agent.

8. method according to claim 7, wherein, the surfactant and with metallic atom The mol ratio of the consumption of the soluble compound of the active metal component of meter is 0.001-2:1, preferably 0.001-1:1, more preferably 0.01-0.8：1.

9. the method according to claim 7 or 8, wherein, the surfactant selected from it is cloudy from At least one in subtype surfactant, amphoteric surfactant and nonionic surfactant； Preferably stearic acid, Oleic acid, lauric acid, lecithin, dodecyl alanine, alkyl dimethyl At least one in glycine betaine, fatty glyceride, polyhydric alcohol, polysorbate60 and P123；It is further excellent Elect at least one in P123, Oleic acid and polysorbate60 as.

10. the method according to any one in claim 7-9, wherein, with metal atoms, The soluble compound of the auxiliary agent with the mol ratio of the soluble compound of the active metal component is 0.01-5:1, preferably 0.1-2:1.

11. methods according to any one of claims of claim 7-10, wherein, the auxiliary agent can Soluble compound is selected from alkaline earth and/or rare earth metal soluble compound；Preferably, the auxiliary agent can Soluble compound is in magnesium salt, calcium salt, strontium salt, barium salt, cerium salt, lanthanum salt, zirconates and yttrium salt It is at least one；It is highly preferred that the soluble compound of the auxiliary agent selected from magnesium salt, barium salt, lanthanum salt and At least one in yttrium salt, more preferably lanthanum salt and/or magnesium salt.

12. methods according to any one in claim 7-11, wherein, the concentration of impregnation liquid With consumption so that on the basis of the gross weight of the catalyst, with elemental metal, the active metal The content of component is 2-20 weight %, preferably 3-15 weight %, more preferably 4-10 weight %；

Preferably, the soluble compound of the active metal component is selected from Ni (NO₃)₂·6H₂O、 Co(NO₃)₂·6H₂O、Ni(acac)₂、Co(acac)₃、Ni(CH₃COO)₂·6H₂O and Co(CH₃COO)₂·6H₂At least one in O, more preferably Ni (NO₃)₂·6H₂O and/or Co(NO₃)₂·6H₂O；The carrier is single component oxide carrier or bi-component or three component composite oxygens Compound carrier, preferably SiO₂、TiO₂、MgO、Al₂O₃、ZrO₂、CeO₂、La₂O₃、 SiO₂-Al₂O₃、TiO₂-SiO₂、Al₂O₃- MgO and TiO₂-SiO₂-Al₂O₃In one or more.

The supported catalyst that 13. preparation methoies by described in claim 7-12 any one are prepared Agent.

Loaded catalyst in 14. claim 1-6 and 13 described in any one is in methane dry reforming Prepare the application in synthesis gas.

A kind of 15. methods of methane dry reforming preparing synthetic gas, the method are included in the synthesis of methane dry reforming system Under the conditions of gas, methane and carbon dioxide is contacted with catalyst, it is characterised in that the catalyst is power Profit requires the catalyst in 1-6 and 13 described in any one.

16. methods according to claim 15, wherein, the methane dry reforming preparing synthetic gas are adopted With fixed bed reactors or fluidized-bed reactor, the condition of the methane dry reforming preparing synthetic gas includes：First The mol ratio of alkane and carbon dioxide is 0.7-1.1:1, preferably 0.8-1：1；Reaction temperature is 550-850 DEG C, Preferably 600-800 DEG C；Pressure is 0-3MPa, preferably 0-1MPa；Total air speed of unstripped gas is 2000-120000ml·g^-1·h^-1, preferably 60000-120000mlg^-1·h^-1。