CN112403473B - Synthesis method for preparing reforming catalyst through MOFs - Google Patents

Synthesis method for preparing reforming catalyst through MOFs Download PDF

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CN112403473B
CN112403473B CN202011229347.5A CN202011229347A CN112403473B CN 112403473 B CN112403473 B CN 112403473B CN 202011229347 A CN202011229347 A CN 202011229347A CN 112403473 B CN112403473 B CN 112403473B
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reaction
catalyst
mofs
auxiliary agent
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CN112403473A (en
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孙予罕
王慧
杜洋
马春辉
张磊
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Shanghai Cluster Rui Low Carbon Energy Technology Co ltd
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Abstract

The invention discloses a synthesis method for preparing a reforming catalyst by MOFs, which is characterized in that an auxiliary agent precursor M1 and an organic ligand are simultaneously added into an organic solvent, so that the auxiliary agent precursor M1 is fully dissolved to form a transparent clear solution; transferring the mixture into a reaction kettle, heating the mixture for reaction, naturally cooling the mixture to room temperature after the reaction is finished to obtain turbid liquid, and centrifuging, washing and drying the turbid liquid to obtain an M1-MOFs precursor; mixing M1-MOFs precursor and Ni (NO) 3 ) 2 ·6H 2 Dissolving O and an auxiliary agent precursor M2 in deionized water, adding ammonia water, reacting, and cooling to room temperature; and drying the obtained filter cake in an oven, and roasting in a muffle furnace to obtain the oxidation precursor catalyst. The catalyst has good threshold effect during the coprecipitation reaction by synthesizing MOFs precursors, thereby controlling the dispersion degree and size of Ni, prolonging the service life of the catalyst in the reforming reaction process and ensuring higher catalytic efficiency.

Description

Synthetic method for preparing reforming catalyst through MOFs
Technical Field
The invention belongs to the technical field of petrochemical industry, and relates to a synthesis method and application of a reforming catalyst obtained by synthesizing MOFs structures.
Background
With the development of industry, the emission of carbon dioxide in human society is increasing year by year. The excessively high carbon dioxide content in the atmosphere has a great negative effect on the climate and ecological balance, and methane, as a clean energy source, although having a high application value, is a "greenhouse gas" which has an adverse effect on the environment. Therefore, how to utilize and reduce the emission of carbon dioxide/methane has been a focus of attention. The synthesis gas prepared by reforming methane and carbon dioxide has good economic and environmental protection values while eliminating two greenhouse gases.
Catalysts for catalytic reforming of methane and carbon dioxide can be classified into two types: noble metals and non-noble metals. Among them, the noble metals Rh, ru and Ir have the best catalytic activity. Although the noble metal catalyst has good catalytic activity and carbon deposit resistance, the industrial application of the noble metal catalyst is poor in economic benefit due to limited resources and high price. On the contrary, although the catalytic activity and the carbon deposit resistance of the non-noble metal are not as good as those of noble metals, the non-noble metal is low in price and rich in resources, so that the main research content is still the non-noble metal catalyst. Wherein the catalytic activity sequence of the non-noble metal is Ni & gt Co & gt Cu & gt Fe. Therefore, the nickel-based catalyst has been the focus of research on the carbon dioxide reforming reaction of methane.
Patent CN106391020A discloses a method for preparing a methane carbon dioxide reforming catalyst prepared by using a carbon material as a carrier to load active metal. The process is carried out by sub-critical H 2 The O-CO modified lignite is used for preparing a carbon material which is a methane and carbon dioxide reforming catalyst carrier, and the carbon material is used as a carrier for loading active metal to prepare a reforming catalyst. The catalyst can be used at lower temperature, saves energy, but has the defects of complex synthesis process and difficult control of conditions, and is difficult to apply on a large scale.
Patent CN102240566B discloses a preparation method of methane carbon dioxide reforming catalyst. The method comprises the steps of immersing semicoke in hydrogen peroxide for modification, impregnating with an auxiliary agent precursor, and roasting with nitrogen to obtain a catalyst precursor. The catalyst prepared by the method has high activity, but hydrogen peroxide is used in the synthesis process, so that the catalyst has certain danger; air is isolated during the calcination, and higher cost is required, so that the preparation method is not favorable for large-scale preparation.
The synthesis gas prepared by reforming methane and carbon dioxide is an important component of C1 chemical research, and is an effective path for methane conversion and carbon dioxide utilization. The VIII transition metals (Ni, co, fe, cu, etc.) are favored for their low cost and high activity, especially for Ni-based catalysts, which exhibit superior performance. However, the Ni-based catalyst has a serious carbon deposit phenomenon, and partial sintering of metal particles occurs during the reaction at a high temperature, and the catalyst is deactivated by the combined action of the two. Therefore, the control of the size of Ni metal particles on the surface of the catalyst and the improvement of the dispersion degree not only solve the problem of carbon deposition, but also solve the key of the problem of catalyst sintering.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: how to control the size of the Ni metal particles on the catalyst surface.
In order to solve the technical problems, the invention provides a synthesis method for preparing a reforming catalyst by MOFs, which is characterized by comprising the following steps:
step 1): slowly adding the auxiliary agent precursor M1 and the organic ligand into the organic solvent under the condition of vigorous stirring simultaneously, so that the auxiliary agent precursor M1 is fully dissolved to form a transparent clear solution; the auxiliary agent precursor M1 is Zn (NO) 3 ) 2 ·5H 2 O、Fe(NO 3 ) 3 ·9H 2 O and Mg (NO) 3 ) 2 ·6H 2 At least one of O; the organic ligand is terephthalic acid
Figure BDA0002764656020000021
Isophthalic acid
Figure BDA0002764656020000022
Trimesic acid
Figure BDA0002764656020000023
Or an organic compound containing one of these three types of substructures;
step 2): transferring the solution obtained in the step 1) into a reaction kettle, heating for reaction, naturally cooling to room temperature after the reaction is finished to obtain turbid liquid, and centrifuging, washing and drying the turbid liquid to obtain an M1-MOFs precursor;
and step 3): mixing M1MOFs precursor, ni (NO) 3 ) 2 ·6H 2 Dissolving O and an auxiliary agent precursor M2 in deionized water, slowly adding ammonia water to control the pH value to be 9-10, violently stirring for reaction, cooling to room temperature, filtering, washing with the deionized water until the filtrate is neutral, and obtaining a filter cake; the auxiliary agent precursor M2 is Ce (NO) 3 ) 3 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 O and Zr (NO) 3 ) 4 ·5H 2 At least one of O;
step 4): and drying the obtained filter cake in an oven, and roasting in a muffle furnace to obtain the oxidation precursor state catalyst.
Preferably, the molar ratio of the organic ligand to the auxiliary precursor M1 in step 1) is 1: (0.1 to 2), preferably 1: (0.5-1).
Preferably, the organic solvent in step 1) is N, N-dimethylformamide.
Preferably, the amount of the organic solvent used in step 1) is 200mL of the organic solvent per 0.1mol of the promoter precursor M1.
Preferably, the reaction temperature in the step 2) is 120 ℃ and the reaction time is 24h.
Preferably, the reaction temperature in the step 3) is 90 ℃ and the reaction time is 24h.
Preferably, M2 in the filter cake obtained in the step 3) a+ And Ni 2+ And M1 b+ The molar ratio of the sum of the moles of (a) is 0.25 to 2.5:1; ni 2+ And M1 b+ In a molar ratio of 0.2 to 2:1.
preferably, the drying temperature in the step 4) is 80 ℃, and the time is 12 hours; the roasting temperature is 750 ℃ and the roasting time is 5h.
Preferably, the oxidation precursor catalyst obtained in step 4) comprises an active component, an auxiliary agent precursor M1, an auxiliary agent precursor M2, and an organic ligand, wherein the active component is Ni, the auxiliary agent precursor M1 is at least one of Zn, mg, and Fe, and the auxiliary agent precursor M2 is at least one of Ce, al, and Zr.
The invention provides a synthesis method for forming a metal organic framework material (M1-MOFs) by an aid precursor M1 and an organic ligand, then carrying out coprecipitation reaction on the metal organic framework material, ni and another aid precursor M2, and finally obtaining a reforming catalyst through washing, drying and roasting. The catalyst effectively synthesizes MOFs precursor, and has good threshold limiting effect during coprecipitation reaction, thereby controlling the dispersion degree and particle size of Ni, prolonging the service life of the catalyst in the reforming reaction process, and simultaneously ensuring higher catalytic efficiency.
Compared with the prior art, the invention has the following advantages:
(1) The MOFs structure has a certain size of pore diameter, the dispersion degree and size of Ni in the pore diameter can be effectively controlled during synthesis, and the particle size of the finally synthesized oxidation precursor catalyst is smaller than that of a common preparation method, so that better catalytic activity and stability are obtained.
(2) The coprecipitation preparation method is simple and easy to operate and low in cost.
Detailed Description
In order that the invention may be more readily understood, preferred embodiments will now be described in detail.
The evaluation procedure for the reforming reaction using the catalyst prepared in the example was as follows:
mixing oxide precursor catalyst (0.1g, 80-100 mesh) with analytically pure quartz sand (0.9g, 80-100 mesh), and adding into H 2 /N 2 Atmosphere (50% each by volume, flow rate 120 mL/min), 700 ℃ pre-reduction for 1h. After completion of reduction, at H 2 /N 2 The reaction temperature is raised to 850 ℃ under the atmosphere (50 percent by volume), and the temperature is switched to CO after being raised to 850 DEG C 2 /CH 4 The mixed gas (molar ratio 1.2. After the reaction was stable, the composition of the product was measured on-line by gas chromatography.
Example 1
Weighing Zn (NO) 3 ) 2 ·5H 2 O (0.1mol, 42.93g) was dissolved in 200mL DMF, terephthalic acid (0.02mol, 3.32g) was added with vigorous stirring, and after completion of the dissolution, the mixture was transferred to a stainless steel reaction vessel lined with polytetrafluoroethylene, and the vessel was placed in a constant temperature oven and allowed to reverse at 120 ℃ to room temperatureAfter cooling for 24h, the product was collected by centrifugation and washed several times with DMF to give Zn-MOFs. Prepared Zn-MOFs (0.1 mol) and Ni (NO) 3 ) 2 ·6H 2 O(0.2mol，58.16g)、Al(NO 3 ) 3 ·9H 2 O (0.075mol, 28.14g) is dissolved in 500mL deionized water, under the condition of vigorous stirring, 50mL ammonia water is slowly dripped, the mixture is vigorously stirred at 90 ℃ for 24 hours for reaction, the mixture is cooled to room temperature, filtered, washed by deionized water until the filtrate is neutral to obtain a filter cake, and then dried at 80 ℃ for 12h, and roasted at 750 ℃ for 5h to obtain the oxidation precursor state catalyst.
Calculating to obtain CO 2 Conversion rate 82.01%, CH 4 Conversion of 87.58% and H in the effluent 2 The ratio of/CO is 0.82, the reaction lasts for 300h 2 、CH 4 Conversion and H 2 the/CO ratio remains substantially unchanged.
Example 2
Weighing Mg (NO) 3 ) 2 ·6H 2 O (0.1mol, 25.64g) was dissolved in 200mL of DMF, 2, 5-dihydroxyterephthalic acid (0.15mol, 29.72g) was added with vigorous stirring, and after completion of the dissolution, the mixture was transferred to a stainless steel reaction vessel lined with polytetrafluoroethylene, the reaction vessel was placed in a constant temperature oven and reacted at 120 ℃ for 24 hours, after cooling, the product was collected by centrifugation and washed several times with DMF to give Mg-MOFs. Mixing prepared Mg-MOFs (0.1 mol) and Ni (NO) 3 ) 2 ·6H 2 O(0.05mol，14.54g)、Zr(NO 3 ) 4 ·5H 2 Dissolving O (0.225mol, 93.48g) in 500mL of deionized water, slowly dropwise adding 65mL of ammonia water under the condition of vigorous stirring, reacting at 90 ℃ for 24h under vigorous stirring, cooling to room temperature, filtering, washing with deionized water until the filtrate is neutral to obtain a filter cake, drying at 80 ℃ for 12h, and roasting at 750 ℃ for 5h to obtain the oxidation precursor catalyst.
Calculating to obtain CO 2 Conversion rate 82.15%, CH 4 Conversion 91.62%, H in the output 2 The ratio of/CO is 0.85, the reaction lasts for 300h 2 、CH 4 Conversion and H 2 the/CO ratio remains substantially unchanged.
Example 3
Weighing Mg (NO) 3 ) 2 ·6H 2 O (0.1mol, 25.64g) was dissolved in 200mL of DMF, 2, 5-dihydroxyterephthalic acid (0.1mol, 19.81g) was added with vigorous stirring, and after completion of the dissolution, the mixture was transferred to a stainless steel reaction vessel lined with polytetrafluoroethylene, and the reaction vessel was placed in a constant temperature oven to react at 120 ℃ for 24 hours, after cooling, the product was collected by centrifugation, and washed several times with DMF to obtain Mg-MOFS. Mixing prepared Mg-MOFS (0.1 mol) and Ni (NO) 3 ) 2 ·6H 2 O(0.1mol，29.08g)、Al(NO 3 ) 3 ·9H 2 Dissolving O (0.2mol, 75.02g) in 500mL of deionized water, slowly dropwise adding 55mL of ammonia water under the condition of vigorous stirring, reacting for 24 hours under the condition of vigorous stirring at 90 ℃, cooling to room temperature, filtering, washing with deionized water until the filtrate is neutral to obtain a filter cake, then drying at 80 ℃ for 12h, and roasting at 750 ℃ for 5 hours to obtain the oxidation precursor state catalyst.
Calculating to obtain CO 2 Conversion 88.64%, CH 4 Conversion 95.21%, H in the output 2 The ratio of/CO is 0.89, the reaction time is 300h 2 、CH 4 Conversion and H 2 the/CO ratio remains substantially unchanged.
Example 4
Weighing Mg (NO) 3 ) 2 ·6H 2 O (0.1mol, 25.64g) was dissolved in 200mL of DMF, 2, 5-dihydroxyterephthalic acid (0.2mol, 39.62g) was added with vigorous stirring, and after completion of the dissolution, the mixture was transferred to a stainless steel reaction vessel lined with polytetrafluoroethylene, the reaction vessel was placed in a constant temperature oven and reacted at 120 ℃ for 24 hours, after cooling, the product was collected by centrifugation and washed several times with DMF to give Mg-MOFs. Prepared Mg-MOFs (0.1 mol) and Ni (NO) 3 ) 2 ·6H 2 O(0.02mol，5.82g)、Ce(NO 3 ) 3 ·6H 2 Dissolving O (0.3 mol, 130.27g) in 500mL of deionized water, slowly dropwise adding 65mL of ammonia water under the condition of vigorous stirring, reacting at 90 ℃ for 24 hours under vigorous stirring, cooling to room temperature, filtering, washing with deionized water until the filtrate is neutral to obtain a filter cake, drying at 80 ℃ for 12h, and roasting at 750 ℃ for 5 hours to obtain the oxidation precursor catalyst.
Calculating to obtain CO 2 Conversion 82.25%, CH 4 The conversion rate is 86.54 percent,h in the output 2 The ratio of/CO is 0.81, the reaction lasts for 300h 2 、CH 4 Conversion and H 2 the/CO ratio remains substantially unchanged.
Example 5
Weighing Fe (NO) 3 ) 3 ·9H 2 O (0.1mol, 40.4 g) is dissolved in 200mL DMF, 1,3, 5-trimesic acid (0.08mol, 16.81g) is added under vigorous stirring, the solution is transferred to a stainless steel reaction kettle with a polytetrafluoroethylene lining, the reaction kettle is placed in a constant-temperature oven and reacts for 24 hours at 120 ℃, after cooling, the product is collected by centrifugation and washed with DMF for a plurality of times to obtain Fe-MOFs. Mixing prepared Mg-MOFs (0.1 mol) and Ni (NO) 3 ) 2 ·6H 2 O(0.15mol，43.62g)、Al(NO 3 ) 3 ·9H 2 Dissolving O (0.125mol, 46.90g) in 500mL of deionized water, slowly dropwise adding 55mL of ammonia water under the condition of vigorous stirring, reacting at 90 ℃ for 24 hours under vigorous stirring, cooling to room temperature, filtering, washing with deionized water until the filtrate is neutral to obtain a filter cake, drying at 80 ℃ for 12h, and roasting at 750 ℃ for 5 hours to obtain the oxidation precursor catalyst.
Calculating to obtain CO 2 Conversion 86.11%, CH 4 Conversion rate of 92.84%, H in the output 2 The ratio of/CO was 0.86, the reaction was 300h 2 、CH 4 Conversion and H 2 the/CO ratio remains substantially unchanged.
Example 6
Weighing Zn (NO) 3 ) 2 ·5H 2 O (0.1mol, 42.93g) is dissolved in 200mL DMF, isophthalic acid (0.15mol, 24.92g) is added under vigorous stirring, the mixture is transferred to a stainless steel reaction kettle with a polytetrafluoroethylene lining after dissolution is finished, the reaction kettle is placed in a constant-temperature oven to react for 24 hours at 120 ℃, and after cooling, products are collected by centrifugation and washed with DMF for a plurality of times to obtain Zn-MOFs. Prepared Zn-MOFs (0.1 mol) and Ni (NO) 3 ) 2 ·6H 2 O(0.1mol，29.08g)、Al(NO 3 ) 3 ·9H 2 Dissolving O (0.4 mol, 150.05g) in 500mL deionized water, slowly dropwise adding 75mL ammonia water under the condition of vigorous stirring, reacting for 24h under vigorous stirring at 90 ℃, cooling to room temperature, and filteringFiltering, washing with deionized water until the filtrate is neutral to obtain a filter cake, drying at 80 ℃ for 12h, and roasting at 750 ℃ for 5h to obtain the oxidation precursor catalyst.
Calculating to obtain CO 2 Conversion 83.89%, CH 4 Conversion rate 89.01%, H in the output 2 The ratio of/CO is 0.83, the reaction lasts for 300h 2 、CH 4 Conversion and H 2 the/CO ratio remains substantially unchanged.
Comparative example 1
Nickel nitrate hexahydrate (0.1mol, 29.08g) and Mg (NO) were weighed out 3 ) 2 ·6H 2 O(0.1mol，25.64g)，Al(NO 3 ) 3 ·9H 2 Dissolving O (0.1mol, 75.02g) in 500mL of deionized water, slowly dropwise adding 55mL of ammonia water under the condition of vigorous stirring, reacting at 90 ℃ for 24 hours under vigorous stirring, cooling to room temperature, filtering, washing with deionized water until the filtrate is neutral to obtain a filter cake, drying at 80 ℃ for 12h, and roasting at 750 ℃ for 5 hours to obtain the oxidation precursor catalyst.
Calculating to obtain CO 2 Conversion 71.26%, CH 4 Conversion 74.61%, H in the effluent 2 The ratio of/CO is 0.74, the obvious inactivation phenomenon appears after the reaction is carried out for 300 hours, and the carbon deposition is serious in thermogravimetric analysis of the catalyst.
Table 1 shows a comparison of the performance of the catalysts of examples 1 to 6 and comparative example 1. As can be seen from the experimental steps of catalyst synthesis, in examples 1-6, M1-MOFs is prepared first, and is subjected to coprecipitation reaction with Ni and an auxiliary agent precursor M2, and then the precursor-state catalyst is obtained through washing, drying and roasting. The comparative example is the preparation of the catalyst directly by coprecipitation. From the data in the table, it can be clearly found that the average particle size of examples 1-6 is significantly smaller than that of the comparative example, while the difference trend of the specific surface area is just opposite, and the smaller particle size and the larger specific surface area can effectively prevent the generation of carbon, improve the carbon deposition resistance of the catalyst, and ensure the high stability and good activity of the catalyst. The catalysts of examples 1-6 and comparative example 1 were used for carbon dioxide reforming of methane, and example 3 had the highest CO 2 And CH 4 Conversion rate and CO after 300h operation 2 And CH 4 The conversion rate is basically kept unchangedThe catalyst has good activity and stability. The activity of the catalyst of other examples is slightly lower than that of the catalyst of example 3 at first, but the catalyst of other examples also basically maintains stable after running for 300 hours, and has good stability and higher catalytic activity. The initial reactivity of the catalysts of example 3 and comparative example was similar, but the CO of the comparative example was similar 2 And CH 4 The conversion rate is rapidly reduced along with the progress of the reforming reaction, and after the reaction for 300 hours, CO is obtained 2 And CH 4 The conversion was much lower than that of example 3 2 And CH 4 The conversion rate is also greatly lower than that of CO in other examples 2 And CH 4 And (4) conversion rate. Meanwhile, the catalyst bed has serious carbon deposition, which proves that the catalyst in the comparative example has poor carbon deposition resistance, and the activity and the stability of the catalyst are far inferior to those of the catalyst prepared by M1-MOFs.
Therefore, the M1-MOFs is synthesized, the threshold effect of the M1-MOFs can be utilized to effectively control the dispersion degree of metal Ni during coprecipitation, and then the metal Ni is dried and roasted to obtain the oxidation precursor state catalyst, so that the particle size of the Ni catalyst is effectively reduced, the specific surface area is increased, and the high CO content is obtained 2 And CH 4 The reforming catalyst with high conversion rate and high stability has simple and easy operation in the synthesis process, and has large-scale preparation and application prospects.
Table 1 comparison of the performance of examples 1-6 with the catalyst of comparative example 1 over 300h of operation
Figure BDA0002764656020000081

Claims (6)

1. Use of a reforming catalyst prepared from MOFs for the carbon dioxide reforming of methane, characterized in that the synthesis of said catalyst comprises the following steps:
step 1): slowly adding the auxiliary agent precursor M1 and the organic ligand into the organic solvent under a violent stirring state at the same time, so that the auxiliary agent precursor M1 is fully dissolved to form a transparent clear solution, wherein the molar ratio of the organic ligand to the auxiliary agent precursor M1 is 1: (0.1 to 2); the auxiliary agent precursor M1 is Zn (NO) 3 ) 2 ·5H 2 O、 Fe(NO 3 ) 3 ·9H 2 O and Mg (NO) 3 ) 2 ·6H 2 At least one of O; the organic ligand is terephthalic acid, isophthalic acid or trimesic acid;
step 2): transferring the solution obtained in the step 1) into a reaction kettle, heating for reaction, naturally cooling to room temperature after the reaction is finished to obtain turbid liquid, and centrifuging, washing and drying the turbid liquid to obtain an M1-MOFs precursor;
and step 3): mixing M1-MOFs precursor and Ni (NO) 3 ) 2 ·6H 2 Dissolving O and an auxiliary agent precursor M2 in deionized water, slowly adding ammonia water to control the pH to be 9 to 10, violently stirring for reaction, cooling to room temperature, filtering, and washing with deionized water until the filtrate is neutral to obtain a filter cake; the auxiliary agent precursor M2 is Ce (NO) 3 ) 3 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 O and Zr (NO) 3 ) 4 ·5H 2 At least one of O; m2 in the resulting filter cake a+ And Ni 2+ And M1 b+ The molar ratio of the sum of the moles of (a) is 0.25 to 2.5:1; ni 2+ And M1 b+ The molar ratio of (A) to (B) is 0.2 to 2:1;
step 4): and drying the obtained filter cake in an oven, and roasting in a muffle furnace to obtain the oxidation precursor state catalyst.
2. The use according to claim 1, wherein the organic solvent in step 1) is N, N-dimethylformamide.
3. The use according to claim 1, wherein the amount of the organic solvent used in step 1) is 200mL of the organic solvent per 0.1mol of the auxiliary precursor M1.
4. The use according to claim 1, wherein the reaction in step 2) is carried out at a temperature of 120 ℃ for a time of 24h.
5. The use according to claim 1, wherein the reaction in step 3) is carried out at a temperature of 90 ℃ for a period of 24h.
6. The use according to claim 1, wherein the drying in step 4) is carried out at a temperature of 80 ℃ for a period of 12h; the roasting temperature is 750 ℃ and the roasting time is 5h.
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