CN112916017A - Raw material gas activation method for copper-based catalyst for hydrogen production by methanol steam reforming - Google Patents
Raw material gas activation method for copper-based catalyst for hydrogen production by methanol steam reforming Download PDFInfo
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- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
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Abstract
The invention relates to a raw material gas activation method for a copper-based catalyst for hydrogen production by methanol steam reforming, which comprises the following steps: loading a copper-based catalyst into a reactor; continuously introducing inert gas into the reactor, and setting the gas flow rate so that the space velocity reaches and is kept to tau1Heating to an activation temperature T at a predetermined heating rate1The time required for temperature rise is t1(ii) a Introducing O into the reactor2And H2O、CH3The mixed gas of OH mixed gas is adjusted in flow rate so that the space velocity is tau2Self-heating temperature up to T2Time of stabilization t2And the activation process is completed. Compared with the prior art, the activation process is simple and easy to control, the reduction is simple, the activation cost is lower, and commercial Cu/ZnO/Al is improved2O3The catalyst activation process optimizes the catalyst structure, further improves the activity and stability of the methanol reforming hydrogen production reaction, and is suitable for industrial application.
Description
Technical Field
The invention relates to the field of methanol hydrogen production, in particular to a raw material gas activation method for a copper-based catalyst for hydrogen production by methanol steam reforming.
Background
In the present day when environmental issues become a focus of world attention, there is a need to find and develop new clean energy. Among them, hydrogen is an ideal clean energy source because it can be efficiently converted into energy without generating toxic substances or greenhouse gases, and particularly, its use in the field of fuel cell vehicles makes it possible and necessary to view hydrogen as an energy source worldwide, and its development and utilization have become one of the future world development trends. However, the direct application of hydrogen to fuel cell vehicles has heretofore been limited by hydrogen storage technology, namely: a hydrogen storage vessel and a hydrogen storage material. Based on this, hydrogen production in situ by using hydrogen storage materials is an alternative method for applying hydrogen energy on fuel cell vehicles.
The methanol has the advantages of high hydrogen content, low price, convenient storage and transportation at room temperature, and the like, and is an excellent hydrogen carrier. And the methanol has wide sources, can be produced on the basis of fossil energy, and can also be produced from carbon dioxide and renewable hydrogen. Although carbon dioxide is generated in the process of producing hydrogen from methanol, with the popularization of the technology of producing methanol by hydrogenating carbon dioxide, carbon resources can be effectively recycled, and the problem can be better solved. Around this line of technology, the concept of "methanol economy" has also been proposed by the Nobel prize winner, George Andrew Olah. Therefore, methanol has a very high feasibility for in-situ hydrogen supply for fuel cell vehicles, and is also receiving more and more attention from academia and industry.
Studies have shown that methanol steam reforming releases hydrogen in situ, with higher hydrogen yields and lower carbon monoxide yields compared to partial oxidation of methanol or autothermal reforming of methanol, and can be carried out at lower temperatures of 200-. Currently, the production of hydrogen by steam reforming of methanol mainly uses a copper-based catalyst from an economic viewpoint. Before the catalyst is used, the catalyst generally needs to be activated, a traditional copper-based catalyst activation mode generally uses hydrogen for reduction, and meanwhile, nitrogen or other inert gases are selected for dilution according to specific process requirements, so that the catalyst is not easy to store and transport, the risk of the whole equipment is improved, and the cost is increased.
In order to reduce the production cost, in view of the high development cost and long cycle of the new catalyst, a simple and continuous activation method based on the existing commercial catalyst is urgently needed to be found so as to improve the activity and stability of the catalyst in the hydrogen production by methanol steam reforming.
Disclosure of Invention
The present invention is directed to overcoming the above-mentioned drawbacks of the prior art and providing a raw material gas activation method for copper-based catalyst for methanol steam reforming hydrogen production, which employs two-step continuous activation steps, and in the second step, directly employs mixed gas of air and raw material gas to reduce commercial Cu/ZnO/Al2O3The method is simple and easy to control, can improve the activity and stability of the copper-based catalyst, and can be seamlessly connected with the subsequent reforming hydrogen production reaction step.
The purpose of the invention can be realized by the following technical scheme:
the raw material gas activation method for the copper-based catalyst for hydrogen production by methanol steam reforming comprises the following steps:
s1: filling a specific amount of a copper-based catalyst into a reactor;
s2: at a predetermined rate of temperature rise by t0Time to raise the reactor temperature to T0Then continuously introducing a mixed gas of water and methanol into the reactor, and setting the feeding speed so that the space velocity of the mixed gas reaches and is kept to tau1Then through t1Time to slowly raise the reactor temperature to T1Obtaining a preliminary reduced copper-based catalyst;
s3: continuously introducing a mixed gas of air, water and methanol into the reactor, and setting the feeding speed so that the space velocity of the mixed gas reaches and is kept to tau2Rapidly raising the temperature to T with the aid of self-heating2Time of stabilization t2And obtaining the deeply activated copper-based catalyst.
Further, the copper-based catalyst is commercial Cu/ZnO/Al2O3A catalyst.
Further, the commercial Cu/ZnO/Al2O3The catalyst comprises Cu/ZnO/Al2O3And other adjuvants.
Further, the reactor is a tubular reactor.
Further, in S2, the copper-based catalyst is preliminarily reduced by using hydrogen gas generated by the reduction or reforming reaction of methanol itself
Furthermore, the volume ratio of water to methanol in the mixed gas in the S2 is 1: 1-2: 1.
Further, t in S201 to 24 hours, T0Is 100 to 150 ℃.
Further, τ in S2130000-1500000L/(kg)cat·h)，T1At 175-225 ℃, said t1Is 1-200 h. In practice this value depends on the catalyst loading, T1And τ1The specific numerical value of (A) is based on the premise of avoiding temperature runaway caused by heat release of reduction in the reduction process of the catalyst
Furthermore, the exothermic characteristic of the oxidative reforming reaction is utilized in S3 to assist the temperature rise of the catalytic bed layer, so that the energy consumption is saved. Meanwhile, the interaction between the copper particles and the carrier can be optimized by keeping the copper particles in the high-temperature area for a certain time, and the reaction activity is improved. And stopping air feeding, and directly starting stable hydrogen production reaction when the temperature is reduced to the working temperature of the catalyst.
Further, the volume ratio V of the mixed gas of air, water and methanol in S3Air (a)：VWater + methanolThe volume ratio of water to methanol in the mixed gas of water and methanol is 1: 1-2: 1.
Further, τ in S3230000-1500000L/(kg)cat·h)，T2The temperature is 300-400 ℃, and the stabilization time t is2Is 0.0833-24 h.
Further, after S3, the air feeding is stopped, the water and methanol mixed gas feeding is not changed, and the methanol steam reforming hydrogen production reaction is started when the temperature of the reactor is reduced to the working temperature of the copper-based catalyst with deep activation.
Further, the temperature of the methanol steam reforming hydrogen production reaction is 175-275 ℃, and the reaction pressure is normal pressure.
Compared with the prior art, the invention has the following technical advantages:
1) the activation method only uses raw material gas and air, does not need additional hydrogen for activation, has simple operation process, easy control, high activation efficiency and strong operability, and can be widely used in occasions which cannot obtain or use hydrogen due to condition limitation. The air feeding is stopped only after the step S3, the stable hydrogen production reaction can be directly started after the temperature is reduced to the working temperature of the catalyst, the continuity of the activation step and the reaction step is extremely high, and the method is particularly suitable for continuous industrial production.
2) In the activation method of the copper-based catalyst, the strong interaction between copper and the carrier is promoted by adding water and methanol in the activation atmosphere, so that the methanol conversion rate of the supported copper-based catalyst at the same temperature is higher than that of the supported copper-based catalyst adopting the traditional hydrogen reduction method, and simultaneously, the extremely low carbon monoxide selectivity is kept.
3) Compared with the common hydrogen activation method, the activation method of the copper-based catalyst has the advantages that the load capacity of the active components and the reaction conditions are the same, the reforming hydrogen production performance and the stability of the deeply activated catalyst have remarkable advantages, and the activation method has good industrial application prospect.
Drawings
FIG. 1 is a graph of activity data (at different reaction temperatures) for each of the catalyst samples of example 1 and comparative example;
FIG. 2 is a graph of the stability of each catalyst sample of example 1 and comparative example (at different reaction times);
FIG. 3 is H for catalyst samples of example 1 and comparative example2-a TPR map;
fig. 4 XRD patterns of different activation condition catalyst samples in example and comparative example 1.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
S1: 200mg of Cu/ZnO/Al2O3Catalyst loadingInto a reactor, Cu/ZnO/Al2O3The mass fraction of CuO in the composite oxide is 40%, and the reactor adopted by the reaction is a tubular reactor;
s2: the temperature of the reactor is raised to 100 ℃ through 1h at a preset temperature raising rate, then the mixed gas of water and methanol is continuously introduced into the reactor, and the feeding speed is set so that the space velocity of the mixed gas reaches and maintains 30000L/(kg)catH), keeping for 1h, and then slowly raising the temperature of the reactor to 200 ℃ through 20min to obtain a primarily reduced copper-based catalyst;
s3: continuously introducing a mixed gas of air, water and methanol into the reactor, and setting the feeding speed so as to ensure that the space velocity of the mixed gas reaches and maintains to 30000L/(kg)catH), rapidly raising the temperature to 300 ℃ with the aid of self-heating action, and stabilizing for 10min to obtain the deeply activated copper-based catalyst.
Wherein H2O and CH3H in OH mixed gas2O and CH3OH ratio 1.3:1, O in air was maintained in S32And CH3The OH proportion was 0.192.
Example 2
S1: 200mg of Cu/ZnO/Al2O3Catalyst is filled into the reactor, Cu/ZnO/Al2O3The mass fraction of CuO in the composite oxide is 40%, and the reactor adopted by the reaction is a tubular reactor;
s2: the temperature of the reactor is raised to 150 ℃ through 18h at a preset temperature raising rate, then a mixed gas of water and methanol is continuously introduced into the reactor, and the feeding speed is set so that the space velocity of the mixed gas reaches and is kept to 80000L/(kg)catH), keeping for 1h, and then slowly raising the temperature of the reactor to 225 ℃ through 20min to obtain a primarily reduced copper-based catalyst;
s3: continuously introducing a mixed gas of air, water and methanol into the reactor, and setting the feeding speed so as to ensure that the space velocity of the mixed gas reaches and maintains to 80000L/(kg)catH) rapidly raising the temperature to 400 ℃ with the aid of autothermic action and stabilizing for 10min to obtain the deeply activated copper-based catalyst.
Wherein H2O and CH3H in OH mixed gas2O and CH3OH ratio of 1:1, maintaining O in air in S32And CH3The OH proportion was 0.768.
Example 3
S1: 200mg of Cu/ZnO/Al2O3Catalyst is filled into the reactor, Cu/ZnO/Al2O3The mass fraction of CuO in the composite oxide is 40%, and the reactor adopted by the reaction is a tubular reactor;
s2: the temperature of the reactor is raised to 150 ℃ through 18h at a preset temperature raising rate, then a mixed gas of water and methanol is continuously introduced into the reactor, and the feeding speed is set so that the space velocity of the mixed gas reaches and is kept to 150000L/(kg)catH), keeping for 1h, and then slowly raising the temperature of the reactor to 225 ℃ through 20min to obtain a primarily reduced copper-based catalyst;
s3: continuously introducing a mixed gas of air, water and methanol into the reactor, and setting the feeding speed so as to ensure that the space velocity of the mixed gas reaches and maintains to 150000L/(kg)catH), rapidly raising the temperature to 300 ℃ with the aid of self-heating action, and stabilizing for 10min to obtain the deeply activated copper-based catalyst.
Wherein H2O and CH3H in OH mixed gas2O and CH3OH ratio of 2:1, maintaining O in air in S32And CH3The OH proportion was 0.192.
Comparative example 1
In this comparative example, commercial Cu/ZnO/Al is used as compared to example 12O3Hydrogen (10% H) of catalyst2Ar) activation at 300 ℃ for 1h, see example 1 for further parameters.
Comparative example 2
In this comparative example, commercial Cu/ZnO/Al is used as compared to example 12O3The catalyst is activated by water and alcohol, the activation temperature is 300 ℃, the activation time is 1h, and other parameters are shown in example 1.
Comparative example 3
Comparison of this with example 1Examples are commercial Cu/ZnO/Al2O3The catalyst is activated by water and alcohol, the activation temperature is 200 ℃, the activation time is 1h, and other parameters are shown in example 1.
FIG. 1 is a graph showing the activity of steam reforming reaction of methanol in examples and comparative examples at different temperatures, and Table 1 shows the performance data of catalysts in each example and comparative example.
Table 1: catalyst Performance data for each example and comparative example under the catalyst evaluation conditions described above
The result shows that the sectional type raw material gas activation process not only can improve the activity of the catalyst, but also can obviously improve the stability of the catalyst. In addition, the activity and the stability of the catalyst are obviously different by simply regulating and controlling the time of introducing air, thereby providing possibility for the use in a fuel cell.
From H2TPR (FIG. 3) shows that reduction at 200 ℃ for 1h already reduces the majority of Cu to metallic copper, and that different pretreatment pairs Cu/ZnO/Al2O3The catalyst copper particle size had no effect (fig. 4). Therefore, the interaction between the metal and the carrier is changed by adding oxygen in the activation process, so that the copper particles are covered by the zinc oxide layer, the copper particles are stabilized, the sintering of the copper particles in the reaction process is avoided, the stability of the catalyst is improved, more copper-zinc oxide interfaces are provided, and the reaction activity is improved.
In conclusion, the sectional type raw material gas activation method avoids the use of hydrogen, causes the interaction of different metals and carriers, greatly improves the activity and stability of the catalyst, can regulate and control the time of adding oxygen into the catalyst, can realize the optimal microcosmic configuration effect, has mild integral activation condition and strong controllability, and can be applied to large-scale industrial production.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A raw material gas activation method for a copper-based catalyst for hydrogen production by methanol steam reforming is characterized by comprising the following steps:
s1: filling a specific amount of a copper-based catalyst into a reactor;
s2: at a predetermined rate of temperature rise by t0Time to raise the reactor temperature to T0Then continuously introducing a mixed gas of water and methanol into the reactor, and setting the feeding speed so that the space velocity of the mixed gas reaches and is kept to tau1Then through t1Time to slowly raise the reactor temperature to T1Obtaining a preliminary reduced copper-based catalyst;
s3: continuously introducing a mixed gas of air, water and methanol into the reactor, and setting the feeding speed so that the space velocity of the mixed gas reaches and is kept to tau2Rapidly raising the temperature to T with the aid of self-heating2Time of stabilization t2And obtaining the deeply activated copper-based catalyst.
2. The raw material gas activation method for the copper-based catalyst for hydrogen production by methanol steam reforming as claimed in claim 1, wherein the copper-based catalyst is commercial Cu/ZnO/Al2O3A catalyst.
3. The raw material gas activation method for the copper-based catalyst for hydrogen production by methanol steam reforming as claimed in claim 1, wherein the reactor is a tubular reactor.
4. The raw material gas activation method for the copper-based catalyst for hydrogen production by methanol steam reforming as claimed in claim 1, wherein the volume ratio of water to methanol in the mixed gas in S2 is 1: 1-2: 1.
5. The raw material gas activation method for the copper-based catalyst for hydrogen production by methanol steam reforming as claimed in claim 1, wherein t in S201 to 24 hours, T0Is 100 to 150 ℃.
6. The raw material gas activation method for the copper-based catalyst for hydrogen production by methanol steam reforming as claimed in claim 1, wherein τ in S2130000-1500000L/(kg)cat·h)，T1At 175-225 ℃, said t1Is 1-200 h.
7. The method for activating a raw material gas of a copper-based catalyst for hydrogen production by methanol steam reforming as claimed in claim 1, wherein the volume ratio V of the mixed gas of air, water and methanol in S3 isAir (a)：VWater + methanolThe volume ratio of water to methanol in the mixed gas of water and methanol is 1: 1-2: 1.
8. The raw material gas activation method for the copper-based catalyst for hydrogen production by methanol steam reforming as claimed in claim 1, wherein τ in S3230000-1500000L/(kg)cat·h)，T2The temperature is 300-400 ℃, and the stabilization time t is2Is 0.0833-24 h.
9. The raw material gas activation method for the copper-based catalyst for hydrogen production by methanol steam reforming as claimed in claim 1, wherein after S3, air feeding is stopped, water and methanol mixed gas feeding is unchanged, and the methanol steam reforming hydrogen production reaction is started when the temperature of the reactor is reduced to the operating temperature of the copper-based catalyst for deep activation.
10. The raw material gas activation method for the copper-based catalyst for hydrogen production by methanol steam reforming as claimed in claim 9, wherein the temperature of the reaction for hydrogen production by methanol steam reforming is 175-275 ℃, and the reaction pressure is normal pressure.
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| CN116159602A (en) * | 2023-03-01 | 2023-05-26 | 江苏京盈化工新材料有限公司 | Reduction process of copper catalyst for N-methylaniline synthesis |
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