阅读说明：本技术 沼气全组分转化生物甲醇催化剂LaNiO3/SiC-SiO2-Foam及其制备方法 (Biogas full constituent inverting biological catalyst for methanol LaNiO3/SiC-SiO2- Foam and preparation method thereof ) 是由 谢君 张止戈 于 2019-08-29 设计创作，主要内容包括：本发明涉及沼气全组分转化生物甲醇催化剂LaNiO_3/SiC-SiO_2-Foam及其制备方法。所述催化剂LaNiO_3/SiC-SiO_2-Foam,LaNiO_3负载于载体SiC-SiO_2-Foam上,LaNiO_3的负载量为3～7％。本发明制备得到的LaNiO_3/SiC-SiO_2-Foam具有钙钛矿型晶胞结构,所有的镍镧元素都以一定规则有序的排列,将其进行还原后得到的Ni-La_2O_3/SiC-SiO_2-Foam中镍元素按对应的排列顺序析出,分散性高,分布均匀,性能稳定,转化率高,可以很好地催化沼气全组分转化合成气用于合成生物甲醇反应中的应用。本发明的制备方法工艺简单,成本低廉,易于工业化推广生产。(The present invention relates to biogas full constituent inverting biological catalyst for methanol LaNiO 3 /SiC‑SiO 2 - Foam and preparation method thereof.The catalyst LaNiO 3 /SiC‑SiO 2 - Foam, LaNiO 3 It is carried on carrier S iC-SiO 2 On-Foam, LaNiO 3 Load capacity be 3~7%.The LaNiO that the present invention is prepared 3 /SiC‑SiO 2 - Foam has Ca-Ti ore type cell configuration, and all nickel lanthanum elements are all with certain regular arrangement, the Ni-La obtained after being restored 2 O 3 /SiC‑SiO 2 For nickel element by the corresponding precipitation that puts in order, dispersibility is high in-Foam, is evenly distributed, and performance is stablized, high conversion rate, can be catalyzed biogas full constituent transformation of synthetic gas well for the application in the reaction of synthesising biological methanol.Preparation method simple process and low cost of the invention is easy to industrialization promotion production.)

1. a kind of biogas full constituent inverting biological catalyst for methanol LaNiO₃/ SiC-Foam, which is characterized in that LaNiO₃It is carried on On carrier S iC-Foam, LaNiO₃Load capacity be 3~7%；The LaNiO₃/ SiC-Foam is made by the steps to obtain:

S1: SiC-Foam is calcined at 900~1050 DEG C to 2~4h under oxygen-containing atmosphere and obtains SiC-Foam；

S2: SiC-SiO will be added behind lanthanum source and nickel source dissolution_2-Chelating agent is added in Foam, pulverization process, carries out microwave treatment and obtains Gel, it is dry, obtain LaNiO₃/SiC-SiO₂- Foam Ca-Ti ore type precursor；

S3: by LaNiO₃/SiC-SiO₂- Foam Ca-Ti ore type precursor calcines 4~6h under an oxygen-containing atmosphere at 700~800 DEG C Obtain the LaNiO₃/SiC-SiO₂-Foam。

2. LaNiO according to claim 1₃/SiC-SiO₂- Foam, which is characterized in that the LaNiO₃Load capacity be 5%.

3. LaNiO according to claim 1₃/SiC-SiO₂- Foam, which is characterized in that the temperature of calcining described in S1 is 1000 DEG C, time 3h；Oxygen-containing atmosphere described in S1 is air atmosphere.

4. LaNiO according to claim 1₃/SiC-SiO₂- Foam, which is characterized in that nickel source described in S2 is Ni (NO₃)₂Or One or more of nickel acetate；Lanthanum source described in S2 is La (NO₃)₃Or one or more of nickel acetate；It is chelated described in S2 Agent is one or more of citric acid, sodium hydroxide or isopropanol.

5. LaNiO according to claim 1₃/SiC-SiO₂- Foam, which is characterized in that nickel element and lanthanum source in S2 nickel source In lanthanum element molar ratio be 1:1.

6. LaNiO according to claim 1₃/SiC-SiO₂- Foam, which is characterized in that nickel element and lanthanum in S2 in nickel source The summation of lanthanum element in source and the molar ratio of citric acid are 1:1~1.5.

7. LaNiO according to claim 1₃/SiC-SiO₂- Foam, which is characterized in that the temperature of calcining described in S3 is 750 DEG C, time 3h；Oxygen-containing atmosphere described in S3 is air atmosphere.

8. a kind of biogas full constituent inverting biological catalyst for methanol Ni-La₂O₃/SiC-SiO₂- Foam, which is characterized in that by such as Lower process is prepared: by any LaNiO of claim 1~7₃/SiC-SiO₂- Foam is at 750~850 DEG C of atmosphere of hydrogen Lower progress reduction treatment is up to the Ni-La₂O₃/SiC-SiO₂-Foam。

9. Ni-La according to claim 8₂O₃/SiC-SiO₂- Foam, which is characterized in that the temperature of the reduction is 800 DEG C, the time of reduction is 2h.

10. any Ni-La of claim 8~9₂O₃/SiC-SiO₂- Foam is preparing the application in biological methanol.

Technical field

The invention belongs to catalyst technical fields, and in particular to biogas full constituent inverting biological catalyst for methanol LaNiO₃/ SiC-SiO₂- Foam and preparation method thereof.

Background technique

The energy supply of the world today is mainly based on coal, petroleum, natural gas these three non-renewable fossil resources.It is existing The new century is strided forward in the step of globalization, the rapid growth of the size of population steeply risen with economic total volume results in earth money Source is utilized without restraint, although there are still the multiple resources such as deep-sea oil gas, combustible ice, coal bed gas and shale gas at present for exploitation And utilization, the mankind also begin to focus on the potential shortage problem of non-renewable fossil fuel.Be richly stored with biology in nature Matter resource, and gaseous fuel is generated with biomass resource fermentation and is referred to as biogas, main component is methane, with worsening shortages Petroleum resources pay attention to people increasingly the development and utilization of Methane Resources.Methane Resources become future because of its sustainability most It is hopeful to substitute one of main energy sources and industrial chemicals of petroleum.Various countries expert is it is believed that 21st century will be biogas Century.It is predicted according to International Energy Agency, from now on to the year two thousand fifty, biogas consumption figure will be doubled and redoubled.Biogas is in world energy sources Ratio shared by structure also constantly rises in recent years, according to scholarly forecast, arrives middle of century, ratio of the biogas in world's energy resource structure Example is up to 80%, so that substituting petroleum becomes the most important energy in the whole world.Therefore biogas is being changed as a kind of important resource Great concern of the fields such as work and the energy by people.The Methane Resources very abundant in China, because China territory length and breadth of land is raw Physical resources are abundant.Biomass resource abundant provides powerful guarantee to develop biogas chemical industry.Biogas, which removes, is used as clean energy Outside source, acceptable direct hydrogen producing produces liquid fuel and a variety of basic chemicals indirectly, such as prepares methanol, synthesis ammonia and two Methyl ether etc..On the other hand, methane in sewage gas is one of main greenhouse gases in atmosphere, although the methane concentration in atmosphere is remote small In carbon dioxide, but more than 20 times that its greenhouse effects is, the random discharge of a large amount of useless biogas exacerbate greenhouse effects.It is global every The methane that year is thrown by all means in atmosphere reaches 100,000,000 tons, the about total discharge of discharge amount generated by mankind's activity Half of amount or so.Therefore, the methane and carbon dioxide rationally in effective development and utilization biogas has dual meaning, both may be used Effectively to utilize resource, it is possibility to have the greenhouse effects that the control methane of effect generates reduce influence of the methane to global warming.

Synthesis gas means the gaseous mixture of carbon monoxide and hydrogen, CO and H in synthesis gas₂Ratio is with raw material and production method Different and different, molar ratio is 1/2~3/1.Synthesis gas is one of organic synthesis raw material and hydrogen and carbon monoxide There is important role in source in chemical industry.Prepare the raw material of synthesis gas be it is diversified, many containing carbon resource such as coal, Natural gas, petroleum or residual oil etc. may be utilized in fabricating synthesis gas.Liquids and gases fuel, large can be converted to using synthesis gas The fine Organic chemical products of chemicals and high added value.Therefore replace synthesis gas can using reproducible biogas as raw material Environmental pollution and greenhouse effects are effectively reduced, the catalyst pair of efficient catalysis biogas full constituent transformation of synthetic gas is developed In China, current national conditions have far-reaching significance.

In catalysis biogas full constituent transformation of synthetic gas in the reaction of synthesising biological methanol, what application was wide at present to be expensive Metallic catalyst such as (Pd and Pt), uses noble metal higher cost, application difficult；Therefore a kind of low in cost, performance is researched and developed Stablize, the catalyst of excellent catalytic effect has major application prospect.

Summary of the invention

It is an object of the invention to overcome to be catalyzed biogas full constituent transformation of synthetic gas in the prior art for synthesising biological first The noble metal catalyst of alcohol is at high cost, it is difficult to which the defect and deficiency of industrial applications provide a kind of biogas full constituent inverting biological Methanol perovskite type catalyst LaNiO₃/SiC-SiO₂-Foam.The present invention is using SiC-Foam as raw material, by calcining in SiC table Face generates one layer of SiO₂Film obtains carrier S iC-SiO₂-Foam；Then with LaNiO₃For catalytic active component, by load capacity, The optimization of calcination condition, so that Ca-Ti ore type LaNiO₃Particle is smaller, and dispersibility is high, is uniformly dispersed, it is Ni-based to avoid high load Catalyst is easy to the problem reunited, catalytic performance is limited at high temperature.By further progress reduction treatment, Ni- can be obtained La₂O₃/SiC-SiO₂- Foam, Ni-La₂O₃/SiC-SiO₂Dispersed height is precipitated by corresponding put in order in nickel element in-Foam, It is evenly distributed, performance is stablized, high conversion rate, can be catalyzed biogas full constituent transformation of synthetic gas well for synthesising biological methanol Application in reaction.

Another object of the present invention is to provide a kind of biogas full constituent inverting biological catalyst for methanol Ni-La₂O₃/SiC- SiO₂-Foam。

Another object of the present invention is to provide above-mentioned Ni-La₂O₃/SiC-SiO₂- Foam is preparing answering in biological methanol With.

For achieving the above object, the present invention adopts the following technical scheme:

A kind of biogas full constituent inverting biological catalyst for methanol LaNiO₃/ SiC-Foam, LaNiO₃It is carried on carrier S iC- SiO₂On-Foam, LaNiO₃Load capacity be 3~7%；The LaNiO₃/SiC-SiO₂- Foam is made by the steps It arrives:

S1: SiC-Foam is calcined at 900~1050 DEG C to 2~4h under oxygen-containing atmosphere and obtains SiC-SiO₂-Foam；

S2: SiC-SiO will be added behind lanthanum source and nickel source dissolution₂Chelating agent is added in-Foam, pulverization process, carries out at microwave Gel is managed to obtain, it is dry, obtain LaNiO₃/SiC-SiO₂- Foam Ca-Ti ore type precursor；

S3: by LaNiO₃/SiC-SiO₂- Foam Ca-Ti ore type precursor under an oxygen-containing atmosphere at 700~800 DEG C calcining 4~ 6h is up to the LaNiO₃/SiC-SiO₂-Foam。

Research shows that with SiO₂For carrier high load nickel-base catalyst exist at high temperature be easy to reunite, catalytic performance by The shortcomings that limit.And industrially conventional carrier because conduction inequality it is even or it is unstable can lead to the problem of cold spot, so as to cause Active component on carrier is affected because of the differential activities performance of temperature or leads to large area because of the problem of heat conduction Inactivation.Thus, the present invention optimizes high load nickel-base catalyst in terms of carrier and catalyst activity component two.

On the one hand, the present invention is to carry to have the SiC-Foam of the strong constraint power of three cavernous structures and anti-cold spot effect Phosphor bodies make the surface oxidation of silicon carbide SiC generate one layer of SiO by high-temperature calcination₂Film, silicon carbide have thermally conductive uniform heat The SiO for conducting the features such as efficient, while generating₂Film can increase the interaction between active component and carrier and then ask from cold spot It is solved the problems, such as in terms of topic and activity problems two and promotes catalytic reaction process problem encountered and catalytic activity.

On the other hand, the present invention is with LaNiO₃As active constituent, the cell configuration with Ca-Ti ore type, all nickel lanthanums Element is all with certain regular arrangement.Simultaneously by the reduction of hydrogen so that Ca-Ti ore type LaNiO₃In nickel element it is orderly Be precipitated so that nickel particle is smaller, dispersibility is high, is uniformly dispersed, avoid high load nickel-base catalyst be easy to reunite at high temperature, The limited problem of catalytic performance.

The LaNiO that the present invention is prepared₃/SiC-SiO₂- Fiber catalyst surface element is suitable with Ca-Ti ore type structure cell The orderly arrangement of sequence, then Ni-La can be obtained after hydrogen reducing₂O₃/SiC-SiO₂- Foam, Ni-La₂O₃/SiC-SiO₂-Foam Dispersed height is precipitated by corresponding put in order in middle nickel element, is evenly distributed, and performance is stablized, and high conversion rate can urge well Change biogas full constituent transformation of synthetic gas for the application in the reaction of synthesising biological methanol.Preparation method simple process of the invention, It is low in cost, it is easy to industrialization promotion production.

Nickel source, lanthanum source and SiC-SiO₂The dosage of-Foam can be according to LaNiO₃Load capacity selection is adjusted.

LaNiO₃Load capacity have a certain impact to the performance of catalyst tool, if load capacity is too low, LaNiO₃What is be distributed is dilute It dredges and is unable to reach the effect that La and Ni are mutually cooperateed with；Load capacity is too high, LaNiO₃Due to nickel after the too close reduction of cell distribution Element is closely easy to happen very much reunion.By optimizing to load capacity condition, LaNiO can further improve₃/SiC-SiO₂- The catalytic activity of Foam.

It should be understood that load capacity refers to catalytic active component LaNiO₃In entire LaNiO₃/SiC-SiO₂- Foam is urged Mass fraction in agent.

Preferably, the LaNiO₃Load capacity be 5%.

Preferably, the temperature of calcining described in S1 is 1000 DEG C, time 3h.

Preferably, oxygen-containing atmosphere described in S1 is air atmosphere.

Preferably, it is heated up in S1 with the heating rate of 3~5 DEG C/min.

It is further preferable that being heated up in S1 with the heating rate of 5 DEG C/min.

The nickel source of this field routine and lanthanum source are used equally in the present invention.

Preferably, nickel source described in S2 is Ni (NO₃)₂Or one or more of nickel acetate.

Preferably, lanthanum source described in S2 is La (NO₃)₃, one or more of lanthanum acetate.

Preferably, chelating agent described in S2 is one or more of citric acid, sodium hydroxide.

Preferably, the molar ratio of the nickel element in S2 nickel source and the lanthanum element in lanthanum source is 1:1.

Preferably, the molar ratio of the summation and citric acid of the nickel element in S2 in nickel source and the lanthanum element in lanthanum source is 1:1 ~1.5.

Preferably, the temperature of calcining described in S3 is 750 DEG C, time 3h.

Preferably, oxygen-containing atmosphere described in S3 is air atmosphere.

Preferably, it is heated up in S3 with the heating rate of 3~5 DEG C/min.

It is further preferable that being heated up in S3 with the heating rate of 5 DEG C/min.

A kind of biogas full constituent inverting biological catalyst for methanol Ni-La is also claimed in the present invention₂O₃/SiC-SiO₂- Foam is prepared by following process: by above-mentioned LaNiO₃/SiC-SiO₂- Foam is carried out at 750~850 DEG C of atmosphere of hydrogen Reduction treatment is up to the Ni-La₂O₃/SiC-SiO₂-Foam。

LaNiO₃Itself it is not have catalytic activity, forms LaNiO₃Point that structure may make nickel lanthanum element more orderly Cloth forms unified orderly entirety, LaNiO₃(Ni-La is obtained after reduction after hydrogen reducing goes out metallic nickel₂O₃/SiC-SiO₂- Foam) have catalytic activity, restored through cell configuration nickel distribution more added with normalization, more orderly, to each other between Away from almost definite value, the catalytic activity of nickel element just can be more played in this way, it will not be other while improving catalytic activity Some factors are influenced such as reunion, carbon distribution etc..

Preferably, the temperature of the reduction is 800 DEG C, and the time of reduction is 2h.

Above-mentioned Ni-La₂O₃/SiC-SiO₂- Foam is preparing the application in biological methanol also in protection scope of the present invention It is interior.

Preferably, the Ni-La₂O₃/SiC-SiO₂Application of-the Foam in catalysis biogas full constituent transformation of synthetic gas.

Ni-La₂O₃/SiC-SiO₂- Foam can be catalyzed biogas and be changed into synthesis gas (CO and H₂), synthesis gas can be used as synthesis The raw material of synthesising biological fuel methanol.

Under normal circumstances, Ni-La₂O₃/SiC-SiO₂Temperature of-the Foam when being catalyzed biogas is 750~950 DEG C (normal pressure), Wherein, best with 950 DEG C.

Ni-La₂O₃/SiC-SiO₂Dosage of-the Foam when being catalyzed biogas flow velocity and being 80mL/min is 0.2g.

Compared with prior art, the invention has the following beneficial effects:

The present invention generates one layer of SiO in surface of SiC using SiC-Foam as raw material, by calcining₂Film obtains carrier S iC- SiO₂-Foam；Then with LaNiO₃For catalytic active component, by load capacity, the optimization of calcination condition, so that Ca-Ti ore type LaNiO₃Particle is smaller, and dispersibility is high, is uniformly dispersed, and avoids high load nickel-base catalyst and is easy to reunite at high temperature, be catalyzed The problem of limited performance；By further reduction treatment, Ni-La can be obtained₂O₃/SiC-SiO₂- Foam, Ni-La₂O₃/SiC- SiO₂Dispersed height is precipitated by corresponding put in order in nickel element in-Foam, is evenly distributed, and performance is stablized, high conversion rate, can be with Catalysis biogas full constituent transformation of synthetic gas is for the application in the reaction of synthesising biological methanol well.

Detailed description of the invention

Fig. 1 is perovskite type catalyst LaNiO₃/SiC-SiO₂The XRD diagram of-Foam；

Fig. 2 is the conversion ratio figure of methane and carbon dioxide in embodiment 1,3 and 5 reaction products；

Fig. 3 is the conversion ratio figure of methane and carbon dioxide in the reaction product of precious metal catalyst biogas.

Specific embodiment

Below with reference to embodiment, the present invention is further explained.These embodiments are merely to illustrate the present invention rather than limitation The scope of the present invention.Test method without specific conditions in lower example embodiment usually according to this field normal condition or is pressed The condition suggested according to manufacturer；Used raw material, reagent etc., unless otherwise specified, being can be from the business such as conventional market The raw materials and reagents that approach obtains.The variation for any unsubstantiality that those skilled in the art is done on the basis of the present invention And replacement belongs to scope of the present invention.