阅读说明：本技术 沼气全组分转化生物甲醇催化剂LaNiO3/SiC-SiO2-Fiber及制备方法 (Biogas full constituent inverting biological catalyst for methanol LaNiO3/SiC-SiO2- Fiber and preparation method ) 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-Fiber及制备方法。该催化剂LaNiO_3/SiC-SiO_2-Fiber,LaNiO_3负载于载体SiC-SiO_2-Fiber上,LaNiO_3的负载量为3～7％。本发明的LaNiO_3/SiC-SiO_2-Fiber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-Fiber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 - Fiber and preparation method.Catalyst LaNiO 3 /SiC‑SiO 2 - Fiber, LaNiO 3 It is carried on carrier S iC-SiO 2 On-Fiber, LaNiO 3 Load capacity be 3~7%.LaNiO of the invention 3 /SiC‑SiO 2 - Fiber 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-Fiber, 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-SiO₂- Fiber, which is characterized in that LaNiO₃ It is carried on carrier S iC-SiO₂On-Fiber, LaNiO₃Load capacity be 3~7%；The LaNiO₃/SiC-SiO₂- Fiber is logical Following steps are crossed to be prepared:

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

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

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

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

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

5. LaNiO according to claim 1₃/SiC-SiO₂- Fiber, 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- Fiber, 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- Fiber, 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- Fiber, which is characterized in that pass through Following process is prepared: by any LaNiO of claim 1~7₃/SiC-SiO₂- Fiber is in atmosphere of hydrogen 750~850 Reduction treatment is carried out at DEG C up to the Ni-La₂O₃/SiC-SiO₂-Fiber。

9. Ni-La according to claim 8₂O₃/SiC-SiO₂- Fiber, 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- Fiber 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- Fiber and preparation method.

Background technique

The energy is material base necessary to human social development and production and living, and the use of the energy is social development and people People's improvement of living standard is made that huge contribution.Currently, the energy needed in the world still mostlys come from coal, stone Fossil energy based on oil and three large resource of biogas, although the new energy such as solar energy, nuclear energy, wind energy and biomass energy in recent years Development and utilization have new hope, but in one, 20 year following, fossil energy still will be during socio-economic development Play leading role.With the very fast development of China's economy, the demand of the energy also increases increasingly.Production of energy knot in China In structure, the output of coal accounts for very big specific gravity, and statistical result showed in 2011, in China's production of energy total amount, coal is accounted for 77.8%, petroleum accounts for 9.1%, and biogas accounts for 4.3%, and water power, nuclear power, wind-powered electricity generation etc. account for 8.8%.Coal resources in China rich reserves, But the component of coal is complex, bring environmental problem and social concern are also got worse, such as the S element and N in coal It will become SO after Elemental combustion₂And NO_x, and then acid rain is formed, the Dust Capacity of discharge is also larger, the CO formed after especially burning₂ It can aggravate energy-saving and emission-reduction institute facing challenges.Petroleum resources due to exploiting for a long time, and reserves are increasingly poor, and China is main at present Meet the domestic demand to petroleum resources by import, and the Oil Safety in China can be threatened by excessively relying on petroleum resources, And sustainable development is damaged.For coal and petroleum, Methane Resources belong to clean energy resource.There is data to show, To 21 century mid-term, the Methane Resources that biomass ferment generates will become the main energy and industrial chemicals.Biogas it is main at It is divided into methane.China's biomass rich reserves, to slow down China's energy shortage problem and adjustment China's energy security project have it is important Meaning, but at present in China's non-renewable energy consumption structure, the ratio of biogas it is smaller apart from world average level gap compared with Greatly.Produced in biogas base in the biomass that has been developed that, be largely distributed in apart from densely populated industry prosperity area compared with Remote outlying district, transmission & distribution are difficult, directly using at high cost, if being translated into the liquid energy for being easy to transport, can reduce Transportation cost provides convenience for long-distance sand transport and utilization.Methanol is considered as that methane converts optimal liquid product, excellent Point mainly has: 1., methanol remains most energy of methane, and has higher air compression ratio and gasification latent heat, can Using the fuel as clean vehicle fuel and high power fuel cell；2. methanol is a kind of important organic solvent and chemical industry Raw material can be used to produce chloromethanes, formaldehyde, vinylon, acetate fiber, dyestuff, dimethyl ether and adhesive etc.；3. methanol It is liquid at normal temperatures and pressures, is readily transported and stores.When the practical threat that facing mankind fossil energy reserves reduce year by year When, with the reduction of methanol cost and price, a kind of trend is had developed into using methanol as petrochemical materials new sources.

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, Biogas, petroleum or residual oil etc. may be utilized in fabricating synthesis gas.Liquids and gases fuel, great Zong Hua can be converted to using synthesis gas The fine Organic chemical products of product and high added value.Therefore replace synthesis gas that can have using reproducible biogas as raw material The reduction environmental pollution of effect and greenhouse effects, develop the catalyst of efficient catalysis biogas full constituent transformation of synthetic gas for The current national conditions in China 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 Catalyst for methanol LaNiO₃/SiC-SiO₂-Fiber.The present invention is generated using SiC-Fiber as raw material, by calcining in surface of SiC One layer of SiO₂Film obtains carrier S iC-SiO₂-Fiber；Then with LaNiO₃For catalytic active component, pass through load capacity, calcining item The optimization of part, so that Ca-Ti ore type LaNiO₃Particle is smaller, and dispersibility is high, is uniformly dispersed, avoids high load nickel-base catalyst The problem for being easy to reunite, catalytic performance is limited at high temperature.In addition, Ni-La can be obtained after hydrogen reducing₂O₃/SiC-SiO₂- Fiber, Ni-La₂O₃/SiC-SiO₂For nickel element by the corresponding precipitation that puts in order, dispersibility is high in-Fiber, is evenly distributed, property It can stablize, high conversion rate, biogas full constituent transformation of synthetic gas can be catalyzed well for answering in the reaction of synthesising biological methanol With.

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

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

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-SiO₂- Fiber, LaNiO₃It is carried on carrier SiC-SiO₂On-Fiber, LaNiO₃Load capacity be 3~7%；The LaNiO₃/SiC-SiO₂- Fiber is as follows It is prepared:

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

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

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

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, for the present invention with anti-cold spot, the SiC-Fiber that reaction pressure can be maintained stable is carrier element, passes through height Temperature calcining is so that the surface oxidation of silicon carbide SiC generates one layer of SiO₂There is thermally conductive uniform heat conduction efficiently to wait spies for film, silicon carbide Point, while the SiO generated₂Film can increase the interaction between active component and carrier in turn from cold spot problem and activity problems Two aspects solve the problems, such as and promote 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 catalyst LaNiO that the present invention is prepared₃/SiC-SiO₂- Fiber surface-element is suitable with Ca-Ti ore type structure cell Sequence ordered arrangement, then Ni-La can be obtained after hydrogen reducing₂O₃/SiC-SiO₂- Fiber, Ni-La₂O₃/SiC-SiO₂-Fiber For middle nickel element by the corresponding precipitation that puts in order, dispersibility is high, 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-Fiber 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 Fiber.

It should be understood that load capacity refers to catalytic active component LaNiO₃In entire catalyst LaNiO₃/SiC-SiO₂- Mass fraction in Fiber.

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)₂One 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- Fiber is prepared by following process: by above-mentioned LaNiO₃/SiC-SiO₂- Fiber at 750~850 DEG C of atmosphere of hydrogen into Row reduction treatment is up to the Ni-La₂O₃/SiC-SiO₂-Fiber。

LaNiO₃Itself it is not have catalytic activity, forms LaNiO₃Point that structure may make nickel lanthanum element more orderly Cloth forms unified orderly entirety, LaNiO₃(reduction obtains Ni-La after hydrogen reducing goes out metallic nickel₂O₃/SiC-SiO₂- Fiber) 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- Fiber 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 Fiber in catalysis biogas full constituent transformation of synthetic gas.

Ni-La₂O₃/SiC-SiO₂- Fiber 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 Fiber when being catalyzed biogas is 750~950 DEG C (normal Pressure), wherein it is best with 950 DEG C.

Ni-La₂O₃/SiC-SiO₂Dosage of-the Fiber 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-Fiber as raw material, by calcining₂Film obtains carrier S iC- SiO₂-Fiber；The present invention is with LaNiO₃As active constituent, the cell configuration with Ca-Ti ore type, all nickel lanthanum elements are all With certain regular arrangement.Simultaneously by the reduction of hydrogen so that Ca-Ti ore type LaNiO₃In nickel element be orderly precipitated and make It is smaller to obtain nickel particle, dispersibility is high, is uniformly dispersed, and avoids high load nickel-base catalyst and is easy to reunion, catalytic at high temperature The problem that can be limited；Ni-La can be obtained after reduction treatment₂O₃/SiC-SiO₂-Fiber。Ni-La₂O₃/SiC-SiO₂-Fiber For middle nickel element by the corresponding precipitation that puts in order, dispersibility is high, 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.

Detailed description of the invention

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

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.