阅读说明：本技术 沼气全组分转化生物甲醇催化剂SrNiO3/SiC-SiO2-Foam及其制备方法 (Biogas full constituent inverting biological catalyst for methanol SrNiO3/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SrNiO_3/SiC-SiO_2-Foam及其制备方法。该SrNiO_3/SiC-SiO_2-Foam,SrNiO_3负载于载体SiC-SiO_2-Foam上,SrNiO_3的负载量为2～8％。本发明制备的SrNiO_3/SiC-SiO_2-Foam具有钙钛矿型晶胞结构,钙钛矿型SrNiO_3颗粒较小,分散性高,分散均匀,避免了高负载镍基催化剂在高温下易于团聚、催化性能受限的问题；将其进行还原后得到的Ni-SrO/SiC-SiO_2-Foam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 SrNiO 3 /SiC‑SiO 2 - Foam and preparation method thereof.The SrNiO 3 /SiC‑SiO 2 - Foam, SrNiO 3 It is carried on carrier S iC-SiO 2 On-Foam, SrNiO 3 Load capacity be 2~8%.SrNiO prepared by the present invention 3 /SiC‑SiO 2 - Foam has Ca-Ti ore type cell configuration, Ca-Ti ore type SrNiO 3 Particle is smaller, and dispersibility is high, is uniformly dispersed, and avoids the problem that high load nickel-base catalyst is easy to reunite, catalytic performance is limited at high temperature；The Ni-SrO/SiC-SiO obtained after being restored 2 - Foam high conversion rate can be catalyzed biogas full constituent transformation of synthetic gas for the application in the reaction of synthesising biological methanol well.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 SrNiO₃/SiC-SiO₂- Foam, which is characterized in that SrNiO₃It is negative It is loaded in carrier S iC-SiO₂On-Foam, SrNiO₃Load capacity be 2~8%；It is described

SrNiO₃/SiC-SiO₂- 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-SiO₂-Foam；

S2: SiC-SiO will be added after barium source and nickel source dissolution₂Chelating agent is added in-Foam, pulverization process, carries out microwave treatment and obtains Gel, it is dry, obtain SrNiO₃/SiC-SiO₂- Foam Ca-Ti ore type precursor；

S3: by SrNiO₃/SiC-SiO₂- Foam Ca-Ti ore type precursor calcines 4~6h under an oxygen-containing atmosphere at 700~800 DEG C Obtain the SrNiO₃/SiC-SiO₂-Foam。

2. SrNiO according to claim 1₃/SiC-SiO₂- Foam, which is characterized in that the SrNiO₃Load capacity be 6%.

3. SrNiO 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. SrNiO 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；Barium source described in S2 is Sr (NO₃)₃Or one or more of strontium acetate；It is chelated described in S2 Agent is one or more of citric acid, sodium hydroxide or isopropanol.

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

6. SrNiO according to claim 1₃/SiC-SiO₂- Foam, which is characterized in that nickel element and strontium in S2 in nickel source The molar ratio of the summation citric acid of strontium element in source is 1:1~3.

7. SrNiO 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-SrO/SiC-SiO₂- Foam, which is characterized in that by as follows Process is prepared: by any SrNiO of claim 1~7₃/SiC-SiO₂- Foam is at 750~850 DEG C of atmosphere of hydrogen Reduction treatment is carried out up to the Ni-SrO/SiC-SiO₂-Foam。

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

10. any Ni-SrO/SiC-SiO of claim 8~9₂- 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 SrNiO₃/ 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, before the year two thousand fifty, petroleum, natural gas It will be depleted etc. non-renewable natural resources, this viewpoint has obtained the consistent approval of the whole society.A large amount of uses of fossil fuel Lead to carbon dioxide (CO in atmosphere₂) content rises year by year, greenhouse effects are increasingly severe.It is shown according to Global Carbon planning data, The CO2 emissions that global combustion of fossil fuel in 2013 generates reach 36,000,000,000 tons, middle state-two since the nineties in last century It aoxidizes total carbon emission and rapid growth situation is presented in discharge amount per capita.As the predominant gas for leading to greenhouse effects, titanium dioxide Carbon emission reduction and reasonable utilize have become global task.Carbon dioxide discharge-reduction is no longer a kind of morality and justice and social responsibility merely, Its comprehensive utilization has had distinct economic.Preparing synthetic gas by reforming methane with carbon dioxide is very promising two Carbonoxide utilizes technology path, works as H₂/ CO is at 0~0.9, CH₄- CO₂Conversion cost is minimum, traditional CH₄- CO₂Reform system H in the synthesis gas obtained₂/ CO is than general > 3.0, discomfort cooperation carbonylation synthesis and the raw material for producing oxygen-containing organic compound, dioxy Changing carbon part replaces water and methane that reforming reaction occurs, and can reduce production cost and energy consumption, and suitable F- T synthesis and methanol is made The synthesis gas of production.Therefore, which has great strategic significance for environmental protection and the utilization of resources, and research work is by numerous Researcher's concern.

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 SrNiO₃/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 SrNiO₃For catalytic active component, by load capacity, The optimization of calcination condition, so that Ca-Ti ore type SrNiO₃Particle 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 reduction treatment, obtained Ni-SrO/ SiC-SiO₂- Foam high conversion rate can be catalyzed biogas full constituent transformation of synthetic gas well and react for synthesising biological methanol In application.

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

Another object of the present invention is to provide above-mentioned Ni-SrO/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 SrNiO₃/SiC-SiO₂- Foam, SrNiO₃It is carried on carrier SiC-SiO₂On-Foam, SrNiO₃Load capacity be 3~7%；The SrNiO₃/SiC-SiO₂- Foam makes as follows It is standby to obtain:

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 after barium 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 SrNiO₃/SiC-SiO₂- Foam Ca-Ti ore type precursor；

S3: by SrNiO₃/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 SrNiO₃/SiC-SiO₂-Foam。

Research shows that with SiO₂For carrier high load nickel-base catalyst deposit be easy to reunite at high temperature, catalytic performance it is limited The shortcomings that.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 load Active component on body 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 with the SiC-Foam of strong constraint power and anti-cold spot effect with three-dimensional cavernous structure Phosphor bodies make the surface oxidation of silicon carbide SiC generate one layer of silicon carbide SiO by high-temperature calcination₂Film, silicon carbide have thermally conductive The features such as uniform heat conduction is efficient, while the SiO generated₂Film can increase the interaction between active component and carrier so that from It is solved the problems, such as in terms of cold spot problem and activity problems two and promotes catalytic reaction process problem encountered and catalytic activity.

On the other hand, the present invention is with SrNiO₃As active constituent, the cell configuration with Ca-Ti ore type, all nickel strontiums The sequence arrangement that element all has with certain rule.Simultaneously by the reduction of hydrogen so that Ca-Ti ore type SrNiO₃In nickel element have Sequence is precipitated so that nickel particle is smaller, and dispersibility is high, is uniformly dispersed, avoids high load nickel-base catalyst and be easy to roll into a ball at high temperature Problem poly-, catalytic performance is limited.

The SrNiO that the present invention is prepared₃/SiC-SiO₂- Foam catalyst precarsor element with higher is restrictive, tool Regular orderly arrangement of elements structure is provided by the cell configuration of its Ca-Ti ore type, and performance is stablized.After being restored, Metallic nickel is precipitated from structure cell centrally located position intracellular has preferable dispersibility, and strontium element is then first with oxygen remaining in structure cell Element combines the effect for forming the activated carbon that strontium oxide strontia provides strength to inhibit carbon distribution, obtained Ni-SrO/SiC-SiO₂-Foam High conversion rate, can be catalyzed well biogas full constituent transformation of synthetic gas for synthesising biological methanol reaction in application.This The preparation method simple process and low cost of invention is easy to industrialization promotion production.

Nickel source, barium source and SiC-SiO₂The dosage of-Foam can be according to SrNiO₃Load capacity selection is adjusted.

SrNiO₃Load capacity have a certain impact to the performance of catalyst tool, if load capacity is too low, SrNiO₃What is be distributed is dilute It dredges and is unable to reach the effect that Sr and Ni are mutually cooperateed with；Load capacity is too high, SrNiO₃Due 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, SrNiO can further improve₃/SiC-SiO₂- The catalytic activity of Foam.

It should be understood that load capacity refers to catalytic active component SrNiO₃In entire catalyst SrNiO₃/SiC-SiO₂- Mass fraction in Foam.

Preferably, the SrNiO₃Load capacity be 6%.

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 and barium source of this field routine are used equally in the present invention.

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

Preferably, barium source described in S2 is Sr (NO₃)₃, one or more of strontium acetate.

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

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

Preferably, the summation of the strontium element in the nickel element and barium source in S2 in nickel source and the molar ratio of citric acid are 1:1 ~3.

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-SrO/SiC-SiO is also claimed in the present invention₂- Foam, It is prepared by following process: by above-mentioned SrNiO₃/SiC-SiO₂- Foam is restored at 700~850 DEG C of atmosphere of hydrogen It handles up to the Ni-SrO/SiC-SiO₂-Foam。

SrNiO₃Itself it is not have catalytic activity, forms SrNiO₃Perovskite structure may make nickel strontium element more added with The distribution of sequence forms unified orderly entirety, (Ni-SrO/SiC-SiO is obtained after reduction after hydrogen reducing goes out metallic nickel₂- 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 by other while improving catalytic activity Some factors such as reunion carbon distribution etc. influenced.

Preferably, the time of the reduction is 1~3h.

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

Above-mentioned Ni-SrO/SiC-SiO₂- Foam prepare in bio-fuel application it is also within the scope of the present invention.

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

Ni-SrO/SiC-SiO₂- Foam can be catalyzed biogas and be changed into synthesis gas (CO and H₂), synthesis gas can be used as synthesis and close At the raw material of bio-fuel methanol.

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

Ni-SrO/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 SrNiO₃For catalytic active component, by load capacity, the optimization of calcination condition, so that Ca-Ti ore type SrNiO₃Particle 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, obtained Ni-SrO/SiC-SiO₂- Foam high conversion rate, can be fine Ground is catalyzed 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 SrNiO₃/SiC-SiO₂The XRD diagram of-Foam；

Fig. 2 is the conversion ratio figure of methane and carbon dioxide in Examples 1 to 4 reaction product；

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.