阅读说明：本技术 沼气全组分转化生物甲醇催化剂NdNiO3/SiC-SiO2-Foam及其制备方法 (Biogas full constituent inverting biological catalyst for methanol NdNiO3/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NdNiO_3/SiC-SiO_2-Foam及其制备方法。该催化剂NdNiO_3/SiC-SiO_2-Foam,NdNiO_3负载于载体SiC-SiO_2-Foam上,NdNiO_3的负载量为2～8％。该NdNiO_3/SiC-SiO_2-Foam具有钙钛矿型晶胞结构,钙钛矿型NdNiO_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-Nd_2O_3/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 NdNiO 3 /SiC‑SiO 2 - Foam and preparation method thereof.Catalyst n dNiO 3 /SiC‑SiO 2 - Foam, NdNiO 3 It is carried on carrier S iC-SiO 2 On-Foam, NdNiO 3 Load capacity be 2~8%.The NdNiO 3 /SiC‑SiO 2 - Foam has Ca-Ti ore type cell configuration, Ca-Ti ore type NdNiO 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-Nd obtained after being restored 2 O 3 /SiC‑SiO 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 NdNiO₃/SiC-SiO₂- Foam, which is characterized in that NdNiO₃It is negative It is loaded in carrier S iC-SiO₂On-Foam, NdNiO₃Load capacity be 2~8%；The NdNiO₃/SiC-SiO₂- Foam is by such as Lower step is prepared:

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 NdNiO₃/SiC-SiO₂- Foam Ca-Ti ore type precursor；

S3: by NdNiO₃/SiC-SiO₂- Foam Ca-Ti ore type precursor calcines 4~6h under an oxygen-containing atmosphere at 700~800 DEG C Obtain the NdNiO₃/SiC-SiO₂-Foam。

2. NdNiO according to claim 1₃/SiC-SiO₂- Foam, which is characterized in that the NdNiO₃Load capacity be 6%.

3. NdNiO 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. NdNiO 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 Nd (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. NdNiO 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. NdNiO 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. NdNiO 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-Nd₂O₃/SiC-SiO₂- Foam, which is characterized in that by such as Lower process is prepared: by any NdNiO 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-Nd₂O₃/SiC-SiO₂-Foam。

9. Ni-Nd 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-Nd 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 NdNiO₃/ SiC-SiO₂- Foam and preparation method thereof.

Background technique

With the cumulative year after year of China's oil import volume, China's oil safety supply faces the challenge being on the rise.And I State's on the one hand wretched insufficiency per capita in petroleum reserves is on the other hand again very sufficient on biomass resource.Therefore, based on The energy natural endowment in China's " it is oil-poor that rich coal lacks gas ", search for oil replace the energy, China's biomass resource are actively utilized, to China's energy Source safety and economic development have great significance.And it uses biomass to produce biogas for raw material and then prepares synthesis gas (predominantly CO+H₂) high added values such as synthesizing methanol or low carbon mixed alcohol chemical products.So the exploitation biomass clean energy, for me State's national security and economic development are of great significance.When the practical threat that facing mankind fossil energy reserves reduce year by year, With the reduction of methanol cost and price, a kind of trend is had developed into using methanol as petrochemical materials new sources.Though So current global methanol excess capacity, but methanol, as C1 chemistry foundation stone, application range constantly expands, its market prospects quilt It is good extensively.Methanol is both that clean fuel is also important Organic Chemicals, produces downstream chemical industry with by raw material of methanol The continuous Jian of Product Process is sent out, and the market demand of methanol also will necessarily be more and more.According to the data of nitrogen fertilizer industry association, China Statistics, China's methanol Apparent con- sumption reaches 3195.8 ten thousand tons within 2011, improves 40.8% on year-on-year basis.Formaldehyde, acetic acid are to methanol Demand increases by 4% and 10% respectively, and dimethyl ether, methanol fuel (methanol gasoline) are then more than to the demand growth of methanol 50%, methanol prepares alkene and reaches 2,600,000 tons to the demand of methanol.The same year China's methanol import volume is 573.2 ten thousand tons, on year-on-year basis 10.45% is increased, average inlet price is 368.7 beauty yuan/ton, increases 73.7 beauty yuan/ton on year-on-year basis, price goes up on year-on-year basis 25%.Therefore the research and improvement of methanol synthesis technology cause the great attention of various countries.

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 Catalyst for methanol NdNiO₃/SiC-SiO₂-Foam.The present invention generates one in surface of SiC using SiC-Foam as raw material, by calcining Layer SiO₂Film obtains carrier S iC-SiO₂-Foam；Then with NdNiO₃For catalytic active component, pass through load capacity, calcination condition Optimization so that Ca-Ti ore type NdNiO₃Particle is smaller, and dispersibility is high, is uniformly dispersed, avoids high load nickel-base catalyst and exist The problem for being easy to reunite, catalytic performance is limited under high temperature.By further progress reduction treatment, obtained Ni-Nd₂O₃/SiC- SiO₂- Foam high conversion rate can be catalyzed biogas full constituent transformation of synthetic gas in the reaction of synthesising biological methanol well Using.

Another object of the present invention is to provide a kind of biogas full constituent inverting biological catalyst for methanol Ni-Nd₂O₃/SiC- SiO₂-Foam。

Another object of the present invention is to provide above-mentioned Ni-Nd₂O₃/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 NdNiO₃/SiC-SiO₂- Foam, NdNiO₃It is carried on carrier SiC-SiO₂On-Foam, NdNiO₃Load capacity be 3~7%；The NdNiO₃/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 NdNiO₃/SiC-SiO₂- Foam Ca-Ti ore type precursor；

S3: by NdNiO₃/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 NdNiO₃/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 with high-termal conductivity, the SiC-Foam of high thermal stability and high mechanical strength is carrier master Body makes the surface oxidation of silicon carbide SiC generate one layer of SiO by high-temperature calcination₂Film, this can increase active component and carrier Between interaction so that solved in terms of cold spot problem and activity problems two and promote that catalytic reaction process encountered asks Topic and catalytic activity problem.

On the other hand, the present invention is with NdNiO₃As 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 NdNiO₃In 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 NdNiO 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 a preferable dispersibility, strontium element then 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-Nd₂O₃/SiC-SiO₂- The high conversion rate of Foam can be catalyzed biogas full constituent transformation of synthetic gas for answering in the reaction of synthesising biological methanol well With.Preparation method simple process and low cost of the invention is easy to industrialization promotion production.

Nickel source, neodymium source and SiC-SiO₂The dosage of-Foam can be according to NdNiO₃Load capacity selection is adjusted.

NdNiO₃Load capacity have a certain impact to the performance of catalyst tool, if load capacity is too low, NdNiO₃What is be distributed is dilute It dredges and is unable to reach the effect that Nd and Ni are mutually cooperateed with；Load capacity is too high, NdNiO₃Due 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, NdNiO can further improve₃/SiC-SiO₂- The catalytic activity of Foam.

It should be understood that load capacity refers to catalytic active component NdNiO₃In entire NdNiO₃/SiC-SiO₂- Foam is urged Mass fraction in agent.

Preferably, the NdNiO₃Load 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 of this field routine and neodymium 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, barium source described in S2 is Nd (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 nickel element in S2 nickel source and the neodymium element in neodymium 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 neodymium element in neodymium source is 1:1: 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-Nd is also claimed in the present invention₂O₃/SiC-SiO₂- Foam is prepared by following process: by above-mentioned NdNiO₃/SiC-SiO₂- Foam is carried out at 700~850 DEG C of atmosphere of hydrogen Reduction treatment is up to the Ni-Nd₂O₃/SiC-SiO₂-Foam。

NdNiO₃Itself it is not have catalytic activity, forms NdNiO₃Perovskite structure may make nickel strontium element more added with The distribution of sequence forms unified orderly entirety, and metallic nickel is precipitated from structure cell centrally located position intracellular after hydrogen reducing, tool There is a preferable dispersibility, strontium element then forms strontium oxide strontia in conjunction with oxygen element remaining in structure cell and provides the activated carbon of strength Effect inhibits carbon distribution, obtained Ni-Nd₂O₃/SiC-SiO₂The high conversion rate of-Foam can be catalyzed biogas full constituent well Transformation of synthetic gas is 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.

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

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

Above-mentioned Ni-Nd₂O₃/SiC-SiO₂- Foam is preparing the application in biological methanol also in protection scope of the present invention It is interior.

Preferably, the Ni-Nd₂O₃/SiC-SiO₂Application of-the Foam in catalysis biogas full constituent transformation of synthetic gas.

Ni-Nd₂O₃/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-Nd₂O₃/SiC-SiO₂Temperature of-the Foam when being catalyzed biogas is 750~950 DEG C (normal pressure), Wherein, best with 950 DEG C.

Ni-Nd₂O₃/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 NdNiO₃For catalytic active component, by load capacity, the optimization of calcination condition, so that Ca-Ti ore type NdNiO₃Particle 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 progress reduction treatment, metallic nickel is precipitated from structure cell centrally located position intracellular, has Preferable dispersibility, strontium element then form the effect that strontium oxide strontia provides the activated carbon of strength in conjunction with oxygen element remaining in structure cell Fruit inhibits carbon distribution, obtained Ni-Nd₂O₃/SiC-SiO₂The high conversion rate of-Foam can be catalyzed biogas full constituent well and turn Gas is combined to for the application in the reaction of synthesising biological methanol.Preparation method simple process and low cost of the invention, is easy to work Industryization promotes production.

Detailed description of the invention

Fig. 1 is perovskite type catalyst NdNiO₃/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.