阅读说明：本技术 沼气全组分转化生物甲醇催化剂Ni-CeO2/SiC-SiO2及其制备方法与应用 (Biogas full constituent inverting biological catalyst for methanol Ni-CeO2/SiC-SiO2And the preparation method and application 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Ni-CeO_2/SiC-SiO_2及其制备方法和应用。该制备方法包括如下步骤：S1：将SiC煅烧得SiC-SiO_2；S2：将镍源和铈源溶解后加入SiC-SiO_2,粉碎,干燥,得Ni-CeO_2/SiC-SiO_2前体；S3：将Ni-CeO_2/SiC-SiO_2前体煅烧,得NiO-CeO_2/SiC-SiO_2；S4：进一步煅烧,即得所述催化剂。本发明以SiC-SiO_2为载体,以Ni-CeO_2为催化活性成分,并优化条件,使得Ni-CeO_2颗粒较小,分散性高,分散均匀；制备得到的催化剂成本低廉,性能稳定,转化率高,可以很好地催化沼气转化合成气用于合成生物甲醇,具有较好的应用前景。(The present invention relates to biogas full constituent inverting biological catalyst for methanol Ni-CeO 2 /SiC‑SiO 2 And its preparation method and application.The preparation method includes the following steps: S1: SiC is calcined to obtain SiC-SiO 2 ；S2: SiC-SiO will be added after nickel source and the dissolution of cerium source 2 , it crushes, it is dry, obtain Ni-CeO 2 /SiC‑SiO 2 Precursor；S3: by Ni-CeO 2 /SiC‑SiO 2 Precursor calcining, obtains NiO-CeO 2 /SiC‑SiO 2 ；S4: further calcining is to get the catalyst.The present invention is with SiC-SiO 2 For carrier, with Ni-CeO 2 For catalytic active component, and optimal conditions, so that Ni-CeO 2 Particle is smaller, and dispersibility is high, is uniformly dispersed；The catalyst being prepared is low in cost, and performance is stablized, high conversion rate, can be catalyzed biogas transformation of synthetic gas well for synthesising biological methanol, with good application prospect.)

1. a kind of biogas full constituent inverting biological catalyst for methanol Ni-CeO₂/SiC-SiO₂Preparation method, which is characterized in that packet Include following steps:

S1: SiC is calcined at 950~1100 DEG C to 2~4h under oxygen-containing atmosphere and obtains SiC-SiO₂；；

S2: SiC-SiO will be added after nickel source and the dissolution of cerium source₂, pulverization process is dry, obtains Ni-CeO₂/SiC-SiO₂Precursor；

S3: by Ni-CeO₂/SiC-SiO₂Precursor, in 750~850 DEG C of 2~3h of calcining, obtains NiO-CeO under oxygen-containing atmosphere₂/SiC- SiO₂；

S4: by NiO-CeO₂/SiC-SiO₂Under an atmosphere of hydrogen in 750~850 DEG C of 1~3h of calcining to get the biogas full constituent Inverting biological catalyst for methanol Ni-CeO₂/SiC-SiO₂；

The Ni-CeO₂It is carried on carrier S iC-SiO₂On, Ni-CeO₂Load capacity be 4~15%, Ni and Ce mass ratio be 0.6~10:1.

2. preparation method according to claim 1, which is characterized in that the Ni-CeO₂Load capacity be 6~8%.

3. preparation method according to claim 1, which is characterized in that the mass ratio of the Ni and Ce is

4. preparation method according to claim 1, which is characterized in that the temperature of calcining described in S1 is 1000 DEG C, and the time is 3h。

5. preparation method according to claim 1, which is characterized in that oxygen-containing atmosphere described in S1 is air atmosphere.

6. preparation method according to claim 1, which is characterized in that nickel source described in S2 is Ni (NO₃)₂Or in nickel acetate It is one or more of；Cerium source described in S2 is Ce (NO₃)₃Or one or more of cerous acetate.

7. preparation method according to claim 1, which is characterized in that the temperature of calcining described in S3 is 800 DEG C, and the time is 3h。

8. preparation method according to claim 1, which is characterized in that the temperature of calcining described in S4 is 800 DEG C, and the time is 2h。

9. a kind of biogas full constituent inverting biological catalyst for methanol Ni-CeO₂/SiC-SiO₂, which is characterized in that pass through claim 1~8 any preparation method is prepared.

10. any biogas full constituent inverting biological catalyst for methanol Ni-CeO of claim 9₂/SiC-SiO₂In preparation biology Application in methanol.

Technical field

The invention belongs to catalyst technical fields, and in particular to biogas full constituent inverting biological catalyst for methanol Ni-CeO₂/ SiC-SiO₂And the preparation method and application 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.Existing for energy source distribution simultaneously Unbalanced problem such as also leads to and exacerbates oil crisis at the chain contradiction of society of reality.The energy as human civilization existence and What is developed is basic, and for measuring overall national strength and restricting the important indicator of national economy, therefore has for national security Key effect.China's oil reserves and yield are seriously deficient, and current oil consumption activity relies primarily on import, supply foreign countries Heavy dependence should be generated, causes China to face great energy security and threatens.Therefore petroleum resources and national security oneself through jail not It can divide, become the core content of Chinese energy safety strategy aspect.CO₂It is the main component of greenhouse gases, and more than 90% Artificial CO₂Discharge generates when being considered as fossil energy use, and a large amount of greenhouse gas emission makes atmospheric greenhouse gas Concentration increases, greenhouse effects enhance, so as to cause global warming, the problems such as sea level rise.Fossil energy it is big It is also the major reason for causing the present atmosphere polluting problem in China that amount, which uses,.So the substitution clean energy resource of exploitation fossil energy, It is of great significance for China's national security and economic development.When the real prestige that facing mankind fossil energy reserves reduce year by year When the side of body, with the reduction of methanol cost and price, one kind is had developed into as petrochemical materials new sources using methanol and is become Gesture.

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 transformation of synthetic gas in the reaction of synthesising biological methanol, what application was wide at present to be that noble metal is urged It is difficult to be applied to industrialization using noble metal higher cost for agent such as (Pd and Pt)；Therefore a kind of low in cost, property is researched and developed It can stablize, the catalyst of excellent catalytic effect has substantial promise.

Summary of the invention

It is an object of the invention to overcome the noble metal catalyst for being catalyzed biogas full constituent transformation of synthetic gas in the prior art It is at high cost, it is difficult to which that the defect and deficiency of industrial applications provide a kind of biogas full constituent inverting biological catalyst for methanol Ni- CeO₂/SiC-SiO₂Preparation method.The present invention is with SiC-SiO₂For carrier, with Ni-CeO₂For catalytic active component, and pass through The optimization of load capacity, calcination condition etc. so that Ni-CeO₂Particle is smaller, and dispersibility is high, is uniformly dispersed, overcomes high load Nickel-base catalyst is easy to the disadvantage reunited, catalytic performance is limited at high temperature.The Ni-CeO being prepared by the preparation method₂/ SiC-SiO₂Catalyst is low in cost, and performance is stablized, high conversion rate, can be catalyzed the conversion preparation synthesis of biogas full constituent well Gas, with good application prospect.

Another object of the present invention is to provide a kind of biogas full constituent inverting biological catalyst for methanol Ni-CeO₂/SiC- SiO₂。

Another object of the present invention is to provide above-mentioned biogas full constituent inverting biological catalyst for methanol Ni-CeO₂/SiC- SiO₂Application in catalysis biogas full constituent transformation of synthetic gas.

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

A kind of biogas full constituent inverting biological catalyst for methanol Ni-CeO₂/SiC-SiO₂Preparation method, including walk as follows It is rapid:

S1: SiC is calcined at 950~1100 DEG C to 2~4h under oxygen-containing atmosphere and obtains SiC-SiO₂；

S2: SiC-SiO will be added after nickel source and the dissolution of cerium source₂, pulverization process is dry, obtains Ni-CeO₂/SiC-SiO₂Before Body；

S3: by Ni-CeO₂/SiC-SiO₂Precursor, in 750~850 DEG C of 2~3h of calcining, obtains NiO-CeO under oxygen-containing atmosphere₂/ SiC-SiO₂；

S4: by NiO-CeO₂/SiC-SiO₂It is complete to get the biogas in 750~850 DEG C of 1~3h of calcining under an atmosphere of hydrogen Component inverting biological catalyst for methanol Ni-CeO₂/SiC-SiO₂；

The Ni-CeO₂It is carried on carrier S iC-SiO₂On, Ni-CeO₂Load capacity be 4~15%, Ni and Ce quality Than for 0.6~10:1.

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.One side Face, the present invention make the surface oxidation of SiC generate one layer of SiO using SiC as carrier element, by high-temperature calcination₂Film, silicon carbide tool There are the features such as thermally conductive uniform heat conduction is efficient, while the SiO generated₂Film can increase the interaction between active component and carrier And then catalytic reaction process problem encountered and catalysis work are solved and promoted in terms of cold spot problem and activity problems two Property problem.On the other hand, with Ni-CeO₂For catalytic active component, can some by the anti-carbon deposit property of Ce elements and nickel element The advantage and disadvantage of catalytic activity are mutually unified to promote the catalytic performance of catalyst.Meanwhile passing through the regulation to calcination condition and load capacity So that Ni-CeO₂Particle is smaller, and dispersibility is high, is uniformly dispersed, obtained catalyst n i-CeO₂/SiC-SiO₂It is low in cost, property It can stablize, high conversion rate, biogas transformation of synthetic gas can be catalyzed well for synthesising biological methanol, before there is preferable application Scape.

Nickel source, cerium source and SiC-SiO₂Dosage can be according to Ni-CeO₂Load capacity and the mass ratio of Ni and Ce be adjusted It chooses.

Ni-CeO₂Load capacity and the mass ratio of Ni and Ce will have to the performance of catalyst and have a certain impact, as nickel is negative Carrying capacity is too high, and being unevenly distributed and feeling has higher accumulation type to be unfavorable for catalysis reaction, is easy to cause catalyst inactivation；Load Amount is too low, and the too low catalytic activity of the active component content of catalyst is lower.The mass ratio of Ni and Ce is too high, the anti-carbon deposit of Ce elements Performance cannot play well, and mass ratio is too low, and the low catalytic performance of active component content is bad.By to load capacity and mass ratio Condition optimizes, and can further improve Ni-CeO₂/SiC-SiO₂Catalytic activity.

It should be understood that load capacity refers to catalytic active component Ni-CeO₂In entire catalyst n i-CeO₂/SiC- SiO₂In mass fraction.

Preferably, the Ni-CeO₂Load capacity be 6~8%.

Preferably, the mass ratio of the Ni and Ce is

It is further preferable that the Ni-CeO₂Load capacity be 8%, Ni and Ce mass ratio be 5:3.

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.

The nickel source of this field routine and cerium 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, cerium source described in S2 is Ce (NO₃)₃Or one or more of cerous acetate.

Preferably, Ni-CeO is obtained in S2₂/SiC-SiO₂It further include to Ni-CeO after precursor₂/SiC-SiO₂Precursor carries out Washing, dry step.

Preferably, the temperature of calcining described in S3 is 800 DEG C, time 3h.

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

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

Preferably, washing, drying are include thed steps that after calcining in S3.

Preferably, the temperature of calcining described in S4 is 800 DEG C, time 2h.

Preferably, it is heated up in S4 with the heating rate of 3~5 DEG C/min.

It preferably, further include by catalyst n i-CeO after being calcined in S4₂/SiC-SiO₂The step disperse, be filtered, washed, dried Suddenly.

A kind of biogas full constituent inverting biological catalyst for methanol Ni-CeO₂/SiC-SiO₂, prepared by above-mentioned preparation method It obtains.

Above-mentioned biogas full constituent inverting biological catalyst for methanol Ni-CeO₂/SiC-SiO₂Preparing the application in biological methanol Also within the scope of the present invention.

Preferably, the biogas full constituent inverting biological catalyst for methanol Ni-CeO₂/SiC-SiO₂In complete group of biogas of catalysis Divide the application in transformation of synthetic gas.

Biogas full constituent inverting biological catalyst for methanol Ni-CeO₂/SiC-SiO₂Biogas can be catalyzed and be changed into synthesis gas (CO And H₂), synthesis gas can be used as the raw material of synthesising biological methanol.

Under normal circumstances, biogas full constituent inverting biological catalyst for methanol Ni-CeO₂/SiC-SiO₂When being catalyzed biogas Temperature is 750~950 DEG C (normal pressure), wherein best with 800 DEG C.

Catalyst n i-CeO₂/SiC-SiO₂Dosage 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 is with SiC-SiO₂For carrier, with Ni-CeO₂For catalytic active component, and pass through load capacity, calcination condition etc. Optimization so that Ni-CeO₂Particle is smaller, and dispersibility is high, is uniformly dispersed, overcomes high load nickel-base catalyst at high temperature It is easy to the disadvantage reunited, catalytic performance is limited.The Ni-CeO being prepared by the preparation method₂/SiC-SiO₂Catalyst is at low cost Honest and clean, performance is stablized, high conversion rate, can be catalyzed biogas transformation of synthetic gas well for synthesising biological methanol, have preferable Application prospect.

Detailed description of the invention

Fig. 1 is the NiO-CeO that embodiment 1~12 provides₂/SiC-SiO₂XRD diagram；

Fig. 2 is the conversion ratio figure that embodiment 1~12 is catalyzed methane and carbon dioxide in the reaction product of biogas；

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.