阅读说明：本技术 沼气全组分转化生物甲醇催化剂Ni-La2O3/SiC-SiO2及其制备方法与应用 (Biogas full constituent inverting biological catalyst for methanol Ni-La2O3/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-La_2O_3/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：将镍源和镧源溶解后加入SiC-SiO_2,粉碎,干燥,得Ni-La_2O_3/SiC-SiO_2前体；S3：将Ni-La_2O_3/SiC-SiO_2前体煅烧,得NiO-La_2O_3/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-La_2O_3为催化活性成分,并优化条件,使得Ni-La_2O_3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全组分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-La 2 O 3 /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 lanthanum source 2 , it crushes, it is dry, obtain Ni-La 2 O 3 /SiC‑SiO 2 Precursor；S3: by Ni-La 2 O 3 /SiC‑SiO 2 Precursor calcining, obtains NiO-La 2 O 3 /SiC‑SiO 2 ；S4: further calcining is to get the catalyst.The present invention is with SiC-SiO 2 For carrier, with Ni-La 2 O 3 For catalytic active component, and optimal conditions, so that Ni-La 2 O 3 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 full constituent 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-La₂O₃/SiC-SiO₂Preparation method, which is characterized in that Include the 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 lanthanum source₂, pulverization process is dry, obtains Ni-La₂O₃/SiC-SiO₂Precursor；

S3: by Ni-La₂O₃/SiC-SiO₂Precursor, in 750~850 DEG C of 2~3h of calcining, obtains NiO-La under oxygen-containing atmosphere₂O₃/ SiC-SiO₂；

S4: by NiO-La₂O₃/SiC-SiO₂Under an atmosphere of hydrogen in 750~850 DEG C of 1~3h of calcining to get complete group of the biogas Divide inverting biological catalyst for methanol Ni-La₂O₃/SiC-SiO₂；

The Ni-La₂O₃It is carried on carrier S iC-SiO₂On, Ni-La₂O₃Load capacity be 4~15%, Ni and La mass ratio be 0.6~10:1.

2. preparation method according to claim 1, which is characterized in that the Ni-La₂O₃Load capacity be 13~15%.

3. preparation method according to claim 1, which is characterized in that the mass ratio of the Ni and La 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；Lanthanum source described in S2 is La (NO₃)₃Or one or more of lanthanum 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-La₂O₃/SiC-SiO₂, which is characterized in that it is wanted by right 1~8 any preparation method is asked to be prepared.

10. any biogas full constituent inverting biological catalyst for methanol Ni-La of claim 9₂O₃/SiC-SiO₂It is given birth in preparation Application in object methanol.

Technical field

The invention belongs to catalyst technical fields, and in particular to biogas full constituent inverting biological catalyst for methanol Ni-La₂O₃/ 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 full constituent transformation of synthetic gas in the reaction of synthesising biological methanol, what application was wide at present to be expensive It is difficult to be applied to industrialization using noble metal higher cost for metallic catalyst such as (Pd and Pt)；Therefore it researches and develops a kind of at low cost Honest and clean, performance is stablized, and the catalyst of excellent catalytic effect has substantial promise.

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 Noble metal catalyst in alcohol reaction is at high cost, it is difficult to which the defect and deficiency of application provide a kind of biogas full constituent inverting biological Catalyst for methanol Ni-La₂O₃/SiC-SiO₂Preparation method.The present invention is with SiC-SiO₂For carrier, with Ni-La₂O₃It lives for catalysis Property ingredient, and by the optimization of load capacity, calcination condition etc. so that Ni-La₂O₃Particle is smaller, and dispersibility is high, is uniformly dispersed, Overcome the disadvantage that high load nickel-base catalyst is easy to reunite, catalytic performance is limited at high temperature.It is prepared by the preparation method The biogas full constituent inverting biological catalyst for methanol Ni-La arrived₂O₃/SiC-SiO₂Low in cost, performance is stablized, and high conversion rate can It is reacted with being catalyzed biogas full constituent transformation of synthetic gas well for synthesising biological methanol, 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-La₂O₃/SiC- SiO₂。

Another object of the present invention is to provide above-mentioned biogas full constituent inverting biological catalyst for methanol Ni-La₂O₃/SiC- SiO₂Preparing the application in biological methanol.

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-La₂O₃/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 lanthanum source₂, pulverization process is dry, obtains Ni-La₂O₃/SiC-SiO₂Before Body；

S3: by Ni-La₂O₃/SiC-SiO₂Precursor, in 750~850 DEG C of 2~3h of calcining, obtains NiO- under oxygen-containing atmosphere La₂O₃/SiC-SiO₂；

S4: by NiO-La₂O₃/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-La₂O₃/SiC-SiO₂；

The Ni-La₂O₃It is carried on carrier S iC-SiO₂On, Ni-La₂O₃Load capacity be 4~15%, Ni and La 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 SiC has the characteristics that thermally conductive uniform heat conduction is efficient, while the SiO generated₂Film can increase the phase between active component and carrier Interaction solve and promote in terms of cold spot problem and activity problems two in turn catalytic reaction process problem encountered and Catalytic activity problem.On the other hand, with Ni-La₂O₃It, can be by anti-carbon deposit property and the nickel member of lanthanum element for catalytic active component The advantage and disadvantage of the catalytic activity of element are mutually unified to promote the catalytic performance of catalyst.Meanwhile by calcination condition and load capacity Regulation is so that Ni-La₂O₃Particle is smaller, and dispersibility is high, is uniformly dispersed, obtained Ni-La₂O₃/SiC-SiO₂Catalyst is at low cost Honest and clean, performance is stablized, high conversion rate, can be catalyzed biogas full constituent transformation of synthetic gas well for synthesising biological methanol, have Preferable application prospect.

Nickel source, lanthanum source and SiC-SiO₂Dosage can be according to Ni-La₂O₃Load capacity and the mass ratio of Ni and La adjusted Selected parts take.

Ni-La₂O₃Load capacity and the mass ratio of Ni and La 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 La is too high, the anti-carbon deposit of lanthanum element 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-La₂O₃/SiC-SiO₂Catalytic activity.

It should be understood that load capacity refers to catalytic active component Ni-La₂O₃In entire catalyst n i-La₂O₃/SiC- SiO₂In mass fraction.

Preferably, the Ni-La₂O₃Load capacity be 13~15%.

Preferably, the mass ratio of the Ni and La is

It is further preferable that the Ni-La₂O₃Load capacity be 13%, Ni and La mass ratio be 10:3.

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 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)₃Or one or more of lanthanum acetate.

Preferably, Ni-La is obtained in S2₂O₃/SiC-SiO₂It further include to Ni-La after precursor₂O₃/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.

It preferably, further include by catalyst n i-La after being calcined in S3₂O₃/SiC-SiO₂Disperse, be filtered, washed, drying Step.

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

A kind of biogas full constituent inverting biological catalyst for methanol Ni-La₂O₃/SiC-SiO₂, prepared by above-mentioned preparation method It obtains.

Above-mentioned biogas full constituent inverting biological catalyst for methanol Ni-La₂O₃/SiC-SiO₂Preparing answering in biological methanol With also within the scope of the present invention.

Preferably, the biogas full constituent inverting biological catalyst for methanol Ni-La₂O₃/SiC-SiO₂In complete group of biogas of catalysis Divide the application in transformation of synthetic gas.

Catalyst n i-La₂O₃/SiC-SiO₂Biogas can be catalyzed and be changed into synthesis gas (CO and H₂), synthesis gas can be used as synthesis The raw material of biological methanol.

Under normal circumstances, catalyst n i-La₂O₃/SiC-SiO₂Temperature when being catalyzed biogas is 750~950 DEG C (normal Pressure), wherein it is best with 800 DEG C.

Catalyst n i-La₂O₃/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, using Ni-La2O3 as catalytic active component, and pass through load capacity, calcination condition Deng optimization so that Ni-La2O3 particle it is smaller, dispersibility is high, is uniformly dispersed, overcomes high load nickel-base catalyst in height It is easy to the disadvantage reunited, catalytic performance is limited under temperature.The biogas full constituent inverting biological methanol being prepared by the preparation method Catalyst n i-La₂O₃/SiC-SiO₂Low in cost, performance is stablized, high conversion rate, can be catalyzed the conversion of biogas full constituent well Synthesis gas is reacted for synthesising biological methanol, with good application prospect.

Detailed description of the invention

Fig. 1 is the NiO-La that embodiment 1~12 provides₂O₃/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.