CN110508301A - Biogas full constituent inverting biological catalyst for methanol SrNiO3/SiC-SiO2- Foam and preparation method thereof - Google Patents

Biogas full constituent inverting biological catalyst for methanol SrNiO3/SiC-SiO2- Foam and preparation method thereof Download PDF

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CN110508301A
CN110508301A CN201910808599.4A CN201910808599A CN110508301A CN 110508301 A CN110508301 A CN 110508301A CN 201910808599 A CN201910808599 A CN 201910808599A CN 110508301 A CN110508301 A CN 110508301A
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foam
sic
sio
srnio
nickel
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CN110508301B (en
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谢君
张止戈
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South China Agricultural University
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Abstract

The present invention relates to biogas full constituent inverting biological catalyst for methanol SrNiO3/SiC‑SiO2- Foam and preparation method thereof.The SrNiO3/SiC‑SiO2- Foam, SrNiO3It is carried on carrier S iC-SiO2On-Foam, SrNiO3Load capacity be 2~8%.SrNiO prepared by the present invention3/SiC‑SiO2- Foam has Ca-Ti ore type cell configuration, Ca-Ti ore type SrNiO3Particle 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 restored2- 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.

Description

Biogas full constituent inverting biological catalyst for methanol SrNiO3/SiC-SiO2- Foam and its Preparation method
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.
Examples 1 to 4
The present embodiment provides a series of perovskite type catalyst SrNiO3/SiC-SiO2- Foam is prepared via a method which It obtains.
1)SiC-SiO2The preparation of-Foam
By SiC-Foam, 1000 DEG C of calcining 3h obtain SiC-SiO under air atmosphere2-Foam。
2)SrNiO3/SiC-SiO2The preparation of-Foam perovskite type catalyst precursor
By Ni (NO3)2With Sr (NO3)3It is dissolved in 30mL deionized water with corresponding load capacity quality and is persistently stirred, together When corresponding amount treated SiC-SiO is added2-Foam.After solution is placed on breaking-wall cell crusher processing 30min, add Enter citric acid identical with nitrate mole, handles 30min under microwave condition and form green collosol and gel.Gel exists It is drying over night to get SrNiO in the environment of 110 DEG C3/SiC-SiO2- Foam Ca-Ti ore type precursor.To SrNiO3/SiC-SiO2- Foam Ca-Ti ore type precursor be washed with water 3~4 times, makes filtrate to neutrality, and ethyl alcohol is washed three times, dries 8h in 35 DEG C of baking ovens, Obtain SrNiO3/SiC-SiO2- Foam Ca-Ti ore type precursor solid.
Specific additive amount is shown in Table 1 (SrNiO3Load capacity=SrNiO3/(SrNiO3Quality+SiC-SiO2- Foam matter Amount)).
Perovskite type catalyst SrNiO in 1 Examples 1 to 4 of table3/SiC-SiO2- Foam and its dosage control
3) perovskite type catalyst SrNiO3/SiC-SiO2The preparation of-Foam
The SrNiO that will be obtained3/SiC-SiO2The preparation of-Foam Ca-Ti ore type precursor, using the method for calcining, in Muffle furnace It is calcined under middle air atmosphere.The heating rate of calcining is 5 DEG C per minute, is warming up to 750 DEG C, calcines 3 hours.It is cooled to later Room temperature will obtain solid and be added into water, and magnetic stirring apparatus 600r/min revolving speed stirs 8h, filtering, and ethyl alcohol is washed 3 times.It is put into 35 DEG C baking oven drying 3h is to get arriving perovskite type catalyst SrNiO3/SiC-SiO2-Foam。
Embodiment 5
The present embodiment provides a kind of perovskite type catalyst SrNiO3/SiC-SiO2- Foam, preparation method and embodiment 3 Almost the same, difference is, the present embodiment step 1) prepares SiC-SiO in calcining2When-Foam, the temperature of calcining is 900 DEG C, The time of calcining is 2h；Step 3) is in preparation SrNiO3/SiC-SiO2When-Foam, the heating rate of calcining is 3 DEG C per minute, is forged The temperature of burning is 750 DEG C, time 4h.
Embodiment 6
The present embodiment provides a kind of perovskite type catalyst SrNiO3/SiC-SiO2- Foam, preparation method and embodiment 3 Almost the same, difference is, the present embodiment step 1) prepares SiC-SiO in calcining2When-Foam, the temperature of calcining is 1050 DEG C, The time of calcining is 4h；Step 3) is in preparation SrNiO3/SiC-SiO2When-Foam, the heating rate of calcining is 3 DEG C per minute, is forged The temperature of burning is 800 DEG C, time 6h.
Performance test
(1) it characterizes
Using following means, the preparation-obtained catalyst of above-described embodiment is characterized.
1) X ray diffracting spectrum (XRD): as shown in Figure 1.
Fig. 1 is 3 gained perovskite type catalyst SrNiO of embodiment3/SiC-SiO2The XRD of-Foam is set forth in figure Pure perovskite-type compounds SrNiO3Map and SrNiO3The diffraction maximum one of map after load, their diffraction maximum and SiC It causes.List perovskite type catalyst SrNiO3/SiC-SiO2The XRD diagram of-Foam, available and SrNiO3Main diffraction peak symbol It closes.
Catalytic activity
By the resulting perovskite type catalyst SrNiO of Examples 1 to 43Each 0.2g of/SiC-SiO2-Foam distinguishes reactor In.It is first ventilated 5~6 times using nitrogen, drains air in reaction kettle, be subsequently passed after the reduction of 5% hydrogen in-situ (700~850 DEG C 1~3h of lower reduction, specifically obtains Ni-SrO/SiC-SiO after reductase 12 h at 800 DEG C2- Foam), it is warming up to 750~950 immediately It is reacted at DEG C, gas production is carried out after stable reaction.Gained is produced gas and is detected using gas-chromatography, and test result is shown in Fig. 2.
The reaction of synthesis gas, mainly turn of methane and carbon dioxide are prepared generally, for biogas full constituent conversion Change.Methane and carbon dioxide content is lower after reaction, illustrates that catalytic activity is higher.
Figure it is seen that the SrNiO3/SiC-SiO2- Foam perovskite type catalyst is catalyzed the conversion of biogas full constituent and closes It is reacted at gas for synthesising biological methanol.It can be seen that different load percentages not by the catalytic effect of Examples 1 to 4 It is not quite similar at a temperature of for the effect of catalysis, at the same temperature with SrNiO since load capacity 2wt%3Ratio Increase conversion ratio gradually increase, with temperature increase conversion ratio gradually increase.When load capacity is 6wt%, conversion ratio reaches most Big value is the ratio conversion ratio maximum of 6wt% at 800 DEG C and 850 DEG C.With SrNiO3Load capacity is different, and the crystal of formation is living Property site it is different, specific surface also changes, and works as SrNiO3Reaching a timing, the crystal active site of formation is optimal, from And generate best catalytic effect.
In addition, the SrNiO provided with embodiment 33/SiC-SiO2For-Foam, with Pd, Pt noble metal catalyst is compared. Such as 6 (2016) 10372-10384. of document F.Aldoghachi, U.Rashid, T.Y.Yun, Rsc Advances is disclosed At identical 900 DEG C, four kinds of noble metal catalyst (such as table 2) catalysis biogas full constituent conversions prepare the test knot of synthesis gas Fruit, as ((therein 1,2,3 and 4 have respectively represented (1) Pt, Pd, Ni/MgO, (2) Pt, Pd, Ni/Mg to Fig. 30.97Ce0.03 3+O, (3)Pt,Pd,Ni/Mg0.93Ce0.07 3+O and (4) Pt, Pd, Ni/Mg0.85Ce0.15 3+O))。
2 four kinds of noble metal noble metal catalyst sizes of table and composition
From Fig. 2 and Fig. 3 it is found that SrNiO provided by the present application3/SiC-SiO2The Ni-SrO/ that-Foam is obtained after carrying out reduction SiC-SiO2This similar to the conversion ratio containing noble metal catalyst of conversion ratio of-Foam methane at 900 DEG C can also prove this Catalyst is in the developing direction that future is a kind of great potential.
It can be seen from the above, Catalyst Conversion provided by the invention is high, it can be catalyzed the conversion of biogas full constituent well and close At gas for the application in the reaction of synthesising biological methanol.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (10)

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.
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