CN102600854A - Catalyst for carbon dioxide methanation and preparation method thereof - Google Patents
Catalyst for carbon dioxide methanation and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for carbon dioxide methanation and a preparation method of the catalyst, belonging to the technical field of carbon dioxide methanation. The catalyst for carbon dioxide methanation is composed of a composite carrier and an active ingredient at a ratio of 84-90wt%:10-16wt%, wherein the composite carrier is composed of gamma-Al2O3 and water soluble metal oxide at a mass ratio of 77-86:2-10; and the active ingredient is Ni which exists in the catalyst in a form of NiO. The catalyst is high in activity, low in cost and better in stability, and can be used for carbon dioxide methanation reaction under normal pressure condition.
Description
Technical field
The invention belongs to the carbon dioxide methanation technical field, particularly a kind of carbon dioxide methanation is used Catalysts and its preparation method.
Background technology
Carbon dioxide is one of carbon source that reserves enrich the most on the earth.Along with the exhaustion day by day of petroleum resources, in atmosphere, discharge caused serious ecologies of carbon dioxide and environmental problems in a large number, with greenhouse gases CO in addition
2The chemical products that change high added value into become the focus of domestic and international industry and academia's research and discussion.1902, french chemist Paul sabatier reported first the catalytic hydrogenating reduction technology of carbon dioxide (be CO
2Methanation reaction): CO
2(g)+4H
2(g)=CH
4(g)+2H
2O (g) Δ
RH
0298K=-252.9KJmol
-1, with CO
2Hydrogenation synthesizing methane gas is on the one hand with CO
2Turn waste into wealth, realized resources effective utilization (atom economy), the methane of reaction generation can be used as the gas of high-quality on the other hand, and realizes that technological process is simple, small investment, and cost is low.
People such as Jiang Qi (Jiang Qi, Deng Guocai, Chen Rongti, Huang Zhongtao. catalysis journal 18 (1997) 42-45) reported that the aqueous solution with the 10wt% nickel nitrate floods γ-Al
2O
3Carrier, 10wt%Ni/ γ-Al is prepared in 450 ℃ of air atmosphere roastings
2O
3Catalyst is used for CO
2Methanation reaction is found at 300 ℃ of following CO
2Conversion ratio be merely 15.2%, CH
4Selectivity be 97.5%.People such as Chu Wei (Mengdie Cai, Jie Wen, Wei Chu, Xueqing Cheng, Zejun Li.Journal of Natural Gas Chemistry20 (2011): 318-324) reported γ-Al with 12wt%Ni/88%
2O
3Catalyst is used for CO
2Methanation reaction is found having not a particle of reactivity below 240 ℃, along with the rising of reaction temperature, CO
2Conversion ratio and CH
4Productive rate be tangible ascendant trend, CO in the time of 360 ℃
2Conversion ratio be 24.8%, CH
4Productive rate be 24.3%, then investigated 12wt%Ni/ γ-Al
2O
3The reaction stability of catalyst under 360 ℃ found to cause CO behind reaction 50h owing to the carbon distribution of gathering that activity component metal nickel can take place in the course of reaction and reaction
2Conversion ratio drop to 16.5%, explain that the reactivity of this catalyst and performance for stability are poor.
For improving the Ni activity of such catalysts, CN9510367.2 is said like Chinese patent, in catalyst, added the catalyst for preparing behind the noble metal Ru and had greater activity, but the adding of Ru certainly will increase catalyst production cost.Chinese patent CN101884927 discloses a kind of Catalysts and its preparation method that is used for full methanation of carbon dioxide, and the mass percent of each component consists of in its catalyst: γ-Al
2O
3: 60-80%; NiO:10-20%; Fe
2O
3: 5-15%; MgO:1-10%; La
2O
3Or CeO
2: 1-10%, but this catalyst mainly is applicable to the full methanation of the middle 3.0-5.0MPa of pressure carbon dioxide, (this catalyst Main Ingredients and Appearance and proportioning thereof are the catalyst that we report this patent working example 1: 16.9%NiO-6.5%Fe
2O
3-3.3%MgO-2.8%CeO
2-70.5% γ-Al
2O
3) be applied to the carbon dioxide methanation reaction under the condition of normal pressure, find at 360 ℃ of following CO
2Conversion ratio be 87.5%, methane selectively is 100%, but through 100h stability test, CO
2Conversion ratio drop to 80.3%, CH
4Selectivity also is reduced to 99.4%, explains that the disclosed catalyst that is used for full methanation of carbon dioxide of Chinese patent CN101884927 only is applicable to depress CO
2Methanation reaction, and since in the course of reaction catalyst activity component take place to assemble the formation with area carbon, cause activity of such catalysts decline, the reaction stability of this catalyst is relatively poor.
Summary of the invention
The present invention is directed to above-mentioned defective, provide a kind of carbon dioxide methanation to use catalyst, this catalyst activity is high, cost is low, and this catalyst can be used for the carbon dioxide methanation reaction under the condition of normal pressure, and stability better.
Technical scheme of the present invention is:
The invention provides a kind of carbon dioxide methanation and use catalyst, form complex carrier by complex carrier and active component: active component=84-90wt%: 10-16wt%; Wherein, said complex carrier is by γ-Al
2O
3Form γ-Al with the water-soluble metal oxide
2O
3With the mass ratio of water-soluble metal oxide be 77-86: 2-10; Said active component is Ni, and is present in this catalyst with the NiO form.
Said water-soluble metal oxide is CeO
2, ZrO
2Or La
2O
3In at least a.
Preferably, each constituent mass ratio is in this catalyst: complex carrier: active component=84-88: 12-16; γ-Al in the complex carrier
2O
3With the mass ratio of water-soluble metal oxide be 78-86: 2-6.
Preferred, each constituent mass ratio is in this catalyst: complex carrier: active component=84.7: 15.3; γ-Al in the complex carrier
2O
3With the mass ratio of water-soluble metal oxide be 78.7: 6.
Preferred, each constituent mass ratio is in this catalyst: complex carrier: active component=87.3: 12.7; γ-Al in the complex carrier
2O
3With the mass ratio of water-soluble metal oxide be 81.3: 6.
Said complex carrier is CeO
2/ γ-Al
2O
3, ZrO
2/ γ-Al
2O
3Or La
2O
3/ γ-Al
2O
3In at least a; Be preferably CeO
2/ γ-Al
2O
3
Carbon dioxide methanation of the present invention is specially with the Preparation of catalysts method: adopt the dipping-precipitation method to prepare complex carrier earlier, adopt infusion process to make the catalyst precursor complex carrier and active component salting liquid again; The catalyst precursor promptly gets carbon dioxide methanation of the present invention and uses catalyst after drying, plasma treatment.
The present invention prepares above-mentioned carbon dioxide methanation and uses the concrete steps of catalyst method to be:
1) dipping-precipitation method prepare complex carrier: impregnated in γ-Al under the salting liquid room temperature that the water-soluble metal oxide is corresponding
2O
3On the carrier, introducing precipitating reagent to pH value of solution again is 8-10, leaves standstill 2-4 hour after deposition is even, and filtration, washing, drying, heating and decomposition get complex carrier; Wherein, γ-Al
2O
3With the mass ratio of water-soluble metal oxide be 77-86: 2-10; Said precipitating reagent is NH
3H
2O, Na
2CO
3, NaOH;
2) preparation of catalyst precursor: utilize equi-volume impregnating that the active component salting liquid is supported on step 1) gained complex carrier; Wherein, complex carrier: active component=84-90%: 10-16%; Dipping temperature is a normal temperature, and dip time is 3-5 hour;
3) Preparation of catalysts: with step 2) carry out plasma treatment under the normal temperature and pressure after the gained catalyst precursor drying, promptly obtain carbon dioxide methanation of the present invention and use catalyst.
Further, the present invention also provides the method for using of above-mentioned carbon dioxide methanation with catalyst, and the application conditions of this catalyst carbon dioxide methanation reaction is: reaction pressure is a normal pressure, and the unstrpped gas volume space velocity is 8100-15000ml/ (hg
Cat), H
2/ CO
2Mol ratio be 2/1-4/1.
Preferably, the unstrpped gas volume space velocity is 10000ml/ (hg
Cat), H
2/ CO
2Mol ratio be 4: 1.
Beneficial effect of the present invention:
The adding of water-soluble metal oxide has improved active component Ni at base carrier γ-Al in the complex carrier of catalyst of the present invention
2O
3On decentralization, before the water-soluble metal oxide content did not reach the maximum dispersion amount, the decentralization of Ni increased with the increase of water-soluble metal oxide content; The present invention has explored the addition of proper metal oxide (if because its addition is excessive; Reunite easily on the one hand and be unfavorable for the dispersion of NiO at carrier surface; On the other hand, metal oxide possibly form solid solution with NiO and hinder its reduction), obtained catalyst has higher CO
2Conversion ratio and 100% CH
4Selectivity.
In addition; The present invention introduce plasma technique replace high-temperature roasting among the existing preparation method handle (carbon dioxide methanation of the prior art with catalyst usually by the salt of transition metal through dip loading in oxide surface, again through high-temperature roasting, reduction and make); Owing to avoided high-temperature calcination process; Therefore catalyst activity component particles size is little, and active component is more even in the dispersion of carrier surface, and NiO is changed by the amorphous facies pattern of crystal to high dispersive at catalyst surface; Catalyst has high catalytic activity and stable preferably, and this catalyst can be at normal pressure and certain H
2/ CO
2The reaction of condition catalysis full methanation of carbon dioxide.Because method of the present invention need not used noble metal, its cost reduces with respect to noble metal catalyst greatly simultaneously.
The present invention utilizes plasma modified catalyst, places plasma reactor to carry out modification under certain condition catalyst and handles, and the low-temperature catalyzed conversion capability of gained catalyst obviously improves, under 340 ℃～360 ℃, and CO
2Conversion ratio can reach about 85～90%.Compare with traditional method for preparing catalyst, plasma technique prepares catalyst and has easy and simple to handle, advantages such as technological process is short, energy consumption is low, the intuitively easy control of catalyst change procedure, cleanliness without any pollution; The catalyst of using the plasma technique preparation has that specific area is big, rate of reduction fast, the activated centre number is many, catalyst granules is little, the decentralization advantages of higher.
Description of drawings
Fig. 1 is a process chart of the present invention.
Fig. 2 is plasma producing apparatus figure of the present invention.
Fig. 3 is the 12.7wt%NiO/6wt%CeO of embodiment 2 preparations
2/ 81.3wt% γ-Al
2O
312.7wt%NiO/87.3wt% γ-the Al of preparation in catalyst and the Comparative Examples 2
2O
3Temperature programmed reduction test (TPR) figure.By Fig. 3, the catalyst of Comparative Examples 2 preparations has two reduction peak, lays respectively at 318 ℃ and 692 ℃, belongs to respectively and carrier γ-Al
2O
3The weak free NiO crystalline phase that interacts and with carrier γ-Al
2O
3Strong interaction NiAl
2O
4The reduction peak of spinelle.And the catalyst of embodiment 2 preparations has four reduction peak, and the reduction peak area is big than the reduction peak area of Comparative Examples 2 catalyst.This shows interpolation CeO
2After, regulated the interaction between the Ni-Al, promoted surperficial NiO crystalline phase and carrier γ-Al on the one hand
2O
3Between interaction, weakened entering Al on the other hand
2O
3Ni in the lattice
2+With Al
2O
3Between strong interaction, make that nickel element mostly forms xNiO-Al in the catalyst
2O
3Solid solution structure and CeO
2Promoted the reduction of NiO species.The catalyst of embodiment 2 is compared with the catalyst of Comparative Examples 2, and variation has taken place its reduction peak shape, about 402 ℃, acromion occurs, belongs to CeO
2The reduction peak of Lattice Oxygen the main reduction peak except that about 587 ℃, acromion occurs near 742 ℃, belong to NiO-CeO
2The reduction peak of solid solution, NiO and CeO in the catalyst of illustrative embodiment 2 preparations
2Between obviously have strong interaction, and this strong interaction is very beneficial for the reduction of catalyst surface NiO species.
Fig. 4 is the 12.7wt%NiO/6wt%CeO of embodiment 2 preparations
2/ 81.3wt% γ-Al
2O
312.7wt%NiO/87.3wt% γ-the Al of preparation in catalyst and the Comparative Examples 2
2O
3X ray diffracting spectrum after the catalyst roasting (XRD).Can find out by figure; Each characteristic diffraction peak intensity of NiO is all a little less than the catalyst than Comparative Examples 2 preparations in the catalyst of embodiment 2 preparation; Especially on the catalyst of embodiment 2, (220) crystal face of NiO becomes very unclear, and the grain size of the catalyst NiO of illustrative embodiment 2 correspondences is littler than Comparative Examples 2 catalyst respective value; Further specify, add CeO
2The decentralization of the nickel-base catalyst reactive metal NiO that supports of complex carrier of preparation is better, combines the TPR sign, can think the CeO of load
2Exist between species and the NiO to interact, this interaction makes that decentralization increases each other.
Fig. 5 (a) is the 12.7wt%NiO/6wt%CeO of embodiment 2 preparations
2/ 81.3wt% γ-Al
2O
3The ESEM of catalyst and X-ray energy spectrum are analyzed collection of illustrative plates (SEM-EDX).Fig. 5 (b) is the 12.7wt%NiO/87.3wt% γ-Al of Comparative Examples 2 preparations
2O
3The ESEM of catalyst and X-ray energy spectrum are analyzed collection of illustrative plates.Can see from Fig. 5 photo; The catalyst surface active metallic particles size of Comparative Examples 2 preparations is big than the catalyst surface particle of embodiment 2 preparations; And the latter is evenly many, characterizes in conjunction with X ray diffracting spectrum and temperature programmed reduction, further illustrates and adds CeO
2After, auxiliary agent CeO
2Promoted the dispersion of reactive metal Ni with the interaction of reactive metal Ni at catalyst surface.
Fig. 6 is the 12.7wt%NiO/6wt%CeO of embodiment 1 preparation
2/ 81.3wt% γ-Al
2O
312.7wt%NiO/87.3wt% γ-the Al of catalyst and Comparative Examples 2 preparations
2O
3Catalyst is used for CO
2The CO of methanation reaction
2Conversion ratio is with the change curve in reaction time.Can be found out that by Fig. 6 along with the carrying out of reaction, the activity of such catalysts of Comparative Examples 2 preparations descends gradually, active fall off rate is significantly accelerated after 26 hours, 100 hours CO
2Conversion ratio is merely about 41.2%; Though and the catalyst activity of embodiment 1 preparation descends to some extent, fall is little, when reaction proceeds to 100 hours, and CO
2Conversion ratio is still up to about 80.3%.This explanation rare-earth oxide CeO
2Can not only improve the reactivity of nickel-base catalyst, also significantly improve the stability of nickel-base catalyst, prolong the service life of catalyst.
The specific embodiment
The invention provides a kind of carbon dioxide methanation and use catalyst, form complex carrier by complex carrier and active component: active component=84-90wt%: 10-16wt%; Wherein, said complex carrier is by γ-Al
2O
3Form γ-Al with the water-soluble metal oxide
2O
3With the mass ratio of water-soluble metal oxide be 77-86: 2-10; Said active component is Ni, and is present in this catalyst with the NiO form; And process plasma treatment before this catalyst uses.
The present invention introduces plasma technique and replaces the high-temperature roasting among the existing preparation method to handle, owing to avoided high-temperature calcination process, so catalyst activity component particles size is little; It is big that the gained catalyst has specific area, and rate of reduction is fast, and the activated centre number is many; The size of activity of such catalysts component is little; Characteristics such as decentralization height, and sintering and reunion can not take place in the preparation process, therefore in reaction, show advantages of high catalytic activity and stable preferably.
In the catalyst of the present invention, when the active component loading is too small, Ni
2+In roasting process, be prone to get into Al
2O
3Lattice, the NiAl of generation tetrahedral coordination
2O
4, this spinel structure makes that reduction influences active species in hydrogen because of being difficult to; And cross when being higher than when loading, free state NiO occurs, and the appearance of NiO also possibly produce sintering except the waste that causes reactive metal, and this need be avoided; Select suitable loading not only can improve conversion ratio but also can practice thrift cost.The adding of water-soluble metal can improve the physicochemical properties of carrier surface, helps the dispersion of reactive metal, if but the too high water-soluble metal oxide of its loading can be at γ-Al
2O
3Surface aggregation is unfavorable for the dispersion of reactive metal NiO on the surface.
The present invention also provides above-mentioned carbon dioxide methanation to use the Preparation of catalysts method, changes calcination process among the existing preparation method of carbon dioxide methanation catalyst into plasma treatment.Be specially: adopt the dipping-precipitation method to prepare complex carrier earlier, adopt equi-volume impregnating to make the catalyst precursor complex carrier and active component salting liquid again; The catalyst precursor promptly gets carbon dioxide methanation of the present invention and uses catalyst after drying, plasma treatment.
Carbon dioxide methanation of the present invention uses the concrete steps of method for preparing catalyst to be:
1) dipping-precipitation method prepare complex carrier: impregnated in γ-Al through stirring under the salting liquid room temperature that the water-soluble metal oxide is corresponding
2O
3On the carrier, dip time is to make the corresponding salting liquid of water-soluble metal oxide enter into γ-Al fully in 4-6 hour
2O
3In the carrier; Introducing precipitating reagent to pH value of solution value again is 8-10 (pH value>=8 o'clock Ce (OH)
3Deposition begins to form; In the pH value is under the alkaline environment of 8-10, is prone to generate the preferably little crystal grain of dispersiveness, if the pH value is excessive; Particle is sharply reunited), add precipitating reagent and be for better that the water-soluble metal oxide is corresponding salting liquid uniform load at base carrier γ-Al
2O
3The surface; Solution deposition leaves standstill after evenly and crystal grain is formed and grows up to the certain granules size, filters then, washs, dry, heating and decomposition gets complex carrier;
Wherein, γ-Al
2O
3With the mass ratio of water-soluble metal oxide be 77-86: 2-10; Said precipitating reagent is NH
3H
2O, Na
2CO
3, NaOH; Drying condition is 100-120 ℃ to be descended dry 12-24 hour; Heating and decomposition is promptly in 450-600 ℃ of roasting 4-6h, preferred 550 ℃ of following roasting 5h; Precipitating reagent concentration is preferably 0.8mol/L;
2) preparation of catalyst precursor: utilize equi-volume impregnating that the active component salting liquid is supported on step 1) gained complex carrier; Wherein, complex carrier: active component=84-90wt%: 10-16wt%; Dipping temperature is a normal temperature, and dip time is 3-5 hour; Preferred 4 hours;
3) Preparation of catalysts: with step 2) carry out plasma treatment under the normal temperature and pressure after the gained catalyst precursor drying; Wherein, Plasma process conditions is: vacuum is 2～200Pa; Processing time is 45-120min, and drying condition is: descended dry 12-24 hour at 100-120 ℃, promptly obtain carbon dioxide methanation of the present invention and use catalyst.
The present invention introduce plasma technique replace high-temperature roasting among the existing preparation method handle (carbon dioxide methanation of the prior art with catalyst usually by the salt of transition metal through dip loading in oxide surface; Again through high-temperature roasting; Reduction and make), owing to avoided high-temperature calcination process (temperature of plasma discharge is very low), thereby avoided a lot of bad reactions under the high temperature; Be difficult for reuniting and sintering; Gained catalyst activity component particles size is little, and decentralization is better, makes the stability of catalyst also be significantly improved.In addition, plasma technique can strengthen and improve adhesive force and the interaction between metal and the carrier, has increased calculation in reduction degree and the surface-active of catalyst activity metal, thereby has made the reducing power of catalyst strengthen, and decentralization also is improved.Characteristics such as in addition, it is big that the catalyst of application plasma technique preparation has specific area, and rate of reduction is fast, and the activated centre number is many.
The present invention preferably adopts non-equilibrium cold plasma to handle, and is characterized in high electron temperature (10
4-10
5K) and relatively low gas temperature, can effectively avoid the destruction of high-temperature process to catalyst structure and crystal formation; The radio frequency plasma body technique is a kind of as non-equilibrium cold plasma; Can utilize on molecular scale that external energy makes that reactant molecule excites, disassociation and ionization; Produce a large amount of non-equilibrium high energy activation species; Owing to the bombardment on high energy electron, ion pair surface, can reduce the decomposition temperature and the reduction temperature of catalyst precarsor, its fuel factor and chemical effect can effectively promote the interaction between catalyst activity component and the carrier.
The selection of vacuum is based on and handles atmosphere in that not contain under the air influence condition treatment effect better among the present invention, when vacuum is higher than 200Pa, can't ignore air influence.Processing time should be controlled at catalyst surface and have Ni simultaneously
0And NiO two identical depositing, catalyst will have high catalytic activity and stability like this; When the processing time was lower than 45min, catalyst then can be undecomposed complete, and the processing time is higher than 120min, more Ni
0Form mutually, and the plasma processing gas electron temperature is up to 10
4K, the processing time, long meeting influence the interaction between metal and the carrier, was unfavorable for effective dispersion of reactive metal.
Preferably, said method ionic medium body treatment conditions are: input voltage 60-120V, gas flow are 20-45ml/min, radio frequency 13.56MHz; Discharge parameter is: sun stream 100 ± 10mA, grid current 50 ± 10mA; Gas is N
2, H
2, air or Ar.
Further, the present invention also provides the method for using of above-mentioned carbon dioxide methanation with catalyst, and the application conditions of this catalyst carbon dioxide methanation reaction is: reaction pressure is a normal pressure, and the unstrpped gas volume space velocity is 8100-15000ml/ (hg
Cat), H
2/ CO
2Mol ratio be 2/1-4/1.The gas volume air speed is: under the rated condition, and the volume number of unit interval unit mass unstripped gas that catalyst passes through, that is: air speed=feed gas volume flow/catalyst quality.And air speed is big more, and the time of staying is short more, and reaction depth reduces, but disposal ability strengthens; Air speed is more little, and the time of staying is long more, and reaction depth increases, but disposal ability reduces.
Preferably, the unstrpped gas volume space velocity is 10000ml/ (hg
Cat), H
2/ CO
2Mol ratio be 4: 1.
Through embodiment the present invention is specifically described below; It is important to point out that embodiment only is used for further specifying of the present invention; Can not be interpreted as the restriction to protection domain of the present invention, these those skilled in the art can make some nonessential improvement and adjustment according to the present invention.
A at first adopts dipping-precipitation method to prepare CeO
2/ γ-Al
2O
3Complex carrier: promptly take by weighing 1.06g Ce (NO
3)
36H
2O places beaker, adds the 20ml deionized water and stirring and makes its dissolving; Take by weighing 4.65g γ-Al
2O
3Place above-mentioned solution, stir 60min under the room temperature, slowly drip precipitating reagent NH again
3H
2O (0.8mol/L) stirs and made the even back of deposition aging (wear out and promptly under room temperature, leave standstill) 2 hours in 2 hours to pH=9, filters, washs, and 120 ℃ of following dried overnight made CeO in 5 hours in 550 ℃ of roastings then
2/ γ-Al
2O
3Complex carrier, wherein CeO
2Mass fraction be 6.0wt%;
The preparation of B catalyst precursor: take by weighing 2.83g Ni (NO
3)
2(analyzing pure, commercially available) places beaker, adds the 20ml deionized water and stirring and makes its dissolving; Take by weighing the CeO that the 5gA step makes
2/ γ-Al
2O
3Complex carrier places the magnetic crucible, will join Ni (NO
3)
2Dropwise add under the maceration extract normal temperature in the crucible, absorption dipping 4 hours does not stop to stir, and all is impregnated into CeO until all maceration extracts
2/ γ-Al
2O
3In the complex carrier;
The C Preparation of catalysts: B step gained catalyst precursor behind 80 ℃ of water bath methods, is put into drying box 110 ℃ of following dried overnight, and it is subsequent use that dried sample is put into the glass drier; Under the normal temperature, taking by weighing above-mentioned sample 1.0g and be tiled in the discharge glass tube, is plasma treatment under the 100Pa condition in vacuum, feeds discharge gas N
2(flow is 30ml/min) regulated input voltage 100V, radio frequency 13.56MHz, and the processing time is 60min, makes finished catalyst.
Each constituent mass percentage consists of in this catalyst: NiO:12.7%; γ-Al
2O
3: 81.3%; CeO
2: 6.0%.
Embodiment 2-11
Only compare catalytic component content or used nickel salt with embodiment 1 different with the water-soluble metal salt kind, and other processes are identical with embodiment 1, make each finished catalyst.The catalyst composition of embodiment 2 to embodiment 11 and used nickel salt thereof and water-soluble metal salt are as shown in table 1.
Table 1 catalyst is formed table
Embodiment 1-11 gained catalyst is obtained 60-80 purpose catalyst granules after compressing tablet, screening, get 200mg and be filled in the fixed bed reactors, adopt the hydrogen in-situ reducing, 450 ℃ of reduction temperatures, reaction pressure is a normal pressure, the unstripped gas proportioning is n (H
2): n (CO
2)=4: 1, gas volume air speed 10000ml/hg
Cat, investigating temperature range is 240-360 ℃, forms with the TDX01 chromatogram column analysis tail gas of GC-1690 gas chromatograph (TCD), data are by chromatographic work station N2000 record.
The computing formula of conversion ratio, selectivity and the productive rate of reaction is following:
x
p＝f
p·A
p/∑(f
i·A
i)
X(CO
2)＝(F
in·x
in(CO
2)-F
out·x
out(CO
2))/(F
in·x
in(CO
2))×100％
X(H
2)＝(F
in·x
in(H
2)-F
out·x
out(H
2))/(F
in·x
in(H
2))×100％
S(CH
4)＝F
out·x
out(CH
4)/(F
in·x
in(CO
2)-F
out·x
out(CO
2))×100％
Y(CH
4)＝X(CO
2)·S(CH
4)×100％
In the formula: x
pThe percentage composition of-species p; f
pThe correction factor of-species p; The F-gas flow;
A
pThe peak area of-species p; The X-conversion ratio; The Y-productive rate; The S-selectivity
Embodiment 1-11 gained activity of such catalysts test result (is CO
2Conversion ratio X
CO2/ % and CH
4Selectivity S
CH4/ %) as shown in table 2.In addition, we have added up various ce O
2The embodiment gained activity of such catalysts that content is corresponding, its evaluation result (CO
2Conversion ratio) sees table 3.
Comparative Examples 1 12.7wt%NiO/87.3wt% γ-Al
2O
3Preparation of catalysts-plasma method
The present invention is also to γ-Al
2O
3Study for the Raney nickel of single carrier, specifically preparation process is: 1) take by weighing 2.83gNi (NO
3)
2(analyzing pure, commercially available) places beaker, adds the 20ml deionized water and stirring and makes its dissolving; Take by weighing 5g γ-Al
2O
3Place the magnetic crucible, will join maceration extract dropwise add in the crucible, normal temperature is absorption dipping 4 hours down, does not stop to stir, and all is impregnated into γ-Al until all maceration extracts
2O
3In; Behind 80 ℃ of water bath methods, put into drying box afterwards 110 ℃ of following dried overnight; It is subsequent use that dried sample is put into the glass drier.2) under the normal temperature, taking by weighing above-mentioned sample 1.0g and be tiled in the discharge glass tube, is plasma treatment under the 100Pa condition in vacuum, and feeds discharge gas N
2(flow is 30ml/min) regulated input voltage 100V, radio frequency 13.56MHz, and the processing time is 60min, makes finished catalyst.Each constituent mass percentage consists of in this catalyst: γ-Al
2O
3: 87.3%; NiO:12.7%.Gained activity of such catalysts test result (is CO
2Conversion ratio X
CO2/ % and CH
4Selectivity S
CH4/ %) as shown in table 2.
Comparative Examples 2 12.7wt%NiO/87.3wt% γ-Al
2O
3Preparation of catalysts-conventional equi-volume impregnating
The present invention is also according to the NiO/ γ-Al of the conventional immersion process for preparing of bibliographical information
2O
3Catalyst, the practical implementation process is following: adopt equi-volume impregnating, take by weighing 2.83g Ni (NO
3)
2(analyzing pure, commercially available) places beaker, adds the 20ml deionized water and stirring and makes its dissolving; Take by weighing 5g γ-Al
2O
3Place the magnetic crucible, will join maceration extract dropwise add in the crucible, normal temperature is absorption dipping 4 hours down, does not stop to stir, and all is impregnated into γ-Al until all maceration extracts
2O
3In, constantly stir evaporate to dryness 80 ℃ of water-baths afterwards, put into drying box 110 ℃ of following dried overnight, 500 ℃ of roastings 5 hours under air atmosphere then make finished catalyst.Each constituent mass percentage consists of in this catalyst: γ-Al
2O
3: 87.3%; NiO:12.7%; Gained activity of such catalysts test result (is CO
2Conversion ratio X
CO2/ % and CH
4Selectivity S
CH4/ %) as shown in table 2.
Comparative Examples 3 16.9wt%NiO-6.5wt%Fe
2O
3/ 3.3wt%MgO-6wt%CeO
2-70.5wt%Al
2O
3Preparation of catalysts
The present invention also studies the disclosed catalyst of one Chinese patent application CN101884927, and specifically preparation process is: take by weighing Mg (NO
3)
26H
2O1.5g, Ce (NO
3)
36H
2O 0.5g is dissolved in the 20ml deionized water, and stirring and dissolving is processed maceration extract, gets 5g γ-Al
2O
3Place maceration extract, room temperature dipping 4h constantly stirs evaporate to dryness 80 ℃ of water-baths, puts into drying box 110 ℃ of following dried overnight, and 500 ℃ of roastings 5 hours under air atmosphere then make the support samples of dipping adjuvant component; Get Ni (NO
3)
26H
2O 4.68g, Fe (NO
3)
39H
202.32g, be dissolved in the 20ml deionized water, be mixed with the aqueous solution; Again this aqueous solution is mixed with the support samples of dipping adjuvant component, room temperature dipping 4 hours, evaporate to dryness is constantly stirred in 80 ℃ of water-baths again; Put into drying box 110 ℃ of following dried overnight, make finished catalyst.Each constituent mass percentage consists of in this catalyst: γ-Al
2O
3: 70.5%; NiO:16.9%; Fe
2O
3: 6.5%; MgO:3.3%; CeO
2: 6%.
Above-mentioned Comparative Examples catalyst activity evaluation experimental condition is identical with embodiment 1, and test result is seen table 2.
Table 2 catalyst activity evaluation result
Table 3 various ce O
2Content catalyst activity evaluation result
The present invention has also studied CeO
2Content is (with CeO
2Content accounts for the weight ratio of catalyst and representes) to the activity of such catalysts influence, as shown in table 3, can find out rare-earth oxide CeO by table 3
2Introducing can obviously improve NiO/ γ-Al
2O
3The CO of catalyst
2Methanation reaction is active, along with CeO
2The increase of content, activity of such catalysts (CO when being applied to the carbon dioxide methanation reaction
2Conversion ratio increases) increase, but work as CeO
2When content surpassed 6wt%, its catalytic effect descended on the contrary.CeO
2Addition unsuitable in theory too much, prevent that metallic particles from stopping up the duct, cause that the catalyst mechanical strength reduces and cause the catalyst efflorescence.Moreover, metal oxide CeO
2At base carrier Al
2O
3On decentralization have a threshold values, CeO
2When content surpasses threshold values, CeO
2At base carrier Al
2O
3Last dispersion is inhomogeneous, is piled into bulky grain easily, is unfavorable for that reactive metal Ni evenly disperses on carrier, therefore selects metal Ce O
2Addition be 6wt%.
In addition, the present invention is to embodiment 1 gained catalyst (12.7wt%NiO/6.0wt%CeO
2/ 81.3wt% γ-Al
2O
3) carried out stability test, be specially: the catalyst stability experimental apparatus for testing is identical with activity rating, and 200mg catalyst (60-80 order) is filled in the fixed bed reactors; Adopt the hydrogen in-situ reducing; 450 ℃ of reduction temperatures, reaction pressure are normal pressure, and the unstripped gas proportioning is n (H
2): n (CO
2)=4: 1, gas volume air speed 10000ml/hg
Cat, 360 ℃ of reaction temperatures, the gas-chromatography on-line analysis, the TDX-01 post, TCD detects.Catalyst stability is with CO
2Conversion ratio and CH
4Selectivity and reaction time relation represent that the result shows: after the 100h stability test, gained catalyst of the present invention is used for carbon dioxide methanation when reaction CO
2Conversion ratio only descended 5.3%, CH
4Selectivity also is reduced to 99.5%.And the catalyst of one Chinese patent application CN101884927 embodiment 1 report (this catalyst Main Ingredients and Appearance and quality proportioning thereof are: 16.9%NiO-6.5%Fe
2O
3-3.3%MgO-2.8%CeO
2-70.5% γ-Al
2O
3) be applied to the carbon dioxide methanation reaction under the condition of normal pressure, find at 360 ℃ of following CO
2Conversion ratio be 87.5%, methane selectively is 100%, but through 100h stability test, CO
2Conversion ratio drop to 80.3% (CO
2Conversion ratio descended 7.2%), CH
4Selectivity also is reduced to 99.4%.It is thus clear that gained catalyst stability of the present invention is better.
To sum up can know; The present invention is not adding active component Fe and auxiliary agent Mg; And under the lower situation of active component content, the carbon dioxide methanation catalytic reaction better effects if (comparative example 9 and Comparative Examples 3) of gained catalyst applications of the present invention under condition of normal pressure, and gained catalyst stability of the present invention is better; Cost is lower, is more suitable in large-scale industrial production.
Claims (10)
1. carbon dioxide methanation is used catalyst, it is characterized in that, is made up of complex carrier complex carrier and active component: active component=84-90wt%: 10-16wt%; Wherein, said complex carrier is by γ-Al
2O
3Form γ-Al with the water-soluble metal oxide
2O
3With the mass ratio of water-soluble metal oxide be 77-86: 2-10; Said active component is Ni, and is present in this catalyst with the NiO form.
2. carbon dioxide methanation according to claim 1 is used catalyst, it is characterized in that, said water-soluble metal oxide is CeO
2, ZrO
2Or La
2O
3In at least a.
3. carbon dioxide methanation according to claim 1 and 2 is used catalyst, it is characterized in that, each constituent mass ratio is in this catalyst: complex carrier: active component=84-88: 12-16; γ-Al in the complex carrier
2O
3With the mass ratio of water-soluble metal oxide be 78-86: 2-6.
4. carbon dioxide methanation according to claim 1 and 2 is used catalyst, it is characterized in that, each constituent mass ratio is in this catalyst: complex carrier: active component=84.7: 15.3; γ-Al in the complex carrier
2O
3With the mass ratio of water-soluble metal oxide be 78.7: 6.
5. carbon dioxide methanation according to claim 1 and 2 is used catalyst, it is characterized in that, each constituent mass ratio is in this catalyst: complex carrier: active component=87.3: 12.7; γ-Al in the complex carrier
2O
3With the mass ratio of water-soluble metal oxide be 81.3: 6.
6. carbon dioxide methanation according to claim 1 and 2 is used catalyst, it is characterized in that, said complex carrier is CeO
2/ γ-Al
2O
3
7. each described carbon dioxide methanation of claim 1-6 is used the Preparation of catalysts method, it is characterized in that, adopts the dipping-precipitation method to prepare complex carrier earlier, adopts infusion process to make the catalyst precursor complex carrier and active component salting liquid again; The catalyst precursor promptly gets carbon dioxide methanation of the present invention and uses catalyst after drying, plasma treatment.
8. carbon dioxide methanation according to claim 7 is used the Preparation of catalysts method, and concrete steps are:
1) dipping-precipitation method prepare complex carrier: impregnated in γ-Al under the salting liquid room temperature that the water-soluble metal oxide is corresponding
2O
3On the carrier, introducing precipitating reagent to pH value of solution again is 8-10, leaves standstill 2-4 hour after deposition is even, and filtration, washing, drying, heating and decomposition get complex carrier; Wherein, γ-Al
2O
3With the mass ratio of water-soluble metal oxide be 77-86: 2-10; Said precipitating reagent is NH
3H
2O, Na
2CO
3, NaOH;
2) preparation of catalyst precursor: utilize equi-volume impregnating that the active component salting liquid is supported on step 1) gained complex carrier; Wherein, complex carrier: active component=84-90wt%: 10-16wt%; Dipping temperature is a normal temperature, and dip time is 3-5 hour;
3) Preparation of catalysts: with step 2) carry out plasma treatment under the normal temperature and pressure after the gained catalyst precursor drying, promptly obtain carbon dioxide methanation of the present invention and use catalyst.
9. each described carbon dioxide methanation of claim 1-6 is with the method for using of catalyst; It is characterized in that; The application conditions of this catalyst carbon dioxide methanation reaction is: reaction pressure is a normal pressure, and the unstrpped gas volume space velocity is 8100-15000ml/ (hg
Cat), H
2/ CO
2Mol ratio be 2/1-4/1.
10. the described carbon dioxide methanation of claim 9 is characterized in that with the method for using of catalyst, and the unstrpped gas volume space velocity is 10000ml/ (hg
Cat), H
2/ CO
2Mol ratio be 4: 1.
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