CN105268446B - Rear-earth-doped Ni bases BaTiO3‑TiO2Catalyst and preparation method thereof - Google Patents
Rear-earth-doped Ni bases BaTiO3‑TiO2Catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to chemical catalyst area, and in particular to rear-earth-doped Ni bases BaTiO3‑TiO2Catalyst and preparation method thereof.The technical problem to be solved in the present invention is CH4‑CO2The catalyst of catalytic reforming producing synthesis gas reaction is easily inactivated, activity is not high so that CH4Average conversion it is relatively low.The scheme that the present invention solves above-mentioned technical problem is to provide a kind of rear-earth-doped Ni bases BaTiO3‑TiO2Catalyst.The rear-earth-doped Ni bases BaTiO3‑TiO2The chemical composition of catalyst is by mass percentage：La2O3For 0.15%~0.3%, CeO2It is 7%~9%, BaTiO for 0.05%~0.15%, NiO3For 80%~88% and TiO2For 2.55%~10.8%.Present invention also offers above-mentioned rear-earth-doped Ni bases BaTiO3‑TiO2The preparation method of catalyst.The catalyst activity that the present invention is provided is high, and carbon deposit rate is low, is CH with good high-temperature stability4‑CO2The catalyst of catalytic reforming producing synthesis gas reaction provides new selection.
Description
Technical field
The invention belongs to chemical catalyst area, and in particular to rear-earth-doped Ni bases BaTiO3-TiO2Catalyst and its system
Preparation Method.
Background technology
With economic continuous growth and the exhaustion of petroleum resources, global energy crisis is increasingly serious, finds one kind and replaces
For the energy oneself through extremely urgent.From national security and the angle of energy strategy, research and development substitute oil with a carbon resource
As the new chemical production processes of raw material, for such a coal of China is more, oil less, the abundant country of methane resource have important
Meaning.Natural Gas Reserve in World very abundant, prospective reserves is up to 400 tcms.China's natural gas reserves are up to 40,000,000,000,000
Cubic meter, accounts for the 10% of world's gross reserves.Nineteen ninety-five world's natural gas demand is 2.2 tcms, in the world once
23% is accounted in energy-consuming, 25% will be accounted for up to 2.9~3.1 tcms within 2010.By the end of the end of the year 2006, the whole nation is remaining
Recoverable Gas Reserves are about 3.09 tcms, than 2005 0.24 tcms of increase, and increasing degree is about
8.4%.Natural gas by be 21 century world energy sources important component.CH in natural gas4Content be about 75%~90%,
C2~C3Content be about 7%~15%.Therefore the exploitation of natural gas are either solving energy shortage, shortage of resources, also
It is all significant in terms of environmental protection.
Containing substantial amounts of methane and other low-carbon alkanes in natural gas, associated gas, coal bed gas and refinery gas,
Today of petroleum resources increasingly reduction, how methane and low-carbon alkanes effectively to be changed into useful liquid substance and chemical industry is former
Material, there is epochmaking application value.Methane and CO2It is main greenhouse gases, is one of chemically most stable of molecule, CH again4
It is that c h bond can be up to 435kJ/mol, thermodynamically sufficiently stable with the nonpolar molecule similar to inert gas；CO2
It is very stable linear symmetric molecule.Their conversion not only has important Significance for Environment, while in chemical theory research
It is also a challenge.The methane proposed in recent years faces oxygen CO2The new technology of preparing synthetic gas is with its tempting environmental benefit and potential
Industrial application value it is just of increasing concern.The process not only overcomes methane portion oxidation and methane carbon dioxide reformation system
The latent defect of two reactions of synthesis gas, and with H2/ CO is than adjustable special benefits.Obtain how the molecule so stablized
To effective activation, and then rationally conversion is realized, as one of problem most challenging in current heterogeneous catalysis field.With tradition
Steam reformation is compared, methane and carbon dioxide catalytic reforming producing synthesis gas, Yi Jihe low with small investment, efficiency high, energy consumption
Hydrogen and the carbon monoxide ratio advantage such as rationally into gas.But the process is a strong endothermic reaction (Δ H=248kJ/mol), need
Reaction temperature (800 DEG C) that will be higher.Therefore, the catalyst for developing high activity, high selection and high stable is methyl hydride catalyzed reformation
One of key factor of commercial Application is realized, is also the focus in the area research.By methane through synthesis gas again synthetic fuel and
Chemicals is one of most effective approach of gas utilization.It is said that in natural gasification chemical product, 60% product cost and device
Gas making part is invested in, so gas making is always the emphasis of gas chemical industry's developmental research.Methane, which changes into synthesis gas, water steaming
Gas reformation, methane portion oxidation, CO23 kinds of modes and combinations thereof are reformed, wherein steam reforming realizes industry already
Change, but there is high energy consumption, invest big, gained synthesis gas H2/ CO=3, is unsuitable for F-T synthesis and other important subsequent processes etc. and lacks
Point.
The H produced during methane carbon dioxide reformation2/ CO ratios about 1, are the ideals of Fiscber-Tropscb synthesis and carbonylation synthesis
Raw material.The CO 2 reformation of methane：CH4+CO2→2CO+2H2, Δ H298K=247.3kJ/mol.The reaction, which is utilized, causes temperature
The CO of room effect2Gas, is significant to alleviating atmosphere pollution and environmental improvement.Early in nineteen twenty-eight, foreign study people
Fe, Co, Ni, Cu even load on the high temperature resistant mixture such as clay, silica, are found the catalysis using Ni and Co as active component by member
Agent has greater activity to synthesizing gas by reforming methane with co 2.However, being started to the relatively broad in-depth study of the reaction
1990s.1991, A shcroft delivered relevant CH on Nature4-CO2Research paper in terms of reformation, from
This has worldwide triggered the broad interest of researcher.In recent ten years, domestic and foreign scholars are to methane and carbon dioxide weight
Whole reaction has carried out systematic research work, and they are from several sides such as the active component of catalyst, carrier, auxiliary agent, reaction mechanism
Face has made extensive and intensive studies.
The patent of Application No. 201310258286.9 is by auxiliary agent of Nd, Ni is active component, ordered mesoporous silica dioxide
(SBA-15) it is carrier, rare earth metal Nd and active metal component Ni are carried on by the infusion process priority being modified using beta-schardinger dextrin
On carrier, the Ni/Nd/SBA-15 catalyst of rare earth metal Nd modifications is prepared for.Ni/Nd/SBA-15 catalysis prepared by the invention
Agent shows higher active and preferable anti-carbon performance in synthesizing gas by reforming methane with co 2 reaction, but still not
Height, CO2Average conversion only has 94.2%, CH4Average conversion only has 82%.
The patent of Application No. 201210275453 is related to a kind of catalyst for methane carbon dioxide reformation synthesis gas,
The catalyst is in MgO and MgAl2O4Load active component metallic nickel on mixed oxide, its formula is expressed as Ni/MgO+
MgAl2O4, Ni contents account for the 3%-10% of catalyst weight.The catalyst solves the carbon accumulation resisting ability that existing catalyst is present
Difference, preparation method is complicated, catalyst high cost problem.Preparation method described in the invention is simple, and synthesis condition is easy to control, easily
In industrialization, and it is high with catalytic activity, anti-carbon performance and stability are good, and cost is urged than noble metal catalyst and Ni-based modification
The low advantage of agent.But, its catalytic activity is not still high, CO2Average conversion only has 94%, CH4Average conversion only has
87%.
CH4-CO2The research of catalytic reforming producing synthesis gas reaction makes great progress, but is industrialized apart from realizing
There are still a certain distance.Subject matter is that catalyst is easily inactivated because of carbon deposit and sintering etc., therefore develops high activity, height
The catalyst of selectivity and anti-carbon deposit is always the target that research worker pursues.
The content of the invention
The technical problem to be solved in the present invention is CH4-CO2Catalytic reforming producing synthesis gas reaction catalyst easily inactivate,
Activity is not high so that CH4Average conversion it is relatively low.
The scheme that the present invention solves above-mentioned technical problem is to provide a kind of rear-earth-doped Ni bases BaTiO3-TiO2Catalyst.
The rear-earth-doped Ni bases BaTiO3-TiO2The chemical composition of catalyst is by mass percentage：La2O3For 0.15%~
0.3%th, CeO2It is 7%~9%, BaTiO for 0.05%~0.15%, NiO3For 80%~88% and TiO2For 2.55%~
10.8%.
Present invention also offers above-mentioned rear-earth-doped Ni bases BaTiO3-TiO2The preparation method of catalyst, including following step
Suddenly：
A, titanium oxyoxalate acid (H2[TiO(C2O4)2]) preparation of solution：Take dense TiOSO4Solution is diluted with water obtains at normal temperatures
Diluted Ti solution, ammonification water adjustment diluted Ti solution pH value be 0.5~3, it is to be precipitated completely after, filtering, washing, obtain positive metatitanic acid
(H4TiO4) precipitation；Oxalic acid is added in above-mentioned positive metatitanic acid precipitation, water dissolving is added, obtains mixed liquor, and keep mixed liquor
Concentration with TiO2It is calculated as 0.7~1.3kg/L；Above-mentioned mixed liquor is heated to boiling, 0.5~1h of fluidized state is kept, obtains
Titanium oxyoxalate acid solution；The addition of the oxalic acid is that positive metatitanic acid is precipitated (with TiO2Meter) 2 times of mole total amount；It is described boiled
Ammoniacal liquor is added in journey keeps solution ph to be 1.5~2.5；
B, rear-earth-doped Ni base barium chloride solutions preparation：By barium chloride, nickel nitrate, lanthanum acetate (La (Ac)3) and vinegar
Sour cerium (Ce (Ac)3) well mixed, it is dissolved in water completely, obtains rear-earth-doped Ni base barium chloride solutions；The barium chloride, nitre
Sour nickel is precipitated (with TiO with positive metatitanic acid2Meter) mol ratio be the ︰ 1 of 1 ︰ 0.15~0.25；The lanthanum acetate, cerous acetate and barium chloride
Mol ratio be the ︰ 1 of 0.0005~0.002 ︰ 0.0005~0.002, and lanthanum acetate and cerous acetate mole sum be barium chloride
The 0.1%~0.4% of mole；
Under c, normal temperature, the titanium oxyoxalate acid that above-mentioned rear-earth-doped Ni base barium chloride solutions are added to obtained by step a is molten
In liquid, 1.5~2.5h is reacted, the sour barium (BaTiO (C of rear-earth-doped Ni bases titanium oxyoxalate are obtained2O4)2·4H2O) precipitation system；
The mole of barium chloride and titanium oxyoxalate acid solution are (with TiO in the rear-earth-doped Ni base barium chloride solutions2Meter) mole
Than for 1 ︰ 1；
D, by metatitanic acid (H2TiO3) be added in the sour precipitated barium system of above-mentioned rear-earth-doped Ni bases titanium oxyoxalate, fully
Mixing, is washed out precipitation, suction filtration and obtains after filter cake, filter cake drying, then calcine 2h at 750 DEG C~850 DEG C, obtain rare earth
The Ni bases BaTiO of doping3-TiO2Carrier；The addition of the metatitanic acid is positive metatitanic acid precipitation described in step a (with TiO2Meter) rub
The 5%~35% of that amount；
E, by rear-earth-doped Ni bases BaTiO3-TiO2Carrier impregnates 20~60min in saturation nickel nitrate solution, then
Take out, 2h is calcined after drying, then under the conditions of 600 DEG C in atmosphere~650 DEG C, most obtain rear-earth-doped through air-flow crushing afterwards
Ni bases BaTiO3-TiO2Catalyst；In described saturation nickel nitrate solution, nickel nitrate and BaTiO3-TiO2Barium titanate in carrier
Mol ratio is 0.05~0.10 ︰ 1.
Wherein, dense TiOSO described in step a4The concentration of solution is with TiO2It is calculated as 180~250g/L.It is preferred that, it is described dense
TiOSO4The concentration of solution is with TiO2Count 210~230g/L.
Wherein, the concentration of diluted Ti solution described in step a is with TiO2It is calculated as 100~160g/L.The concentration of the diluted Ti solution with
TiO2Meter is preferably 130~150g/L.
As preferred embodiments of the present invention, the pH value of diluted Ti solution described in step a is 1~2.
As preferred embodiments of the present invention, the concentration of mixed liquor is with TiO described in step a2It is calculated as 0.9~1.1kg/L.
Wherein, the pH value of mixed liquor described in step a is 1.9~2.1.
As preferred embodiments of the present invention, the time that fluidized state is kept described in step a is 40~45min.
As preferred embodiments of the present invention, the mole sum of lanthanum acetate described in step b and cerous acetate is rubbed for barium chloride
The 0.2%~0.3% of that amount.
Wherein, the speed that Ni base barium chloride solutions rear-earth-doped described in step c are added in titanium oxyoxalate acid solution is 5
~20mL/min.It is preferred that, the speed that the rear-earth-doped Ni base barium chloride solutions are added in titanium oxyoxalate acid solution is
10~15mL/min.
As preferred embodiments of the present invention, the reaction time described in step c is 1.9~2.1h.
As preferred embodiments of the present invention, metatitanic acid addition described in step d be positive metatitanic acid precipitation obtained by step a (with
TiO2Meter) mole 20%~30%.
As preferred embodiments of the present invention, dip time described in step e is 30~40min.
The beneficial effects of the present invention are：The present invention is creatively in carrier B aTiO3Rare earth and nitre are added in generating process
Sour nickel, i.e., in barium chloride solution add, its be advantageous in that enable rare earth and NiO most possibly scattered adsorption in BaTiO3
Matrix surface and molecular gap, enhance specific surface area and adsorption energy significantly.The present invention creatively employs BaTiO3
And TiO2Mixed carrier, form complementary and reinforcing, and the position of Ti in lattice is replaced by a small amount of Ni, utilize stabilizing anatase
" matrix effect " of structure obtains high dispersive and stable Ni metallics, prepares high-performance Ni base catalyst, both kept
Higher catalytic activity, can greatly suppress carbon deposit, with good high-temperature stability again.The present invention is also creatively simultaneously
Employ La2O3And CeO2Two kinds of auxiliary agents, compensate for the defect of single auxiliary agent atomic radius fixed value, are conducive to catalyst activity
Raising, substantially reduce the coke content of post catalyst reaction, and heat endurance is significantly enhanced.
Brief description of the drawings
Ni bases BaTiO rear-earth-doped Fig. 13-TiO2The XRD diffracting spectrums of catalyst.
Embodiment
Rear-earth-doped Ni bases BaTiO3-TiO2The preparation method of catalyst, comprises the following steps：
A, titanium oxyoxalate acid (H2[TiO(C2O4)2]) preparation of solution：Take dense TiOSO4Solution is diluted with water obtains at normal temperatures
Diluted Ti solution, ammonification water adjustment diluted Ti solution pH value be 0.5~3, it is to be precipitated completely after, filtering, washing, obtain positive metatitanic acid
(H4TiO4) precipitation；Oxalic acid is added in above-mentioned positive metatitanic acid precipitation, water dissolving is added, obtains mixed liquor, and keep mixed liquor
Concentration with TiO2It is calculated as 0.7~1.3kg/L；Above-mentioned mixed liquor is heated to boiling, 0.5~1h of fluidized state is kept, obtains
Titanium oxyoxalate acid solution；The addition of the oxalic acid is that positive metatitanic acid is precipitated (with TiO2Meter) 2 times of mole total amount；It is described boiled
Ammoniacal liquor is added in journey keeps solution ph to be 1.5~2.5；
B, rear-earth-doped Ni base barium chloride solutions preparation：By barium chloride, nickel nitrate, lanthanum acetate (La (Ac)3) and vinegar
Sour cerium (Ce (Ac)3) well mixed, it is dissolved in water completely, obtains rear-earth-doped Ni base barium chloride solutions；The barium chloride,
Nickel nitrate is precipitated (with TiO with positive metatitanic acid2Meter) mol ratio be the ︰ 1 of 1 ︰ 0.15~0.25；The lanthanum acetate, cerous acetate and chlorination
The mol ratio of barium is the ︰ 1 of 0.0005~0.002 ︰ 0.0005~0.002, and the mole sum of lanthanum acetate and cerous acetate is chlorination
The 0.1%~0.4% of barium mole；
Under c, normal temperature, the titanium oxyoxalate acid that above-mentioned rear-earth-doped Ni base barium chloride solutions are added to obtained by step a is molten
In liquid, 1.5~2.5h is reacted, the sour barium (BaTiO (C of rear-earth-doped Ni bases titanium oxyoxalate are obtained2O4)2·4H2O) precipitation system；
The mole of barium chloride and titanium oxyoxalate acid solution are (with TiO in the rear-earth-doped Ni base barium chloride solutions2Meter) mole
Than for 1 ︰ 1；
D, by metatitanic acid (H2TiO3) be added in the sour precipitated barium system of above-mentioned rear-earth-doped Ni bases titanium oxyoxalate, fully
Mixing, is washed out precipitation, suction filtration and obtains after filter cake, filter cake drying, then calcine 2h at 750 DEG C~850 DEG C, obtain rare earth
The Ni bases BaTiO of doping3-TiO2Carrier；The addition of the metatitanic acid is positive metatitanic acid precipitation described in step a (with TiO2Meter) rub
The 5%~35% of that amount；
E, by rear-earth-doped Ni bases BaTiO3-TiO2Carrier impregnates 20~60min in saturation nickel nitrate solution, then
Take out, 2h is calcined after drying, then under the conditions of 600 DEG C in atmosphere~650 DEG C, most obtain rear-earth-doped through air-flow crushing afterwards
Ni bases BaTiO3-TiO2Catalyst；In described saturation nickel nitrate solution, nickel nitrate and BaTiO3-TiO2Barium titanate in carrier
Mol ratio is 0.05~0.10 ︰ 1.
Wherein, dense TiOSO described in step a4Solution concentration is with TiO2It is calculated as 180~250g/L.The dense TiOSO4Solution
Concentration with TiO2Meter is preferably 210~230g/L.
Wherein, the concentration of diluted Ti solution described in step a is with TiO2It is calculated as 100~160g/L.The concentration of the diluted Ti solution with
TiO2Meter is preferably 130~150g/L.If the concentration of diluted Ti solution is too high, not facile hydrolysis；If concentration is too low, the precipitation after hydrolysis
It is difficult to filter.
Wherein, the pH value of diluted Ti solution is adjusted using ammoniacal liquor in step a, is advantageous in that from ammoniacal liquor：Ammoniacal liquor neither
Highly basic, without entering metal impurities ion.
As preferred embodiments of the present invention, the pH value of diluted Ti solution described in step a is 1~2.If pH value is too low, it is difficult
Hydrolysis；If pH value is too high, metatitanic acid (H is easily generated2TiO3)。
As preferred embodiments of the present invention, the concentration of mixed liquor is with TiO described in step a2It is calculated as 0.9~1.1kg/L.
Wherein, the pH value of mixed liquor described in step a is 1.9~2.1.
As preferred embodiments of the present invention, the time that fluidized state is kept described in step a is 40~45min.
As preferred embodiments of the present invention, the mole sum of lanthanum acetate described in step b and cerous acetate is rubbed for barium chloride
The 0.2%~0.3% of that amount.The mole sum of the lanthanum acetate and cerous acetate is too high or too low all to reduce the work of catalyst
Property.
Wherein, the speed that Ni base barium chloride solutions rear-earth-doped described in step c are added in titanium oxyoxalate acid solution is 5
~20mL/min.It is preferred that, the speed that the rear-earth-doped Ni base barium chloride solutions are added in titanium oxyoxalate acid solution is
10~15mL/min.If above-mentioned adding speed is too high, it is unfavorable for the sour barium of generation nanoscale titanium oxyoxalate, easily causes particle thick
Greatly；If speed is too low, efficiency is reduced.
As preferred embodiments of the present invention, the reaction time described in step c is 1.9~2.1h.
As preferred embodiments of the present invention, metatitanic acid addition described in step d be positive metatitanic acid precipitation obtained by step a (with
TiO2Meter) mole 20%~30%.
As preferred embodiments of the present invention, dip time described in step e is 30~40min.
Embodiment 1
Take dense TiOSO4Solution is (with TiO2Meter, concentration is 220g/L) 2L, add 0.5L deionized waters and be sufficiently stirred for, simultaneously
Ammoniacal liquor is added dropwise, the pH value for keeping solution is 1.0, the positive metatitanic acid (H of white flock precipitate to appear4TiO4) it is stable after, filter, wash
Wash.Meanwhile, by taking a small amount of positive 900 DEG C of calcinings of metatitanic acid high temperature, weigh TiO2The mode of the quality of powder calculates the titanic wintercherry
Contained TiO in material2Mass percent.Titanic wintercherry material 29.98g is weighed (with TiO2Meter) it is stand-by.
Weigh 94.64g oxalic acid crystal (TiO in equivalent to 2 times positive metatitanic acids2Mole total amount), it is added to step titanic
In wintercherry material.Plus distilled water makes cumulative volume to 400mL, boiling is heated to, its pH value is adjusted to 2.0 with ammoniacal liquor, continues to boil
Boiling, boils and transparent titanium oxyoxalate acid (H is formed after 45min2[TiO(C2O4)2]) solution.
Weigh barium chloride 84.92g, and add distilled water to allow it fully to dissolve to 850mL.
Weigh nickel nitrate to be dissolved in 100mL distilled water, nickel nitrate is weighed as the 28% of upper one-step chlorination barium mole.
A certain amount of lanthanum acetate (equivalent to the 60% of rare earth acetate total amount) and cerous acetate (phase are added in barium chloride solution
When in rare earth acetate total amount 40%), rare earth acetate addition be chlorination crystal of barium mole 0.25%.Walked add simultaneously on
The 50% of nickel nitrate quality, is sufficiently stirred for.
After transparent titanium oxyoxalate acid solution is formed, at normal temperatures, by rear-earth-doped Ni bases barium chloride solution with
10mL/min speed is added into the sour clear solution of titanium oxyoxalate, and the precipitation reaction 2h in the case of stirring, obtains rare earth
Sour barium (BaTiO (the C of the Ni bases titanium oxyoxalate of doping2O4)2·4H2O) precipitation system.
By metatitanic acid (H2TiO4) be slowly added into the sour precipitated barium system of the rear-earth-doped Ni bases titanium oxyoxalate of step,
The 20% of the mole for the titanic wintercherry material (29.98g) that addition is obtained by the first step is (with TiO2Meter).
Washing of precipitate, suction filtration obtained by upper step are obtained calcining 2h at 800 DEG C again after drying at filter cake, 120 DEG C, contained
NiO、La2O3And CeO2And it is dispersed in BaTiO3And TiO2Rear-earth-doped Ni bases in fine particle surface and gap
BaTiO3-TiO2Carrier.
Using conventional impregnation method, by the rear-earth-doped Ni bases BaTiO obtained by upper step3-TiO2Carrier is dipped in remaining nitric acid
In nickel solution, baking 24h is to dry in Muffle furnace (120 DEG C), then calcines 2h under the conditions of 600 DEG C in atmosphere~650 DEG C, through air-flow
Catalyst is obtained after crushing.
Rear-earth-doped Ni bases BaTiO obtained by the present embodiment3-TiO2The composition of catalyst is constituted：
La2O3For 0.20%, CeO2It is 8.59%, BaTiO for 0.07%, NiO3For 85.29%, TiO2For 5.85%.
Testing result shows：In catalytic activity index, CO2Average conversion is 98.1%, CH4Average conversion is
96.3%, carbon deposit rate is 0.6%.
Embodiment 2
Take dense TiOSO4Solution is (with TiO2Meter, concentration is 220g/L) 2L, add 0.5L deionized waters and be sufficiently stirred for, simultaneously
Ammoniacal liquor is added dropwise, the pH value for keeping solution is 1.0, the positive metatitanic acid (H of white flock precipitate to appear4TiO4) it is stable after, filter, wash
Wash.Meanwhile, by taking a small amount of positive 900 DEG C of calcinings of metatitanic acid high temperature, weigh TiO2The mode of the quality of powder calculates the titanic wintercherry
Contained TiO in material2Mass percent.Titanic wintercherry material 29.98g is weighed (with TiO2Meter) it is stand-by.
Weigh 94.64g oxalic acid crystal (TiO in equivalent to 2 times positive metatitanic acids2Mole total amount), it is added to step titanic
In wintercherry material.Plus distilled water makes cumulative volume to 400mL, boiling is heated to, its pH value is adjusted to 2.0 with ammoniacal liquor, continues to boil
Boiling, boils and transparent titanium oxyoxalate acid (H is formed after 45min2[TiO(C2O4)2]) solution.
Weigh barium chloride 84.92g, and add distilled water to allow it fully to dissolve to 850mL.
Weigh nickel nitrate to be dissolved in 100mL distilled water, nickel nitrate is weighed as the 24% of upper one-step chlorination barium mole.
A certain amount of lanthanum acetate (equivalent to the 40% of rare earth acetate total amount) and cerous acetate (phase are added in barium chloride solution
When in rare earth acetate total amount 60%), rare earth acetate addition be chlorination crystal of barium mole 0.25%.Walked add simultaneously on
The 50% of nickel nitrate quality, is sufficiently stirred for, and obtains rear-earth-doped Ni base barium chloride solutions.
After transparent titanium oxyoxalate acid solution is formed, at normal temperatures, by rear-earth-doped Ni bases barium chloride solution with
10mL/min speed is added into the sour clear solution of titanium oxyoxalate, and the precipitation reaction 2h in the case of stirring, obtains rare earth
Sour barium (BaTiO (the C of the Ni bases titanium oxyoxalate of doping2O4)2·4H2O) precipitation system.
By metatitanic acid (H2TiO4) be slowly added into the sour precipitated barium system of the rear-earth-doped Ni bases titanium oxyoxalate of step,
The 30% of the mole for the titanic wintercherry material (29.98g) that addition is obtained by the first step is (with TiO2Meter).
Washing of precipitate, suction filtration obtained by upper step are obtained calcining 2h at 800 DEG C again after drying at filter cake, 120 DEG C, contained
NiO、La2O3And CeO2And it is dispersed in BaTiO3And TiO2Rear-earth-doped Ni base loads in fine particle surface and gap
Body.
Using conventional impregnation method, by rear-earth-doped Ni bases BaTiO3-TiO2Carrier is dipped in remaining nickel nitrate solution,
Baking 24h is to dry in Muffle furnace (120 DEG C), then calcines 2h under the conditions of 600 DEG C in atmosphere~650 DEG C, is obtained through air-flow crushing
Rear-earth-doped Ni bases BaTiO3-TiO2Catalyst.
Rear-earth-doped Ni bases BaTiO obtained by the present embodiment3-TiO2The composition of catalyst is constituted：
0.13% La2O3, 0.10% CeO2, 7.25% NiO, 83.95% BaTiO3, 8.61% TiO2。
Testing result shows：In catalytic activity index, CO2Average conversion is 98.0%, CH4Average conversion is
96.5%, carbon deposit rate is 0.7%.
Embodiment 3
Take dense TiOSO4Solution is (with TiO2Meter, concentration is 220g/L) 2L, add 0.5L deionized waters and be sufficiently stirred for, simultaneously
Ammoniacal liquor is added dropwise, the pH value for keeping solution is 1.0, the positive metatitanic acid (H of white flock precipitate to appear4TiO4) it is stable after, filter, wash
Wash.Meanwhile, by taking a small amount of positive 900 DEG C of calcinings of metatitanic acid high temperature, weigh TiO2The mode of the quality of powder calculates the titanic wintercherry
Contained TiO in material2Mass percent.Titanic wintercherry material 29.98g is weighed (with TiO2Meter) it is stand-by.
Weigh 94.64g oxalic acid crystal (TiO in equivalent to 2 times positive metatitanic acids2Mole total amount), it is added to step titanic
In wintercherry material.Plus distilled water makes cumulative volume to 400mL, boiling is heated to, its pH value is adjusted to 2.0 with ammoniacal liquor, continues to boil
Boiling, boils and transparent titanium oxyoxalate acid (H is formed after 45min2[TiO(C2O4)2]) solution.
Weigh barium chloride 84.92g, and add distilled water to allow it fully to dissolve to 850mL.
Weigh nickel nitrate to be dissolved in 100mL distilled water, nickel nitrate is weighed as the 28% of upper one-step chlorination barium mole.
A certain amount of lanthanum acetate (equivalent to the 60% of rare earth acetate total amount) and cerous acetate (phase are added in barium chloride solution
When in rare earth acetate total amount 40%), rare earth acetate addition be chlorination crystal of barium mole 0.3%.Walked add simultaneously on
The 80% of nickel nitrate quality, is sufficiently stirred for, and obtains rear-earth-doped Ni base barium chloride solutions.
After transparent titanium oxyoxalate acid solution is formed, at normal temperatures, by rear-earth-doped Ni bases barium chloride solution with
10mL/min speed is added into the sour clear solution of titanium oxyoxalate, and the precipitation reaction 2h in the case of stirring, obtains rare earth
Sour barium (BaTiO (the C of the Ni bases titanium oxyoxalate of doping2O4)2·4H2O) precipitation system.
By metatitanic acid (H2TiO4) be slowly added into the sour precipitated barium system of the rear-earth-doped Ni bases titanium oxyoxalate of step,
The 20% of the mole for the titanic wintercherry material (29.98g) that addition is obtained by the first step is (with TiO2Meter).
Washing of precipitate, suction filtration obtained by upper step are obtained calcining 2h at 800 DEG C again after drying at filter cake, 120 DEG C, contained
NiO、La2O3And CeO2And it is dispersed in BaTiO3And TiO2Rear-earth-doped Ni bases in fine particle surface and gap
BaTiO3-TiO2Carrier.
Using conventional impregnation method, by rear-earth-doped Ni bases BaTiO3-TiO2Carrier is dipped in remaining nickel nitrate solution,
Baking 24h is to dry in Muffle furnace (120 DEG C), then calcines 2h under the conditions of 600 DEG C in atmosphere~650 DEG C, is obtained through air-flow crushing
Rear-earth-doped Ni bases BaTiO3-TiO2Catalyst.
Rear-earth-doped Ni bases BaTiO obtained by the present embodiment3-TiO2The composition of catalyst is constituted：
0.24% La2O3, 0.08% CeO2, 8.59% NiO, 85.25% BaTiO3, 5.85% TiO2。
Testing result shows：In catalytic activity index, CO2Average conversion is 98.9%, CH4Average conversion is
98.5%, carbon deposit rate is 0.3%.
Comparative example：
Take dense TiOSO4Solution is (with TiO2Meter, concentration is 220g/L) 2L, add 0.5L deionized waters and be sufficiently stirred for, simultaneously
Ammoniacal liquor is added dropwise, the pH value for keeping solution is 1.0, the positive metatitanic acid (H of white flock precipitate to appear4TiO4) it is stable after, filter, wash
Wash.Meanwhile, by taking a small amount of positive 900 DEG C of calcinings of metatitanic acid high temperature, weigh TiO2The mode of the quality of powder calculates the titanic wintercherry
Contained TiO in material2Mass percent.Titanic wintercherry material 29.98g is weighed (with TiO2Meter) it is stand-by.
Weigh 94.64g oxalic acid crystal (TiO in equivalent to 2 times positive metatitanic acids2Mole total amount), it is added to step titanic
In wintercherry material.Plus distilled water makes cumulative volume to 400mL, boiling is heated to, its pH value is adjusted to 2.0 with ammoniacal liquor, continues to boil
Boiling, boils and transparent titanium oxyoxalate acid (H is formed after 45min2[TiO(C2O4)2]) solution.
Weigh barium chloride 84.92g, and add distilled water to allow it fully to dissolve to 850mL.
After transparent titanium oxyoxalate acid solution is formed, at normal temperatures, by the barium chloride solution obtained by upper step with 10mL/
Min speed is added into the sour clear solution of titanium oxyoxalate, and the precipitation reaction 2h in the case of stirring, obtains titanium oxyoxalate acid
Barium (BaTiO (C2O4)2·4H2O) precipitation system.
By metatitanic acid (H2TiO4) be slowly added into the sour precipitated barium system of the titanium oxyoxalate of step, addition is the first step
The 20% of the mole of the titanic wintercherry material (29.98g) obtained is (with TiO2Meter).
In the sour barium of titanium oxyoxalate and the BaTiO of metatitanic acid3-TiO2Added in mixed precipitation a certain amount of lanthanum acetate (equivalent to
Rare earth acetate total amount 60%) and cerous acetate (equivalent to the 40% of rare earth acetate total amount), rare earth acetate addition be barium chloride
The 0.25% of crystal mole.Nickel nitrate solution is added simultaneously (to weigh nickel nitrate to be dissolved in 100mL distilled water, nickel nitrate is weighed
For upper one-step chlorination barium mole 28%), be sufficiently stirred for.
Washing of precipitate, suction filtration obtained by upper step are obtained calcining 2h at 800 DEG C again after drying at filter cake, 120 DEG C, urged
Agent carrier.
Using conventional impregnation method, catalyst carrier is dipped in remaining nickel nitrate solution, toasted in Muffle furnace (120 DEG C)
24h is to dry, then calcines 2h under the conditions of 600 DEG C in atmosphere~650 DEG C, and barium phthalate base catalyst is obtained through air-flow crushing.
The composition of barium phthalate base catalyst obtained by this comparative example, which is constituted, is by mass percentage：0.20% La2O3、
0.07% CeO2, 8.59% NiO, 85.29% BaTiO3, 5.85% TiO2.Although barium phthalate base obtained by comparative example is urged
Agent is identical with the chemical composition of embodiment 1, but because rare earth and nickel are in carrier B aTiO3-TiO2What precipitation was just added after being formed,
So the decentralization and structure of catalytic active component are different from embodiment 1~3.
Testing result shows：In catalytic activity index, CO2Average conversion is 96.3%, CH4Average conversion is
94.2%, carbon deposit rate is 0.9%, hence it is evident that be worse than embodiment 1~3.
Claims (13)
1. rear-earth-doped Ni bases BaTiO3-TiO2Catalyst, its chemical composition is by mass percentage：La2O3For 0.15%
~0.3%, CeO2It is 7%~9%, BaTiO for 0.05%~0.15%, NiO3For 80%~88% and TiO2For 2.55%~
10.8%；
The rear-earth-doped Ni bases BaTiO3-TiO2The preparation method of catalyst, comprises the following steps：
A, titanium oxyoxalate acid solution preparation：Take dense TiOSO4Acquisition diluted Ti solution, the adjustment of ammonification water is diluted with water in solution at normal temperatures
The pH value of diluted Ti solution is 0.5~3, it is to be precipitated completely after, filtering, washing obtain positive metatitanic acid precipitation；By oxalic acid be added to it is above-mentioned just
In metatitanic acid precipitation, water dissolving is added, mixed liquor is obtained, and keep the concentration of mixed liquor with TiO2It is calculated as 0.7~1.3kg/L；
Above-mentioned mixed liquor is heated to boiling, 0.5~1h of fluidized state is kept, obtains titanium oxyoxalate acid solution；The addition of the oxalic acid
Measure precipitate mole total amount for positive metatitanic acid 2 times；Ammoniacal liquor is added in the boiling process keeps solution ph to be 1.5~2.5；It is described
Positive metatitanic acid precipitation is with TiO2Meter；
B, rear-earth-doped Ni base barium chloride solutions preparation：Barium chloride, nickel nitrate, lanthanum acetate and cerous acetate are well mixed,
It is dissolved in water completely, obtains rear-earth-doped Ni base barium chloride solutions；Mole that the barium chloride, nickel nitrate are precipitated with positive metatitanic acid
Than for the ︰ 1 of 1 ︰ 0.15~0.25；The mol ratio of the lanthanum acetate, cerous acetate and barium chloride be 0.0005~0.002 ︰ 0.0005~
0.002 ︰ 1, and the mole sum of lanthanum acetate and cerous acetate is the 0.1%~0.4% of barium chloride mole；The positive metatitanic acid sinks
Form sediment with TiO2Meter；
Under c, normal temperature, above-mentioned rear-earth-doped Ni base barium chloride solutions are added in the titanium oxyoxalate acid solution obtained by step a,
1.5~2.5h is reacted, the sour precipitated barium system of rear-earth-doped Ni bases titanium oxyoxalate is obtained；The rear-earth-doped Ni base barium chlorides
The mole of Chlorine in Solution barium is 1 ︰ 1 with the mol ratio of titanium oxyoxalate acid solution；The titanium oxyoxalate acid solution is with TiO2Meter；
D, metatitanic acid is added in the sour precipitated barium system of above-mentioned rear-earth-doped Ni bases titanium oxyoxalate, be sufficiently mixed, Ran Houxi
Wash precipitation, suction filtration to obtain after filter cake, filter cake drying, then 2h is calcined at 750 DEG C~850 DEG C, obtain rear-earth-doped Ni bases
BaTiO3-TiO2Carrier；The addition of the metatitanic acid is 5%~35% of positive metatitanic acid precipitation mole described in step a；It is described
Positive metatitanic acid precipitation is with TiO2Meter；
E, by rear-earth-doped Ni bases BaTiO3-TiO2Carrier impregnates 20~60min in saturation nickel nitrate solution, then takes out,
2h is calcined after drying, then under the conditions of 600 DEG C in atmosphere~650 DEG C, rear-earth-doped Ni bases are most obtained through air-flow crushing afterwards
BaTiO3-TiO2Catalyst；In described saturation nickel nitrate solution, nickel nitrate and BaTiO3-TiO2Mole of barium titanate in carrier
Than for 0.05~0.10 ︰ 1.
2. rear-earth-doped Ni bases BaTiO according to claim 13-TiO2The preparation method of catalyst, it is characterised in that：Bag
Include following steps：
A, titanium oxyoxalate acid solution preparation：Take dense TiOSO4Acquisition diluted Ti solution, the adjustment of ammonification water is diluted with water in solution at normal temperatures
The pH value of diluted Ti solution is 0.5~3, it is to be precipitated completely after, filtering, washing obtain positive metatitanic acid precipitation；By oxalic acid be added to it is above-mentioned just
In metatitanic acid precipitation, water dissolving is added, mixed liquor is obtained, and keep the concentration of mixed liquor with TiO2It is calculated as 0.7~1.3kg/L；
Above-mentioned mixed liquor is heated to boiling, 0.5~1h of fluidized state is kept, obtains titanium oxyoxalate acid solution；The addition of the oxalic acid
Measure precipitate mole total amount for positive metatitanic acid 2 times；Ammoniacal liquor is added in the boiling process keeps solution ph to be 1.5~2.5；It is described
Positive metatitanic acid precipitation is with TiO2Meter；
B, rear-earth-doped Ni base barium chloride solutions preparation：Barium chloride, nickel nitrate, lanthanum acetate and cerous acetate are well mixed,
It is dissolved in water completely, obtains rear-earth-doped Ni base barium chloride solutions；Mole that the barium chloride, nickel nitrate are precipitated with positive metatitanic acid
Than for the ︰ 1 of 1 ︰ 0.15~0.25；The mol ratio of the lanthanum acetate, cerous acetate and barium chloride be 0.0005~0.002 ︰ 0.0005~
0.002 ︰ 1, and the mole sum of lanthanum acetate and cerous acetate is the 0.1%~0.4% of barium chloride mole；The positive metatitanic acid sinks
Form sediment with TiO2Meter；
Under c, normal temperature, above-mentioned rear-earth-doped Ni base barium chloride solutions are added in the titanium oxyoxalate acid solution obtained by step a,
1.5~2.5h is reacted, the sour precipitated barium system of rear-earth-doped Ni bases titanium oxyoxalate is obtained；The rear-earth-doped Ni base barium chlorides
The mole of Chlorine in Solution barium is 1 ︰ 1 with the mol ratio of titanium oxyoxalate acid solution；The titanium oxyoxalate acid solution is with TiO2Meter；
D, metatitanic acid is added in the sour precipitated barium system of above-mentioned rear-earth-doped Ni bases titanium oxyoxalate, be sufficiently mixed, Ran Houxi
Wash precipitation, suction filtration to obtain after filter cake, filter cake drying, then 2h is calcined at 750 DEG C~850 DEG C, obtain rear-earth-doped Ni bases
BaTiO3-TiO2Carrier；The addition of the metatitanic acid is 5%~35% of positive metatitanic acid precipitation mole described in step a；It is described
Positive metatitanic acid precipitation is with TiO2Meter；
E, by rear-earth-doped Ni bases BaTiO3-TiO2Carrier impregnates 20~60min in saturation nickel nitrate solution, then takes out,
2h is calcined after drying, then under the conditions of 600 DEG C in atmosphere~650 DEG C, rear-earth-doped Ni bases are most obtained through air-flow crushing afterwards
BaTiO3-TiO2Catalyst；In described saturation nickel nitrate solution, nickel nitrate and BaTiO3-TiO2Mole of barium titanate in carrier
Than for 0.05~0.10 ︰ 1.
3. rear-earth-doped Ni bases BaTiO according to claim 23-TiO2The preparation method of catalyst, it is characterised in that：Step
Dense TiOSO described in rapid a4The concentration of solution is with TiO2It is calculated as 180~250g/L.
4. rear-earth-doped Ni bases BaTiO according to claim 33-TiO2The preparation method of catalyst, it is characterised in that：Institute
State dense TiOSO4The concentration of solution is with TiO2It is calculated as 210~230g/L.
5. rear-earth-doped Ni bases BaTiO according to claim 23-TiO2The preparation method of catalyst, it is characterised in that：Step
The concentration of diluted Ti solution is with TiO described in rapid a2It is calculated as 100~160g/L.
6. rear-earth-doped Ni bases BaTiO according to claim 53-TiO2The preparation method of catalyst, it is characterised in that：Institute
The concentration of diluted Ti solution is stated with TiO2It is calculated as 130~150g/L.
7. rear-earth-doped Ni bases BaTiO according to claim 23-TiO2The preparation method of catalyst, it is characterised in that：Step
The pH value of diluted Ti solution is 1~2 described in rapid a；The concentration of the mixed liquor is with TiO2It is calculated as 0.9~1.1kg/L；It is described to keep boiling
The time for rising state is 40~45min.
8. rear-earth-doped Ni bases BaTiO according to claim 23-TiO2The preparation method of catalyst, it is characterised in that：Step
The mole sum of lanthanum acetate and cerous acetate is the 0.2%~0.3% of barium chloride mole described in rapid b.
9. rear-earth-doped Ni bases BaTiO according to claim 23-TiO2The preparation method of catalyst, it is characterised in that：Step
The speed that rear-earth-doped Ni base barium chloride solutions described in rapid c are added in titanium oxyoxalate acid solution is 5~20mL/min.
10. rear-earth-doped Ni bases BaTiO according to claim 93-TiO2The preparation method of catalyst, it is characterised in that：
The speed that the rear-earth-doped Ni base barium chloride solutions are added in titanium oxyoxalate acid solution is 10~15mL/min.
11. rear-earth-doped Ni bases BaTiO according to claim 23-TiO2The preparation method of catalyst, it is characterised in that：
Reaction time described in step c is 1.9~2.1h.
12. rear-earth-doped Ni bases BaTiO according to claim 23-TiO2The preparation method of catalyst, it is characterised in that：
Metatitanic acid addition described in step d is 20%~30% of positive metatitanic acid precipitation mole obtained by step a；The positive metatitanic acid precipitation with
TiO2Meter.
13. rear-earth-doped Ni bases BaTiO according to claim 23-TiO2The preparation method of catalyst, it is characterised in that：
Dip time described in step e is 30~40min.
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