CN102029162A - Wide-temperature full methanation catalyst and preparation method thereof - Google Patents
Wide-temperature full methanation catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN102029162A CN102029162A CN2009101876765A CN200910187676A CN102029162A CN 102029162 A CN102029162 A CN 102029162A CN 2009101876765 A CN2009101876765 A CN 2009101876765A CN 200910187676 A CN200910187676 A CN 200910187676A CN 102029162 A CN102029162 A CN 102029162A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- nickel
- carrier
- auxiliary agent
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a wide-temperature full methanation catalyst and a preparation method thereof. The methanation catalyst is characterized in that: nickel is used as a main active ingredient, a composition formed by zirconium oxide and one or more of aluminum oxide and nickel-aluminum compounds is used as a main carrier, and lanthanum oxide is used as a cocatalyst; and a catalyst precursor is prepared by using a chemical precipitation process, and the catalyst precursor is reduced into the catalyst by filtering, washing, roasting, forming and re-roasting. The methanation catalyst has excellent catalytic activity and stability in a use range of between 260 and 750 DEG C, and fully meets the requirements of a full methanation process of synthesis gas on high temperature resistance, high hydrothermal stability and low-temperature high activity of the catalyst.
Description
Technical field
The invention belongs to catalyst and inorganic synthetic chemistry crossed technical, relate to the Catalysts and its preparation method of a kind of carbon monoxide and carbon dioxide methanation, particularly a kind of wide temperature range type full methanation Catalysts and its preparation method.
Background technology
Methanation reaction is a kind of important hydrogenation reaction, and it is of wide application.Utilize methanation technology to the CO in the coal gas
xSubstitute natural gas is made in methanation, when improving fuel gases calorific value greatly, has also increased its transportation and the security of using, and is to improve economic results in society and the effective scheme of alleviating the natural gas shortage.The synthesis gas methanation also is one of optimal path of coal clean utilization simultaneously, and this technology can also significantly reduce the atmosphere pollution that the traditional combustion of coal utilizes mode to cause, as acid rain, photochemical fog etc.In a word, the methanation synthetic natural gas not only can satisfy current growing clean energy resource demand, also will and distribute rationally and play irreplaceable important function the energy and reasonable resources utilization.
Synthesis gas methanation system instead of natural gas is meant CO and H in the synthesis gas
2Under the effect of certain temperature, pressure and catalyst, carry out chemical reaction and generate CH
4Process.This process key reaction is as follows:
CO+3H
2→CH
4+H
2O ΔH
0＝-206KJ/mol (1)
CO
2+4H
2→CH
4+2H
2O ΔH
0＝-165kJ/mol (2)
CO+H
2O→H
2+CO
2 ΔH
0＝-41kJ/mol (3)
2CO→C↓+CO
2ΔH
0＝-173kJ/mol (4)
CH
4→C↓+2H
2 ΔH
0＝75kJ/mol (5)
Can learn that from thermodynamic process methanation reaction (1) belongs to strong exothermal reaction with (2), and generates a large amount of steam; The equilibrium constant reduces rapidly with the rising of temperature, CO
xConversion ratio also decreases, and some side reactions simultaneously (5) also will occur, and this high-temperature stability to methanation catalyst has proposed very high requirement with activity.Adopt the bed temperature rise of lower gas access temperature restriction methanation catalyst, can promote the carrying out that react, this scheme also requires methanation catalyst should have better low temperature activity simultaneously.Certainly, the limiting catalyst bed temperature also needs to take the good thermal process of removing, and for example adopts tubulation heat exchange type reactor, fluid bed catalysis top process for cooling and the circulating fixed bed technology of heat (cold) gas.Methanation belongs to the volume-diminished reaction, improves pressure, also can promote the synthesis gas methanation, adopts 2.0-4.0MPa usually.Generally speaking, full methanation is crossed the range request catalyst should have higher high-temperature hydrothermal stability, and good low temperature active.
The research and development of full methanation catalyst are of long duration, and its system also reaches its maturity.The performance of such catalyst is generally determined jointly by several parts such as active component, carrier and auxiliary agents.Since the seventies in last century, the patented technology of relevant gas methanation catalyst report is many.Most of activity of such catalysts component is a VIII family metallic element, and is cheap and high activity and Ni are optionally arranged is optimal selection.Related carrier has α-or γ-Al
2O
3, Cr
2O
3, ZrO
2, TiO
2, MgO, kaolin and aluminous cement, wherein the trivalent Al that is difficult to reduce
2O
3It is a kind of catalyst carrier of generally using.Alkali metal or alkaline earth oxide are as high-temperature stabiliser, and rare earth also is a promoter important in the methanation catalyst system, have the double action of electron type and structural type auxiliary agent concurrently.The preparation method of catalyst has: (1) carrier, active component and auxiliary agent utilize chemical precipitation technology one step synthetic catalyst predecessor, then after filtration, dry, roasting and forming process be made into the catalyst of different shape; (2) at first utilize chemical precipitation technology synthetic vectors, and then support other components, be made into the catalyst of different shape at last through super-dry, roasting and forming process by technology such as infusion process or deposition sedimentations; (3) direct mechanical of carrier, active component and auxiliary agent (or its precursor) is mixed, and is made into the catalyst of different shape then through roasting and forming process.
The Haldor of Britain BASF, U.S. UCI, Britain Johnson Matthey, Denmark
Obtained much to be correlated with patented technology in this field, just utilized co-precipitation and precipitation from homogeneous solution technology to prepare the full methanation catalyst of high-temperature stable respectively as patent US3988262 representative in the nickel-alumina methanation catalyst system and US3988263.Although it is a lot of to relate to the patented technology of full methanation catalyst, some of them methanation catalyst technology has also realized commercialized running in big plain in u.s.a natural gas factory, but still not at the real record of realizing long-term industry operation more than 600 ℃.So the methanation catalyst system still needs further perfect, especially the full methanation catalyst awaits continuing to optimize at the hydrothermal stability more than 600 ℃.
Dalian Chemical Physics Research Institute has successively applied for three normal pressure part methanation catalyst patented technologies: CN1041968A, CN93110096.8 and CN93115835.4 aspect gas methanation.On the basis of above-mentioned three patented technologies, we have continued to develop a kind of synthesis gas full methanation catalyst that is applicable to HTHP, high hydrothermal stability, and its preparation method is simple, and good reproducibility is easy to industrialization.
Summary of the invention
The invention provides a kind of wide temperature range type full methanation Catalysts and its preparation method, this catalyst is applicable to the synthesis gas full methanation of HTHP, high hydrothermal stability, and its preparation method is simple, and good reproducibility is easy to industrialization.
The invention provides a kind of wide temperature range type full methanation catalyst, this catalyst provides the carrier of physical support by active component, to active component, and have collaborative or the auxiliary catalysis effect to active component, and the auxiliary agent that carrier plays stabilization is formed, it is characterized in that:
Active component is a nickel; Carrier is the composition that one or more and zirconia of aluminium oxide and nickel aluminide forms; Auxiliary agent is a lanthana, or the composition of lanthana and nickel lanthanum compound; Wherein zirconium that is comprised in the carrier and al atomic ratio are between 0.01-1.45;
Active component, carrier and auxiliary agent content are in metal oxide, and the percentage by weight that accounts for active component, carrier and auxiliary agent gross weight is:
Active component: 10-75%;
Auxiliary agent: 0.1-15%;
Carrier: surplus.
Wide temperature range type full methanation catalyst provided by the invention is characterized in that the activity of such catalysts component is a nickel.Can be used for CO and CO
2The catalyst activity component of hydrogenation methanation has transition metal such as Fe, Co, Ni, Rh, Ru, Pd, Pt, Ir, Re, Cu, Mn, Cr, V.Usually, methanation has the metal of catalyst activity to CO, equally to CO
2Methanation also has catalytic activity.Wherein Ni, Ru, Fe are the metals of studying at most.The Ru activity is very high, but it is too expensive, and active unlike common Ni catalyst under proper operating condition, so its commercial value is little.The Fe catalyst activity is low, and poor selectivity, easily ties charcoal.The catalyst based activity of Ni is higher, selectivity is good, under suitable operating condition, can satisfy industrial requirements, so the first-elected Ni of methanation catalyst active component of the present invention also can add a small amount of Co, Cu etc. as second active component certainly according to demand in active component.
Wide temperature range type full methanation catalyst provided by the invention, it is characterized in that active component nickel accounts for the 10-75% of active component, carrier and auxiliary agent gross weight in metal oxide, for the low temperature methanation, the content of such catalyst system nickel is lower, usually less than 30% (in metal oxide, account for the percentage of total catalyst weight), the present invention recommends to use content between 15-25%.For high-temperature methanation, the content of such catalyst system nickel is high slightly, and between 20-75%, the present invention recommends use amount between 20-60% usually, and the economical rationality the most between 35-45% of nickel content.
Wide temperature range type full methanation catalyst provided by the invention is characterized in that catalyst carrier is the composition that one or more and zirconia of aluminium oxide and nickel aluminide forms, and zirconium that is comprised in the carrier and al atomic ratio are between 0.01-1.45; The present invention recommends that zirconium and al atomic ratio are between 0.5-1.45 in the methanation catalyst that low temperature uses, and zirconium and al atomic ratio are between 0.05-0.7 in the methanation catalyst of high temperature use.As the wide temperature range type methanation catalyst, the best of zirconium that is comprised in its carrier and aluminium atom is than between 0.1-0.7.
The carrier that is used for methanation catalyst is also many, as α-or γ-Al
2O
3, Cr
2O
3, ZrO
2, TiO
2, MgO, kaolin and aluminous cement, and mordenite, zeolite beta and faujasite etc. with the crystal sial network in definite aperture all can be used as the methanation catalyst carrier.Al
2O
3It is a kind of catalyst carrier of generally using.γ-Al
2O
3Lip-deep Al
3+And O
2-Ion has very strong residue bonding power, with the O among the NiO
2-And Ni
2+Interacting forms strong surface ion key, helps NiO at γ-Al
2O
3Disperse on the surface, improve the stability of Ni crystal grain; But NiO and Al
2O
3Cross strong interaction and can cause the catalyst reduction difficulty.Therefore, well behaved Ni/Al
2O
3Catalyst must be taken into account the effect of above-mentioned two aspects of carrier, selects proper A l
2O
3Structural form, addition and preparation method.ZrO
2Material also is the splendid material of a kind of high-temperature hydrothermal stability, so ZrO
2It also is one of methanation catalyst carrier of using always.As everyone knows, be lower than under 300 ℃ the service condition, activity of such catalysts component Ni easily and CO form hypertoxic carbonyl Ni, cause the loss of Ni; And ZrO
2The use of carrier can also solve the low temperature losing issue of Ni catalyst.For the CO methanation, carrier is Al to the sex strong and weak order of catalyst activity
2O
3＜ZrO
2And for CO
2Methanation is ZrO then
2＞Al
2O
3So, ZrO in the carrier
2With Al
2O
3Adding proportion be one the decision catalyst performance important parameter.Full methanation catalyst carrier of the present invention is characterized in that utilizing zirconia and the aluminium oxide excellent properties as carrier, has optimized both component compatibilities simultaneously, takes into account both advantages to the full extent, to reach best catalytic effect.
Wide temperature range type full methanation catalyst provided by the invention is characterized in that the content of nickel aluminide accounts for the 5-80% of total weight of carrier in the carrier; And the ratio that the content of nickel aluminide accounts for total weight of carrier is between 30-50% the time, and catalyst effect is better.
Wide temperature range type full methanation catalyst provided by the invention is characterized in that nickel aluminide comprises NiAl in the catalyst carrier
2O
4Spinel structure.
The full methanation reaction is a strong exothermic process, generates a large amount of water simultaneously, so require catalyst carrier that good high-temperature hydrothermal stability will be arranged.As everyone knows, γ-Al
2O
3Use in the thermal and hydric environment more than 500 ℃, hydration will soon occur and cave in, cause specific surface area of catalyst to descend rapidly, reunite in the activated centre, catalyst activity reduction.Even in catalyst, add high temperature resistance carriers such as zirconia, still be difficult to accomplish the end in view.Yet Ni and Al
2O
3Be easy to generate the nickel aluminate structure, this spinel structure itself is a kind of high temperature resistance material of excellence, and very high stability is arranged under the high-temperature water heat condition.One of feature of the present invention is exactly to utilize the nickel aluminate high-temperature stability to improve the high-temperature hydrothermal stability energy of catalyst in catalyst.
In the full methanation catalyst, keep the hydrothermal stability that a certain amount of nickel aluminate not only can improve catalyst, can also keep the high activity of catalyst.The full methanation catalyst can also utilize the reducing atmosphere reduced nickel aluminate slowly in the reaction system when using more than 500 ℃, be active component in the catalyst to replenish, and improves the long-time stability of catalyst activity greatly.
The atomic ratio that embodiments more of the present invention require Al and Ni can guarantee to exist in the full methanation catalyst a certain amount of nickel aluminate structure between 1-3.But in the catalyst that low temperature uses, should increase the ratio of Zr, cause low temperature active decline problem to eliminate nickel aluminate as far as possible.
Wide temperature range type full methanation catalyst provided by the invention is characterized in that the auxiliary agent of catalyst is a lanthana, or the composition of lanthana and nickel lanthanum compound.The auxiliary agent lanthanum that adds in the component has strengthened the high-temperature hydrothermal stability of catalyst: the interpolation of lanthanum has strengthened the anti-hydro-thermal performance of catalyst carrier in the 500-750 ℃ of scope of application; And can strengthen the CO of full methanation catalyst
2Methanation activity: the interpolation of lanthanum is to CO in 260-450 ℃ the scope of application
2Methanation shows great enhancing effect.
CO concentration height and H in the coal gas
2/ CO is lower, so not only thermal discharge is big for methanation, and may produce the disproportionation knot charcoal of CO.At the high requirements of gas methanation catalyst, can add some special auxiliary agents and improve catalyst character in this respect heat endurance and resistive connection charcoal ability.Rare earth is a promoter important in the methanation catalyst system, has the double action of electron type and structural type auxiliary agent concurrently.The effect of rare earth in methanation catalyst mainly shows: improve catalyst activity, stability, anti-carbon deposit performance.One pack system or multicomponent rare-earth metal La, Ce, Y, Sm be as the methanation catalyst of auxiliary agent, is beneficial to CO and dissociates at nickel surface and form the active surface carbon species, also can stop growing up of nickel crystallite simultaneously.Wherein La, Y and Sm can effectively improve the CO of catalyst
2The methanation reaction activity, the while can also increase the surface area of catalyst.In addition, La can stablize Al
2O
3Carrier is avoided the sintering of catalyst, prolongs catalyst life.
Wide temperature range type full methanation catalyst provided by the invention is characterized in that, when the addition (in metal oxide) of the auxiliary agent lanthanum of catalyst accounted for total catalyst weight 0.5-10%, catalyst was applicable to the HTHP methanation reaction; The ratio that accounts for total catalyst weight when the addition of auxiliary agent lanthanum in the component more is applicable to coal gas full methanation process between 1-7% the time.
Wide temperature range type full methanation catalyst provided by the invention is characterized in that the nickel lanthanum compound contains LaNiO in the catalyst carrier
3Structure, this structure also is a kind of exotic material, has good hydrothermal stability.The existence of nickel lanthanum compound can improve the hydrothermal stability of catalyst in the full methanation catalyst, can also keep the high activity of catalyst.The full methanation catalyst can also utilize the reducing atmosphere reduced nickel lanthanum compound slowly in the reaction system when using more than 500 ℃, with the active component in the make-up catalyst, can improve the long-time stability of catalyst activity.The content of nickel lanthanum compound, in metal oxide nickel addition between 1-75%; The best results when content of nickel lanthanum compound is the 2.5-25% of nickel (in metal oxide) addition.
The present invention also provides a kind of wide temperature range type full methanation Preparation of catalysts method, it is characterized in that step is as follows:
(a) with the raw material of synthetic required each component of catalyst, the composition requirement according to catalyst is mixed with mixed solution, carries out chemical precipitation under liquid-phase condition, obtains the catalyst precursor;
(b) filter gained catalyst precursor, and wash twice, product under 60-120 ℃ of condition dry 8-24 hour with deionized water;
(c) drying back products therefrom is warming up to 500 ℃ of roastings 2 hours with 1-2 ℃/min speed, and products therefrom adds 2-4% graphite and the 2-4% cellulose grinds evenly, after the moulding,, reduces and forms catalyst after 2 hours through high temperature 500-1000 ℃ roasting again.
Wherein the raw material of each component is selected from carbonate, subcarbonate or the nitrate of nickel, aluminium, zirconium or lanthanum, and in addition, the raw material that relates to aluminium also can be selected from aluminium hydroxide or boehmite.Add nitric acid dissolve when the carbonate of nickel, aluminium, zirconium or lanthanum and subcarbonate and aluminium hydroxide or boehmite use and form solution.
Wide temperature range type full methanation Preparation of catalysts method provided by the invention is characterized in that the liquid phase chemical precipitation process of catalyst precursor can adopt homogeneous chemistry precipitation or chemical coprecipitation method.
The concrete steps that adopt the homogeneous chemistry precipitation process to prepare full methanation catalyst precursor are:
(a) with the raw material of synthetic required each component of catalyst, the composition requirement according to catalyst is mixed with mixed solution I;
(b) precipitate needed alkali number according to effects of ion, needed water-soluble slow-releasing type alkali is mixed with solution, and join formation mixed solution I I in the mixed solution I; Wherein water-soluble slow-releasing type alkali is selected from one or more in urea, the monoethanolamine, and the use amount of water-soluble slow-releasing type alkali is each component precipitates institute's alkali needed in nickel, aluminium, zirconium and the lanthanum raw material mixed solution 1-6 a times.
(c) mixed solution I I is inserted reactor, under stirring condition, be heated to 80-120 ℃, reacted 1-40 hour, after reaction finished, final PH was between 6-8.
The characteristics of homogeneous chemistry deposition process maximum are exactly the precipitating reagent concentration in the control solution, and making it increases lentamente, then makes the precipitation in the solution be in poised state, and precipitation can occur in whole solution equably.Control by solution temperature, precipitating reagent is slowly decomposed, thereby overcome and in solution, added precipitating reagent by the outside and cause the local inhomogeneities of precipitating reagent, the shortcoming that precipitation can not evenly be occurred in whole solution, so the material that is obtained by this method is homogeneous more, can overcome high-temperature calcination and handle impurity or the fault of construction of introducing.In the precipitation from homogeneous solution process, the use amount of alkali, temperature are the parameters that is mutually related, the PH of this two common decision solution, the just settling velocity of species and time.After precipitation was complete, certain heavyization time helped the crystallization of precipitating species, and still the long heavyization time also can be caused serious destruction to the crystallization of species, and the suitable reaction time is also very important.
Homogeneous chemistry precipitation synthetic method of the present invention is characterized in that the difference according to used precipitating reagent, and reaction temperature is between 80-120 ℃, and the reaction time about the about 4-5 of PH, was reacted final PH between 6-8 between 1-40 hour when precipitation occurring.The temperature range that urea relatively is fit to is 80-100 ℃, along with rising reaction time of temperature can shorten, does not wait between 1-40 hour; And for monoethanolamine, be more suitable for 100-120 ℃ pyroreaction, the crystallization of the more favourable crystal of pyroreaction.
The concrete steps that adopt the chemical coprecipitation process to prepare full methanation catalyst precursor are:
(a) with the raw material of synthetic required each component of catalyst, the composition requirement according to catalyst is mixed with mixed solution I, and is heated to 40-100 ℃ under stirring condition;
(b) precipitate needed alkali number according to effects of ion, needed water-soluble alkali dissolving is formed solution II; Wherein water-soluble alkali is selected from one or more in ammoniacal liquor, ammonium hydrogencarbonate, the ammonium carbonate, and the use amount of water-soluble alkali is 1-2 a times of the required alkali number of precipitated cationic in nickel, aluminium, zirconium and the lanthanum precursor solution.
(c) under intense stirring condition, the water-soluble alkali solution II is joined in the mixed solution I, keep solution temperature between 40-100 ℃, between time remaining 30-80 minute of the adding solution II, final PH is between 6-8.
Chemical coprecipitation is the conventional process of industrial extensive synthetic powder material, and coprecipitation is not high to equipment, specification requirement, and is easy and simple to handle, and cost is lower.In the chemical coprecipitation process, in solution, add the local inhomogeneities that precipitating reagent can cause precipitating reagent by the outside, thereby precipitation can not evenly occur in whole solution, so there is certain inhomogeneity in the material that this method obtains, but can revise by the high-temperature calcination processing procedure, to satisfy industrial requirement.The chemical coprecipitation process is the competitive mode homeostasis process of a complexity, the rate of deposition of various ions and precipitation order depend on the sedimentation equilibrium constant, initial concentration, precipitation of various ions can force constant and the dissolving power constant between interaction.So have many factors that reaction rate, product rerum natura are exerted an influence in the chemical coprecipitation process process,, determine the character of product jointly as parameters such as the kind of the adding speed of the use amount of alkali, alkali, alkali and solution mixing speeds.In the chemical coprecipitation process, certain heavyization time helps the crystallization of precipitating species, and to improve the homogeneity of material, still the long heavyization time also can be caused serious destruction to the crystallization of species, and the suitable heavyization time is also very important.
Chemical coprecipitation synthetic method of the present invention, it is characterized in that under intense stirring condition, water-soluble alkali is joined in the raw material mixed solution, keep solution temperature between 40-100 ℃, joining day after reaction finishes, kept fluid temperature constant between 30-80 minute, heavyization 1-2 hour, final PH was between 6-8.Wherein, mixing speed is different according to reactor size and stirring apparatus, and mixing speed is adjustable, such as anchor formula stirred reactor, and mixing speed is between 100-500 rev/min.
Wide temperature range type full methanation Preparation of catalysts method provided by the invention is characterized in that described dry run is gained sediment under 60-120 ℃ of temperature dry 8-24 hour; The pressure of dry environment can be normal pressure, also can be vacuum condition.When the baking temperature that is adopted is lower than 100 ℃, can keep certain vacuum, to accelerate rate of drying.
Wide temperature range type full methanation catalyst provided by the present invention is specially adapted to the HTHP synthetic natural gas process of coal gasification gained synthesis gas; This catalyst has good catalytic activity and hydrothermal stability in 260-750 ℃ the scope of application; And this catalyst is specially adapted to the synthesis gas full methanation reaction of temperature between 280-650 ℃.In addition, the pressure scope of application of this catalyst and is specially adapted to the high-pressure methanation process of pressure limit between 2MPa-4MPa between 0.1MPa-6MPa.
The present invention provides a kind of good catalyst and simple and convenient preparation method thereof for carbon monoxide, carbon dioxide methanation, especially for the synthesis gas full methanation provide a kind of cheapness, efficiently, the Catalysts and its preparation method of high hydrothermal stability; Innovative point of the present invention also is to utilize the high-temperature hydrothermal stability of nickel aluminide raising full methanation catalyst and the long-time stability of catalytic activity, uses rare-earth lanthanum oxide to strengthen the high-temperature hydrothermal stability and the CO of catalyst
2Methanation activity.
The invention has the beneficial effects as follows: adopt cheap raw material, utilize simple chemical precipitation technology, prepared a kind of full methanation of wide temperature range type efficiently catalyst.Provide guarantee for satisfying current growing clean energy resource demand, the enhancing to international energy and resource resource security simultaneously has irreplaceable important function.
Description of drawings
Fig. 1 is the aging rear catalyst bed moving curve of embodiment 1 gained catalyst A;
Fig. 2 is the aging rear catalyst bed moving curves of comparative example 2 gained catalyst D.
The specific embodiment
The evaluating catalyst process:
The performance evaluation of catalyst is in two sub-sections: (1) is tested the gained catalyst at first according to full methanation catalyst reaction appreciation condition (A) under 650 ℃ of conditions of high temperature; (2) according to full methanation catalyst hydro-thermal accelerated ageing experiment condition (B) catalyst is carried out accelerated ageing then, methanation catalyst reaction evaluating condition (A) is recovered in aging back, under 650 ℃ of high temperature, 400 ℃, 350 ℃ of low temperature and 300 ℃ of conditions catalyst is tested respectively once more;
(A) full methanation catalyst reaction appreciation condition:
Air speed: 20000h
-1
Pressure: 3-3.5Mpa;
Beds gas composition: H
245%; CO 10%; CO
23.5%; CH
412%; H
2O 30%;
Beds inlet temperature: 300 ℃;
Catalyst bed layer height: 40mm.
(B) full methanation catalyst hydro-thermal accelerated ageing experiment condition:
Air speed: 20000h
-1
Pressure: 3-3.5Mpa;
Gas composition: H
210%; H
2O 90%;
Reaction bed temperature control: 700 ℃;
The catalyst accelerated ageing time: 200h;
Catalyst bed layer height: 40mm.
Embodiment 1: catalyst A
(1) takes by weighing 124.5g Ni (NO
3)
2.6H
2O, 223.5g Al (NO
3)
3.9H
2O, 15g La (NO
3)
3.6H
2O, 1M Zr (NO
3)
4Solution 97.5mL adds deionized water dissolving to 1000mL;
(2) take by weighing 150g urea, add deionized water 500mL dissolving;
(3) with solution (1) with after mix (2), add deionized water to 2000mL;
(4) under stirring condition, solution is heated to 90 ℃, keep reaction 40 hours, PH rises to 4.5 from 2.3 and precipitation occurs, last PH about about 7;
(5) filtering precipitate, twice of 1000mL deionization washing; 110 ℃ of dryings 12 hours; Dry back sample places Muffle furnace, is 2 ℃/min with programming rate, 500 ℃ of roastings 2 hours; Products therefrom adds 3% graphite and 2% cellulose grinds evenly, and moulding formed the catalyst precursor in 2 hours in 500 ℃ of roastings again in Muffle furnace.
Gained catalyst precursor is 80g altogether, consists of 40%NiO-38%Al
2O
3-15%ZrO
2-7%La
2O
3Reduction is 4 hours under 400 ℃ of hydrogen conditions, catalyst A, according to methanation catalyst appreciation condition and accelerated aging test condition, estimate, it the results are shown in Table 1 and table 2.
Constant according to the step described in the embodiment 1, precipitating reagent 150g urea is replaced into the mixture of 120g urea and 50g monoethanolamine, the evaluation result of gained catalyst is with the catalyst A unanimity.
Constant according to the step described in the embodiment 1, reaction temperature is become 85 ℃, precipitation dosage is adjusted into 200g from 150g urea, and the evaluation result of gained catalyst is with the catalyst A unanimity.
Constant according to the step described in the embodiment 1, reaction temperature is become 95 ℃, the reaction time is adjusted into 30 hours, and the evaluation result of gained catalyst is with the catalyst A unanimity.
Constant according to the step described in the embodiment 1, reaction temperature is become 95 ℃, precipitating reagent 150g urea amount is adjusted into 130g, the evaluation result of gained catalyst is with the catalyst A unanimity.
Beds outlet CO and CO under the table 1 catalyst A different evaluation condition
2Concentration
Embodiment 2: catalyst B
(1) takes by weighing 124.5g Ni (NO
3)
2.6H
2O, 223.5g Al (NO
3)
3.9H
2O, 15gLa (NO
3)
3.6H
2O adds deionized water dissolving to 1000mL, under stirring condition, and is heated to 50 ℃;
(2) measure 1M Zr (NO
3)
4Solution 97.5mL joins in the mixed solution (1), stirs to form mixed solution in 20 minutes;
(3) take by weighing the NH of 275g
4HCO
3, add deionized water and form 500mL solution, under intense stirring condition, evenly be added drop-wise in the mixed solution (2) 70 minutes times spent then; PH less than
8, keep fluid temperature to be 50 ℃ and stirred 2 hours;
(4) filtering precipitate; Twice of 1000mL deionization washing; 110 ℃ of dryings 12 hours;
Dry back sample places Muffle furnace, is that 2 ℃/min is warming up to 500 ℃ of roastings 2 hours with programming rate; Products therefrom adds 3% graphite and 2% cellulose, and moulding formed the catalyst precursor in 2 hours in 800 ℃ of roastings again in Muffle furnace.
Gained catalyst precursor is 80g altogether, consists of
40%NiO-38%Al
2O
3-15%ZrO
2-7%La
2O
3Reduction is 4 hours under 400 ℃ of hydrogen conditions, gets catalyst B, according to methanation catalyst appreciation condition and accelerated aging test condition, estimates, and it the results are shown in Table 2.
Constant according to the step described in the embodiment 2, the temperature of solution (1) remained on respectively under 60 ℃, 70 ℃, 80 ℃, 90 ℃ the condition and drip aqueous slkali, the evaluation result of gained catalyst series is with the catalyst B unanimity.
Constant according to the step described in the embodiment 2, with precipitating reagent 275g NH
4HCO
3Be replaced into 260mL 25% ammoniacal liquor, 150g ammonium carbonate, 185g ammonium hydrogencarbonate and 80mL25% ammonia water mixture respectively, 100g ammonium carbonate and 90mL25% ammonia water mixture, the evaluation result of gained catalyst series is with the catalyst B unanimity.
Comparative example 1: catalyst C
Do not add the contrast experiment of zirconia and auxiliary agent;
(1) takes by weighing 124.5g Ni (NO
3)
2.6H
2O, 353g Al (NO
3)
3.9H
2O adds deionized water dissolving to 1000mL;
(2) take by weighing 180g urea, add deionized water 500mL dissolving;
(3) with solution (1) with after mix (2), add deionized water to 2000mL,
(4) under stirring condition, solution is heated to 90 ℃, keep reaction 40 hours, PH rises to 4.5 from 2.3 and precipitation occurs, last PH about about 7;
(5) filtering precipitate, twice of 1000mL deionization washing; 110 ℃ of dryings 12 hours; Dry back sample places Muffle furnace, is 2 ℃/min with programming rate, 500 ℃ of roastings 2 hours; Products therefrom adds 3% graphite and 2% cellulose grinds evenly, and moulding formed the catalyst precursor in 2 hours in 500 ℃ of roastings again in Muffle furnace.
Gained catalyst precursor is 80g altogether, consists of 40%NiO-60%Al
2O
3Reduction is 4 hours under 500 ℃ of hydrogen conditions, gets catalyst C, according to methanation catalyst appreciation condition and accelerated aging test condition, estimates, and it the results are shown in Table 2.
Comparative example 2: catalyst D
The contrast experiment of adding assistant not;
(1) takes by weighing 124.5g Ni (NO
3)
2.6H
2O, 247g Al (NO
3)
3.9H
2O, 1M Zr (NO
3)
4Solution 117mL adds deionized water dissolving to 1000mL;
(2) take by weighing 150g urea, add deionized water 500mL dissolving;
(3) with solution (1) with after mix (2), add deionized water to 2000mL,
(4) under stirring condition, solution is heated to 90 ℃, keep reaction 40 hours, PH rises to 4.5 from 2.3 and precipitation occurs, last PH about about 7;
(5) filtering precipitate, twice of 1000mL deionization washing; 110 ℃ of dryings 12 hours; Dry back sample places Muffle furnace, is 2 ℃/min with programming rate, 500 ℃ of roastings 2 hours; Products therefrom adds 3% graphite and 2% cellulose grinds evenly, and moulding formed the catalyst precursor in 2 hours in 500 ℃ of roastings again in Muffle furnace.
Gained catalyst precursor is 80g altogether, consists of 40%NiO-42%Al
2O
3-18%ZrO
2Reduction is 4 hours under 400 ℃ of hydrogen conditions, gets catalyst D, according to methanation catalyst appreciation condition and accelerated aging test condition, estimates, and it the results are shown in Table 2.
Comparative example 3: catalyst E
Do not add the contrast experiment of auxiliary agent;
(1) takes by weighing 124.5g Ni (NO
3)
2.6H
2O, 247g Al (NO
3)
3.9H
2O adds deionized water dissolving to 1000mL, under stirring condition, is heated to 50 ℃;
(2) measure 1M Zr (NO
3)
4Solution 117mL joins in the mixed solution (1), stirs to form mixed solution in 20 minutes;
(3) take by weighing the NH of 280g
4HCO
3, add deionized water and form 500mL solution, under intense stirring condition, evenly be added drop-wise in the mixed solution (2) 70 minutes times spent then; PH keeps fluid temperature to be 50 ℃ and stirred 2 hours less than 8;
(4) filtering precipitate; Twice of 1000mL deionization washing; 110 ℃ of dryings 12 hours; Dry back sample places Muffle furnace, is that 2 ℃/min is warming up to 500 ℃ of roastings 2 hours with programming rate; Products therefrom adds 3% graphite and 2% cellulose grinds evenly, and moulding formed the catalyst precursor in 2 hours in 800 ℃ of roastings again in Muffle furnace.
Gained catalyst precursor is 80g altogether, consists of 40%NiO-42%Al
2O
3-18%ZrO
2, reduction is 4 hours under 400 ℃ of hydrogen conditions, according to methanation catalyst appreciation condition and accelerated aging test condition, estimates, and it the results are shown in Table 2.
Embodiment 3: catalyst F
(1) takes by weighing 71.5g Ni (NO
3)
2.6H
2O, 323g Al (NO
3)
3.9H
2O, 15g La (NO
3)
3.6H
2O, 1M Zr (NO
3)
4Solution 97.5mL adds deionized water dissolving to 1000mL;
(2) take by weighing 160g urea, add deionized water 500mL dissolving;
(3) with solution (1) with after mix (2), add deionized water to 2000mL;
(4) under stirring condition, solution is heated to 90 ℃, keep reaction 40 hours, PH rises to 4.5 from 2.3 and precipitation occurs, last PH about about 7;
(5) filtering precipitate, twice of 1000mL deionization washing; 110 ℃ of dryings 12 hours; Dry back sample places Muffle furnace, is 2 ℃/min with programming rate, 500 ℃ of roastings 2 hours; Products therefrom adds 3% graphite and 2% cellulose grinds evenly, and moulding formed the catalyst precursor in 2 hours in 500 ℃ of roastings again in Muffle furnace.
Gained catalyst precursor is 80g altogether, consists of 23%NiO-55%Al
2O
3-15%ZrO
2-7%La
2O
3Reduction is 4 hours under 400 ℃ of hydrogen conditions, gets catalyst F, according to methanation catalyst appreciation condition and accelerated aging test condition, estimates, and it the results are shown in Table 2.
Embodiment 4: catalyst G
(1) takes by weighing 234g Ni (NO
3)
2.6H
2O, 88g Al (NO
3)
3.9H
2O, 15g La (NO
3)
3.6H
2O, 1M Zr (NO
3)
4Solution 19.5mL adds deionized water dissolving to 1000mL;
(2) take by weighing 120g urea, add deionized water 500mL dissolving;
(3) with solution (1) with after mix (2), add deionized water to 2000mL;
(4) under stirring condition, solution is heated to 90 ℃, keep reaction 40 hours, PH rises to 4.5 from 2.3 and precipitation occurs, last PH about about 7;
(5) filtering precipitate, twice of 1000mL deionization washing; 110 ℃ of dryings 12 hours; Dry back sample places Muffle furnace, is 2 ℃/min with programming rate, 500 ℃ of roastings 2 hours; Products therefrom adds 3% graphite and 2% cellulose grinds evenly, and moulding formed the catalyst precursor in 2 hours in 500 ℃ of roastings again in Muffle furnace.
Gained catalyst precursor is 80g altogether, consists of 75%NiO-15%Al
2O
3-3%ZrO
2-7%La
2O
3Reduction is 4 hours under 400 ℃ of hydrogen conditions, gets catalyst G, according to methanation catalyst appreciation condition and accelerated aging test condition, estimates, and it the results are shown in Table 2.
Embodiment 5: catalyst H
(1) takes by weighing 124.5gNi (NO
3)
2.6H
2O, 253gAl (NO
3)
3.9H
2O, 15gLa (NO
3)
3.6H
2O, 1MZr (NO
3)
4Solution 65mL adds deionized water dissolving to 1000mL;
(2) take by weighing 150g urea, add deionized water 500mL dissolving;
(3) with solution (1) with after mix (2), add deionized water to 2000mL;
(4) under stirring condition, solution is heated to 90 ℃, keep reaction 40 hours, PH rises to 4.5 from 2.3 and precipitation occurs, last PH about about 7;
(5) filtering precipitate, twice of 1000mL deionization washing; 110 ℃ of dryings 12 hours; Dry back sample places Muffle furnace, is 2 ℃/min with programming rate, 500 ℃ of roastings 2 hours; Products therefrom adds 3% graphite and 2% cellulose grinds evenly, and moulding formed the catalyst precursor in 2 hours in 500 ℃ of roastings again in Muffle furnace.
Gained catalyst precursor is 80g altogether, consists of 40%NiO-43%Al
2O
3-10%ZrO
2-7%La
2O
3Reduction is 4 hours under 400 ℃ of hydrogen conditions, gets catalyst H, according to methanation catalyst appreciation condition and accelerated aging test condition, estimates, and it the results are shown in Table 2.
Embodiment 6: catalyst I
(1) takes by weighing 124.5g Ni (NO
3)
2.6H
2O, 88g Al (NO
3)
3.9H
2O, 15g La (NO
3)
3.6H
2O, 1MZr (NO
3)
4Solution 247mL adds deionized water dissolving to 1000mL;
(2) take by weighing 130g urea, add deionized water 500mL dissolving;
(3) with solution (1) with after mix (2), add deionized water to 2000mL;
(4) under stirring condition, solution is heated to 90 ℃, keep reaction 40 hours, PH rises to 4.5 from 2.3 and precipitation occurs, last PH about about 7;
(5) filtering precipitate, twice of 1000mL deionization washing; 110 ℃ of dryings 12 hours; Dry back sample places Muffle furnace, is 2 ℃/min with programming rate, 500 ℃ of roastings 2 hours; Products therefrom adds 3% graphite and 2% cellulose grinds evenly, and moulding formed the catalyst precursor in 2 hours in 500 ℃ of roastings again in Muffle furnace.
Gained catalyst precursor is 80g altogether, consists of 40%NiO-15%Al
2O
3-38%ZrO
2-7%La
2O
3Reduction is 4 hours under 400 ℃ of hydrogen conditions, gets catalyst I, according to methanation catalyst appreciation condition and accelerated aging test condition, estimates, and it the results are shown in Table 2.
Embodiment 7: catalyst J
(1) takes by weighing 124.5gNi (NO
3)
2.6H
2O, 241gAl (NO
3)
3.9H
2O, 2gLa (NO
3)
3.6H
2O, 1MZr (NO
3)
4Solution 117mL adds deionized water dissolving to 1000mL;
(2) take by weighing 150g urea, add deionized water 500mL dissolving;
(3) with solution (1) with after mix (2), add deionized water to 2000mL;
(4) under stirring condition, solution is heated to 90 ℃, keep reaction 40 hours, PH rises to 4.5 from 2.3 and precipitation occurs, last PH about about 7;
(5) filtering precipitate, twice of 1000mL deionization washing; 110 ℃ of dryings 12 hours; Dry back sample places Muffle furnace, is 2 ℃/min with programming rate, 500 ℃ of roastings 2 hours; Products therefrom adds 3% graphite and 2% cellulose grinds evenly, and moulding formed the catalyst precursor in 2 hours in 500 ℃ of roastings again in Muffle furnace.
Gained catalyst precursor is 80g altogether, consists of 40%NiO-41%Al
2O
3-18%ZrO
2-1%La
2O
3Reduction is 4 hours under 400 ℃ of hydrogen conditions, gets catalyst J, according to methanation catalyst appreciation condition and accelerated aging test condition, estimates, and it the results are shown in Table 2.
Embodiment 8: catalyst K
(1) takes by weighing 124.5gNi (NO
3)
2.6H
2O, 235gAl (NO
3)
3.9H
2O, 8.5gLa (NO
3)
3.6H
2O, 1MZr (NO
3)
4Solution 104mL adds deionized water dissolving to 1000mL;
(2) take by weighing 150g urea, add deionized water 500mL dissolving;
(3) with solution (1) with after mix (2), add deionized water to 2000mL;
(4) under stirring condition, solution is heated to 90 ℃, keep reaction 40 hours, PH rises to 4.5 from 2.3 and precipitation occurs, last PH about about 7;
(5) filtering precipitate, twice of 1000mL deionization washing; 110 ℃ of dryings 12 hours; Dry back sample places Muffle furnace, is 2 ℃/min with programming rate, 500 ℃ of roastings 2 hours; Products therefrom adds 3% graphite and 2% cellulose grinds evenly, and moulding formed the catalyst precursor in 2 hours in 500 ℃ of roastings again in Muffle furnace.
Gained catalyst precursor is 80g altogether, consists of 40%NiO-40%Al
2O
3-16%ZrO
2-4%La
2O
3Reduction is 4 hours under 400 ℃ of hydrogen conditions, gets catalyst K, according to methanation catalyst appreciation condition and accelerated aging test condition, estimates, and it the results are shown in Table 2.
Embodiment 9: catalyst L
(1) takes by weighing 124.5gNi (NO
3)
2.6H
2O, 212gAl (NO
3)
3.9H
2O, 22gLa (NO
3)
3.6H
2O, 1MZr (NO
3)
4Solution 91mL adds deionized water dissolving to 1000mL;
(2) take by weighing 140g urea, add deionized water 500mL dissolving;
(3) with solution (1) with after mix (2), add deionized water to 2000mL;
(4) under stirring condition, solution is heated to 90 ℃, keep reaction 40 hours, PH rises to 4.5 from 2.3 and precipitation occurs, last PH about about 7;
(5) filtering precipitate, twice of 1000mL deionization washing; 110 ℃ of dryings 12 hours; Dry back sample places Muffle furnace, is 2 ℃/min with programming rate, 500 ℃ of roastings 2 hours; Products therefrom adds 3% graphite and 2% cellulose grinds evenly, and moulding formed the catalyst precursor in 2 hours in 500 ℃ of roastings again in Muffle furnace.
Gained catalyst precursor is 80g altogether, consists of 40%NiO-36%Al
2O
3-14%ZrO
2-10%La
2O
3Reduction is 4 hours under 400 ℃ of hydrogen conditions, gets catalyst L, according to methanation catalyst appreciation condition and accelerated aging test condition, estimates, and it the results are shown in Table 2.
Embodiment 10: catalyst M
(1) takes by weighing 124.5gNi (NO
3)
2.6H
2O, 241gAl (NO
3)
3.9H
2O, 0.85gLa (NO
3)
3.6H
2O, 1MZr (NO
3)
4Solution 121mL adds deionized water dissolving to 1000mL;
(2) take by weighing 150g urea, add deionized water 500mL dissolving;
(3) with solution (1) with after mix (2), add deionized water to 2000mL;
(4) under stirring condition, solution is heated to 90 ℃, keep reaction 40 hours, PH rises to 4.5 from 2.3 and precipitation occurs, last PH about about 7;
(5) filtering precipitate, twice of 1000mL deionization washing; 110 ℃ of dryings 12 hours; Dry back sample places Muffle furnace, is 2 ℃/min with programming rate, 500 ℃ of roastings 2 hours; Products therefrom adds 3% graphite and 2% cellulose grinds evenly, and moulding formed the catalyst precursor in 2 hours in 500 ℃ of roastings again in Muffle furnace.
Gained catalyst precursor is 80g altogether, consists of 40%NiO-41%Al
2O
3-18.6%ZrO
2-0.4%La
2O
3Reduction is 4 hours under 400 ℃ of hydrogen conditions, gets catalyst M, according to methanation catalyst appreciation condition and accelerated aging test condition, estimates, and it the results are shown in Table 2.
Embodiment 11: catalyst n
(1) takes by weighing 124.5gNi (NO
3)
2.6H
2O, 235gAl (NO
3)
3.9H
2O, 8.5gLa (NO
3)
3.6H
2O adds deionized water dissolving to 1000mL, under stirring condition, is heated to 50 ℃;
(2) measure 1MZr (NO
3)
4Solution 104mL joins in the mixed solution (1), stirs to form mixed solution in 20 minutes;
(3) take by weighing the NH of 280g
4HCO
3, add deionized water and form 500mL solution, under intense agitation, evenly be added drop-wise in the mixed solution (2) 70 minutes times spent then; PH keeps fluid temperature to be 50 ℃ and stirred 2 hours less than 8;
(4) filtering precipitate; Twice of 1000mL deionization washing; 110 ℃ of dryings 12 hours; Dry back sample places Muffle furnace, is that 2 ℃/min is warming up to 500 ℃ of roastings 2 hours with programming rate; Products therefrom adds 3% graphite and 2% cellulose grinds evenly, and moulding formed the catalyst precursor in 2 hours in 800 ℃ of roastings again in Muffle furnace.
Gained catalyst precursor is 80g altogether, consists of 40%NiO-40%Al
2O
3-16%ZrO
2-4%La
2O
3Reduction is 4 hours under 400 ℃ of hydrogen conditions, gets catalyst n, according to methanation catalyst appreciation condition and accelerated aging test condition, estimates, and it the results are shown in Table 2.
Embodiment 12: catalyst O
(1) takes by weighing 124.5gNi (NO
3)
2.6H
2O, 88gAl (NO
3)
3.9H
2O, 10.6gLa (NO
3)
3.6H
2O adds deionized water dissolving to 1000mL, under stirring condition, is heated to 50 ℃;
(2) measure 1MZr (NO
3)
4Solution 260mL joins in the mixed solution (1), stirs to form mixed solution in 20 minutes;
(3) take by weighing the NH of 235g
4HCO
3, add deionized water and form 500mL solution, under intense agitation, evenly be added drop-wise in the mixed solution (2) 70 minutes times spent then; PH keeps fluid temperature to be 50 ℃ and stirred 2 hours less than 8;
(4) filtering precipitate; Twice of 1000mL deionization washing; 110 ℃ of dryings 12 hours; Dry back sample places Muffle furnace, is that 2 ℃/min is warming up to 500 ℃ of roastings 2 hours with programming rate; Products therefrom adds 3% graphite and 2% cellulose grinds evenly, and moulding formed the catalyst precursor in 2 hours in 800 ℃ of roastings again in Muffle furnace.
Gained catalyst precursor is 80g altogether, consists of 40%NiO-15%Al
2O
3-40%ZrO
2-5%La
2O
3Reduction is 4 hours under 400 ℃ of hydrogen conditions, gets catalyst O, according to methanation catalyst appreciation condition and accelerated aging test condition, estimates, and it the results are shown in Table 2.
Evaluating catalyst result among table 2 embodiment
The explanation of embodiment experimental result
By in the evaluation result of table 2 as can be seen, catalyst provided by the invention all has extraordinary high-temperature stability, 650 ℃ of high temperature hotspot all do not move after the high temperature accelerated ageing, compare with contrast experiment's gained catalyst C, D, E in the present embodiment, have the thermally-stabilised advantage of tangible high-temperature water.At some catalyst such as A, H, I, J, K, when 300 ℃ of aging back low temperature were estimated, the bed focus did not still move, and further specifies some catalyst of the present invention and has excellent high-temperature hydrothermal stability.
From table 1 in the catalyst A evaluation result as can be seen, aging back CO and CO
2Conversion ratio all can be realized the chemical thermodynamics balance under 300 ℃ temperature, this shows that also some catalyst of the present invention has excellent high-temperature hydrothermal stability, can show that also some catalyst of the present invention has good low temperature active simultaneously.
Catalyst A in the table 2-B evaluation result shows that the preparation method who the present invention relates to all is applicable to Preparation of Catalyst of the present invention, and catalyst has good hydrothermal stability; But the high-temperature hydrothermal stability that relates to some preparation scheme gained catalyst of homogeneous chemistry precipitation process can be better than relating to some preparation scheme of chemical coprecipitation process.
Can learn that from the evaluation result of embodiment 1 gained catalyst employed precipitating reagent can be the mixture of urea, urea and monoethanolamine in some catalyst embodiments of the present invention, the gained catalyst has high-temperature hydrothermal stability preferably.
From the evaluation result of embodiment 1 gained catalyst, can also learn, employed reaction temperature, precipitating reagent use amount and reaction time are to adjust in some catalyst embodiments of the present invention, in theme thinking scheme of the present invention, catalyst has kept its high-temperature hydrothermal stability; There are certain correlation the temperature, the time that show catalyst precursor building-up process simultaneously, and promptly the higher the reaction time of reaction temperature can shorten, and the low the reaction time of reaction temperature needs to prolong; The reaction temperature and the urea use amount of catalyst precursor building-up process also have certain correlation, i.e. urea use amount increase can corresponding reduction reaction temperature, and reaction temperature improves the use amount that can save precipitating reagent.In a word, reaction temperature, precipitating reagent use amount are related each other synthetic parameters with the reaction time to a certain extent, and according to technical scheme of the present invention, the catalyst that is obtained all has high-temperature hydrothermal stability preferably.
From the evaluation result of embodiment 2 gained catalyst, can find, employed precipitation temperature is adjustable in some catalyst embodiments of the present invention, under 50,60,70,80,90 ℃ condition, all can obtain to have the catalyst of high-temperature hydrothermal stability preferably.
From the evaluation result of embodiment 2 gained catalyst, can also find, employed precipitating reagent can be the mixture of mixture, ammonium carbonate and the ammoniacal liquor of carbonic hydroammonium, ammonium carbonate, ammoniacal liquor, carbonic hydroammonium and ammoniacal liquor in some catalyst embodiments of the present invention, and the gained catalyst all has high-temperature hydrothermal stability preferably.
Catalyst A, C, D evaluation result show in the table 2, high temperature ZrO in some catalyst embodiments of the present invention
2The interpolation of carrier has improved the high-temperature stability of catalyst; The interpolation of auxiliary agent lanthanum has further improved the high-temperature hydrothermal stability of catalyst in some embodiment of while.
The data of Fig. 1 and Fig. 2 show, add the auxiliary agent lanthanum in certain embodiments of the present invention, have not only improved the high-temperature hydrothermal stability of catalyst, have improved the low temperature active of catalyst simultaneously greatly.
Catalyst F, G evaluation result show in the table 2, and the content of nickel is adjustable in some catalyst embodiments of the present invention, and in theme thinking scheme of the present invention, catalyst has kept its high-temperature hydrothermal stability; Show that simultaneously catalysis wants the high-temperature hydrothermal stability of obtained performance excellence, the use amount of nickel will suitably increase.
Catalyst H-I evaluation result shows in the table 2, and aluminium zirconium ratio can be adjusted in some catalyst embodiments of the present invention, and in theme thinking scheme of the present invention, catalyst has kept its high-temperature hydrothermal stability; Show that simultaneously catalyst wants the high-temperature hydrothermal stability of obtained performance excellence, it is crucial keeping suitable aluminium atomic percent zirconium.
Catalyst J-M evaluation result shows in the table 2, the addition of auxiliary agent lanthanum can strengthen the high-temperature hydrothermal stability of catalyst greatly in some catalyst embodiments of the present invention a bigger scope, but want the high-temperature hydrothermal stability of obtained performance excellence, the addition of auxiliary agent lanthanum should not be very little.
Catalyst n, O evaluation result further show in the table 2, relate to the production program of chemical coprecipitation process in some catalyst embodiments of the present invention, can make catalyst obtain high-temperature hydrothermal stability preferably; Addition by aluminium atomic percent zirconium and lanthanum is regulated, and can strengthen its high-temperature hydrothermal stability energy.
The foregoing description only illustrates principle of the present invention and effect thereof, but not is used to limit the present invention.Any person of ordinary skill in the field all can be in the scope of inventive concept and spirit, and the foregoing description is made amendment and changed.Therefore, the scope of the present invention should be as the criterion so that claim is listed.
Claims (20)
1. wide temperature range type full methanation catalyst, this catalyst be by active component, provide the carrier of physical support to active component, and active component is had collaborative or auxiliary catalysis effect, and the auxiliary agent that carrier plays stabilization is formed, and it is characterized in that:
Active component is a nickel; Carrier is the composition that one or more and zirconia of aluminium oxide and nickel aluminide forms; Auxiliary agent is a lanthana, or the composition of lanthana and nickel lanthanum compound; Wherein zirconium that is comprised in the carrier and al atomic ratio are between 0.01-1.45;
Active component, carrier and auxiliary agent content are in metal oxide, and the percentage by weight that accounts for active component, carrier and auxiliary agent gross weight is:
Active component: 10-75%;
Auxiliary agent: 0.1-15%;
Carrier: surplus.
2. according to the described wide temperature range type full methanation of claim 1 catalyst, it is characterized in that the content of described catalyst activity component nickel, count the 20-60% of active component, carrier and auxiliary agent gross weight with metal oxide.
3. according to the content of the described catalyst activity component of claim 2 nickel, it is characterized in that the content of catalyst activity component nickel, count the 35-45% of active component, carrier and auxiliary agent gross weight with metal oxide.
4. according to the described a kind of wide temperature range type full methanation catalyst of claim 1, it is characterized in that the zirconium that comprised in the described carrier and al atomic ratio are between 0.1-0.7.
5. according to the described a kind of wide temperature range type full methanation catalyst of claim 1, it is characterized in that the content of nickel aluminide in the described carrier accounts for the 5-80% of total weight of carrier.
6. according to the described a kind of wide temperature range type full methanation catalyst of claim 1, it is characterized in that the content of nickel aluminide in the described carrier accounts for the 30-50% of total weight of carrier.
7. according to the described a kind of wide temperature range type full methanation catalyst of claim 1, it is characterized in that nickel aluminide contains NiAl in the described carrier
2O
4Spinel structure.
8. according to the described a kind of wide temperature range type full methanation catalyst of claim 1, it is characterized in that the addition of described auxiliary agent lanthanum, account for the 0.5-10% of active component, carrier and auxiliary agent gross weight in metal oxide.
9. according to the addition of the described auxiliary agent lanthanum of claim 8, it is characterized in that the addition of lanthanum, account for the 1-7% of active component, carrier and auxiliary agent gross weight in metal oxide.
10. according to the described a kind of wide temperature range type full methanation catalyst of claim 1, it is characterized in that the content of nickel lanthanum compound in described auxiliary agent, for account for the 1-75% of nickel addition in metal oxide.
11. according to the content of nickel lanthanum compound in the described auxiliary agent of claim 10, it is characterized in that the content of nickel lanthanum compound in the auxiliary agent, for account for the 2.5-25% of nickel addition in metal oxide.
12., it is characterized in that described nickel lanthanum compound contains LaNiO according to the described a kind of wide temperature range type full methanation catalyst of claim 1
3Structure.
13. the described wide temperature range type full methanation of claim 1 a Preparation of catalysts method is characterized in that:
(a) with the raw material of synthetic required each component of catalyst, the composition requirement according to catalyst is mixed with mixed solution, carries out chemical precipitation under liquid-phase condition, obtains the catalyst precursor;
(b) filter gained catalyst precursor, and wash twice, product under 60-120 ℃ of condition dry 8-24 hour with deionized water;
(c) drying back products therefrom is warming up to 500 ℃ of roastings 2 hours with 1-2 ℃/min speed, and products therefrom adds 2-4% graphite and the 2-4% cellulose grinds evenly, after the moulding,, reduces and forms catalyst after 2 hours through 500-1000 ℃ of roasting again.
14. according to the described wide temperature range type full methanation of claim 13 Preparation of catalysts method, it is characterized in that the chemical precipitation employing homogeneous chemistry intermediate processing in the described step (a), its process is: with the raw material of synthetic required each component of catalyst, composition requirement according to catalyst is mixed with mixed solution I; Needed water-soluble slow-releasing type alkali is mixed with solution, and joins formation mixed solution I I in the mixed solution I; I inserts reactor with mixed solution I, under stirring condition, is heated to 80-120 ℃, reacts 1-40 hour; Wherein the use amount of water-soluble slow-releasing type alkali is 1-6 times that each component precipitates institute's alkali needed in nickel, aluminium, zirconium and the lanthanum raw material mixed solution.
15. according to the described wide temperature range type full methanation of claim 13 Preparation of catalysts method, it is characterized in that the chemical precipitation employing chemical coprecipitation method in the described step (a), its process is: with the raw material of synthetic required each component of catalyst, composition requirement according to catalyst, be mixed with mixed solution I, and under stirring condition, be heated to 40-100 ℃; Needed water-soluble alkali dissolving is formed solution II; Under intense stirring condition, the water-soluble alkali solution II is joined in the mixed solution I, keep solution temperature between 40-100 ℃, between time remaining 30-80 minute of the adding solution II; Wherein the use amount of water-soluble alkali be the required alkali number of precipitated cationic in nickel, aluminium, zirconium and the lanthanum precursor solution 1-2 doubly.
16., it is characterized in that described raw material is selected from the carbonate of nickel, aluminium, zirconium or lanthanum, subcarbonate or nitrate according to the described raw material of claim 13-15.
17., it is characterized in that component aluminium is selected from aluminium hydroxide or boehmite in the described raw material according to the described raw material of claim 13-15.
18., it is characterized in that adding when the carbonate of described nickel, aluminium, zirconium or lanthanum and subcarbonate and aluminium hydroxide or boehmite use nitric acid dissolve and form solution according to claim 16,17 described raw materials.
19., it is characterized in that described water-soluble slow-releasing type alkali is selected from a kind of or mixture in urea, the monoethanolamine according to the described homogeneous chemistry intermediate processing of claim 14.
20., it is characterized in that described water-soluble alkali is selected from one or more in ammoniacal liquor, ammonium hydrogencarbonate, the ammonium carbonate according to the described chemical coprecipitation method of claim 15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910187676 CN102029162B (en) | 2009-09-28 | 2009-09-28 | Wide-temperature full methanation catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910187676 CN102029162B (en) | 2009-09-28 | 2009-09-28 | Wide-temperature full methanation catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102029162A true CN102029162A (en) | 2011-04-27 |
| CN102029162B CN102029162B (en) | 2013-01-16 |
Family
ID=43882943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910187676 Active CN102029162B (en) | 2009-09-28 | 2009-09-28 | Wide-temperature full methanation catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102029162B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513124A (en) * | 2011-12-15 | 2012-06-27 | 大连凯特利催化工程技术有限公司 | Catalyst for methanating coke oven gas and preparation method thereof |
| CN104888783A (en) * | 2014-03-03 | 2015-09-09 | 中国石油化工股份有限公司 | Methanation catalyst, preparation method and application thereof |
| CN105214675A (en) * | 2015-10-10 | 2016-01-06 | 新奥科技发展有限公司 | The preparation method of cobalt and cerium compound oxide catalyst and cobalt and cerium compound oxide catalyst |
| CN105709747A (en) * | 2014-12-01 | 2016-06-29 | 中国科学院大连化学物理研究所 | Integrally extruded-type nickel-based catalyst, and preparation method and applications thereof |
| CN105709748A (en) * | 2014-12-01 | 2016-06-29 | 中国科学院大连化学物理研究所 | CO methanation catalyst with water-vapor conversion function and preparation method and application thereof |
| CN105709749A (en) * | 2014-12-03 | 2016-06-29 | 中国科学院大连化学物理研究所 | High-strength integrally-extruded nickel-based methanation catalyst and preparation method thereof |
| CN107073451A (en) * | 2014-07-19 | 2017-08-18 | 日立造船株式会社 | The preparation method of methanation reaction catalyst, the preparation method of methanation reaction catalyst and methane |
| CN107376925A (en) * | 2017-07-21 | 2017-11-24 | 中国华能集团公司 | A kind of low temperature high activity carbon dioxide methanation catalyst and preparation method thereof |
| CN110479280A (en) * | 2019-07-17 | 2019-11-22 | 华南理工大学 | A kind of CO cryogenic selective methanation Ni-ZrO2/NiAl2O4Catalyst and its preparation method and application |
| CN111229228A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | CO (carbon monoxide)2Complete methanation catalyst and preparation and application thereof |
| CN115400764A (en) * | 2022-07-20 | 2022-11-29 | 国网浙江省电力有限公司丽水供电公司 | Carbon dioxide methanation catalyst with good high-temperature activity and preparation method thereof |
| CN116283243A (en) * | 2023-05-17 | 2023-06-23 | 湖南大学 | Preparation method of high-toughness aluminum oxide sheet |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1505254A (en) * | 1974-07-03 | 1978-03-30 | Haldor Topsoe As | Catalyst and process for preparing methane rich gas |
| CN1024536C (en) * | 1988-10-19 | 1994-05-18 | 中国科学院大连化学物理研究所 | Active non-uniform catalyzer for ordinary pressure water-gas methanides and its making method |
| CN100567461C (en) * | 2006-03-17 | 2009-12-09 | 中国石油天然气股份有限公司 | A kind of nickel series hydrogenating catalyst and preparation method thereof, application |
-
2009
- 2009-09-28 CN CN 200910187676 patent/CN102029162B/en active Active
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513124A (en) * | 2011-12-15 | 2012-06-27 | 大连凯特利催化工程技术有限公司 | Catalyst for methanating coke oven gas and preparation method thereof |
| CN104888783A (en) * | 2014-03-03 | 2015-09-09 | 中国石油化工股份有限公司 | Methanation catalyst, preparation method and application thereof |
| CN107073451A (en) * | 2014-07-19 | 2017-08-18 | 日立造船株式会社 | The preparation method of methanation reaction catalyst, the preparation method of methanation reaction catalyst and methane |
| CN107073451B (en) * | 2014-07-19 | 2020-07-03 | 日立造船株式会社 | Catalyst for methanation reaction, method for producing catalyst for methanation reaction, and method for producing methane |
| CN105709748B (en) * | 2014-12-01 | 2018-08-31 | 中国科学院大连化学物理研究所 | CO methanation catalysts and its preparation method and application with water-gas shift function |
| CN105709748A (en) * | 2014-12-01 | 2016-06-29 | 中国科学院大连化学物理研究所 | CO methanation catalyst with water-vapor conversion function and preparation method and application thereof |
| CN105709747A (en) * | 2014-12-01 | 2016-06-29 | 中国科学院大连化学物理研究所 | Integrally extruded-type nickel-based catalyst, and preparation method and applications thereof |
| CN105709747B (en) * | 2014-12-01 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of integral extruding type nickel-base catalyst and its preparation method and application |
| CN105709749B (en) * | 2014-12-03 | 2019-02-05 | 中国科学院大连化学物理研究所 | Ni-based methanation catalyst of a kind of high intensity integral extruding type and preparation method thereof |
| CN105709749A (en) * | 2014-12-03 | 2016-06-29 | 中国科学院大连化学物理研究所 | High-strength integrally-extruded nickel-based methanation catalyst and preparation method thereof |
| CN105214675A (en) * | 2015-10-10 | 2016-01-06 | 新奥科技发展有限公司 | The preparation method of cobalt and cerium compound oxide catalyst and cobalt and cerium compound oxide catalyst |
| CN107376925A (en) * | 2017-07-21 | 2017-11-24 | 中国华能集团公司 | A kind of low temperature high activity carbon dioxide methanation catalyst and preparation method thereof |
| CN111229228A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | CO (carbon monoxide)2Complete methanation catalyst and preparation and application thereof |
| CN110479280A (en) * | 2019-07-17 | 2019-11-22 | 华南理工大学 | A kind of CO cryogenic selective methanation Ni-ZrO2/NiAl2O4Catalyst and its preparation method and application |
| CN110479280B (en) * | 2019-07-17 | 2022-09-13 | 华南理工大学 | CO low-temperature selective methanation Ni-ZrO 2 /NiAl 2 O 4 Catalyst, preparation method and application thereof |
| CN115400764A (en) * | 2022-07-20 | 2022-11-29 | 国网浙江省电力有限公司丽水供电公司 | Carbon dioxide methanation catalyst with good high-temperature activity and preparation method thereof |
| CN115400764B (en) * | 2022-07-20 | 2024-01-30 | 国网浙江省电力有限公司丽水供电公司 | Carbon dioxide methanation catalyst with good high-temperature activity and preparation method thereof |
| CN116283243A (en) * | 2023-05-17 | 2023-06-23 | 湖南大学 | Preparation method of high-toughness aluminum oxide sheet |
| CN116283243B (en) * | 2023-05-17 | 2023-07-21 | 湖南大学 | Preparation method of high-toughness aluminum oxide sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102029162B (en) | 2013-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102029162B (en) | Wide-temperature full methanation catalyst and preparation method thereof | |
| CN102029161B (en) | Method for preparing complete methanation catalyst for hydrothermal chemical process | |
| CN101716513B (en) | Coal gasification catalyst completely methanated by synthesis gas and preparation and application thereof | |
| CN103071507B (en) | Completely-methanated catalyst as well as preparation method and application thereof | |
| CN100594977C (en) | Noble metal catalyst for high temperature steam reforming preparing hydrogen from methyl alcohol | |
| CN103752319A (en) | Anti-carbon-deposition Ni-based catalyst for hydrogen production by methane steam reforming and preparation method thereof | |
| CN102631932A (en) | Nickel-base metal catalyst for preparing hydrogen by hydrazine decomposition at room temperature, as well as preparation and application thereof | |
| US20120264597A1 (en) | CEAlO3 PEROVSKITES CONTAINING TRANSITION METAL | |
| CN104028270A (en) | Methanation catalyst and preparation method thereof | |
| CN100376326C (en) | Method for preparing supported nano copper nickel catalyst and application thereof in oxidative dehydrogenation reaction of alkylol amine | |
| CN101444740A (en) | Catalyst for hydrogen production by bio-oil steam reforming and preparation method thereof | |
| CN110102295A (en) | A kind of ruthenium catalyst and preparation method thereof for synthesizing ammonia | |
| CN104971727A (en) | Preparation method of high-efficiency nickel-based catalyst for producing hydrogen in methanol-steam reforming | |
| CN106268852A (en) | A kind of catalyst for one-step method from syngas coproduction mixed alcohol and alhpa olefin and preparation method and application | |
| CN104190427A (en) | Multiphase nickel-based catalyst as well as preparation methods and application thereof | |
| CN114272950A (en) | CH (physical channel)4、CO2Catalyst for reforming preparation of synthesis gas and preparation method and application thereof | |
| CN104741131A (en) | Preparation method of Ni-Mn-Mg-O/MgAl2O4 reformed composite oxide catalyst | |
| CN102674413B (en) | Catalyst for methanation of CO and H2, and preparation method thereof | |
| CN102145876A (en) | Method for producing hydrogen by reforming methanol steam | |
| CN102091617B (en) | Cu-based low-temperature water gas conversion catalyst under hydrogen rich reformed gas and preparation method thereof | |
| CN101306361A (en) | Method for preparing hexa-aluminate catalyst using reversed phase micro-emulsion method | |
| US9079165B2 (en) | Ethanol reforming catalyst composition and method of producing ethanol reforming catalyst | |
| CN113952970A (en) | Catalyst with nickel loaded on hydroxyapatite, preparation method and application thereof | |
| CN105363460B (en) | A kind of non-loading type deep hydrogenation catalyst and preparation method thereof | |
| CN105126852A (en) | Dynamic ferrate oxygen storage material and application of dynamic ferrate oxygen storage material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |