CN103055876B - Preparation method of wide-temperature methanation catalyst - Google Patents
Preparation method of wide-temperature methanation catalyst Download PDFInfo
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- CN103055876B CN103055876B CN201310023997.8A CN201310023997A CN103055876B CN 103055876 B CN103055876 B CN 103055876B CN 201310023997 A CN201310023997 A CN 201310023997A CN 103055876 B CN103055876 B CN 103055876B
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Abstract
The invention provides a preparation method of a wide-temperature methanation catalyst. The wide-temperature methanation catalyst comprises the following components in percentage by mass: 5-75% of a carrier, 10-90% of NiO as an active constituent and 1-50% of a metal oxide adjuvant. In the preparation method, the wide-temperature methanation catalyst is obtained in a way of combining a precipitation process and an impregnation method. The obtained catalyst has good methanation activity in a wide-temperate range of 260-800 DEG C, stable performance, long service life and strong practicality, so that the catalyst is suitable for the application in a diversified coal methane industry.
Description
Technical field
The present invention relates to oxycarbide methanation field, particularly wide temperature methanation catalyst of one and preparation method thereof.
Background technology
In recent years, along with international community is to the concern of global warming problem, the quickening of China's energy-saving and emission-reduction paces in addition, coal-based gaseous energy industry starts to be subject to extensive concern.Wherein, preparing methane from coal technical process has the high feature of heat utilization rate, has become an important directions of coal-based gaseous energy industry.China is vast in territory, and coal reserves is very abundant, and comparatively speaking, petroleum and natural gas reserves are very not enough.Thus, being met any particular energy source structure of China's " rich coal oil starvation weak breath " by coal gas methane, is also the effective means solving the utilization of coal in China extensive style.Methanation catalyst is one of core technology of preparing methane from coal, has important strategic importance.
At present, coal preparing natural gas is existing industrial applications device abroad, typical technology has that Shandong is strange, Top's rope and Britain DAVY, but the domestic research and development for methanation catalyst are also in the starting stage, and a considerable amount of methanation catalyst is mainly used in purifying ammonia synthesis process, is only applicable to the conversion of low concentration CO.
In Chinese patent application CN102500379A (name is called " a kind of for methanation catalyst and preparation method thereof ") and CN101391218 (name is called " a kind of coke-oven gas methanation catalyst and preparation method thereof "), the preparation method adopted is infusion process, first obtained catalyst carrier, and then the nitrate solution of impregnated activated component and auxiliary agent, through super-dry, roasting and obtained catalyst.The catalytic benefits adopting infusion process to obtain is: because methanation reaction speed is exceedingly fast, active constituent nickel should distribute and be advisable on the surface of the catalyst, infusion process be able to make Ni be distributed in carrier surface with thin-shell type, and thus catalyst light-off temperature is low, and under low temperature, catalytic activity is good; Shortcoming is: the Ni content of dipping gained catalyst is lower, and the CO being not suitable for high concentration transforms.To improve Ni content, need repeatedly flood, production operation is numerous and diverse, and the pore size distribution$ of catalyst is unreasonable, easy sintering deactivation under the condition of high temperature, high liquid to steam ratio, is not suitable for the high-temperature methanation reaction at 600 DEG C-800 DEG C.
In Chinese patent application CN102259004A (name is called " Catalysts and its preparation method for coal preparing natural gas methanator ") and CN102513116A (name is called " a kind of preparation method of thermometal methanation catalyst with high-temperature resistance "), the preparation method adopted is homogeneous chemistry precipitation process, catalytic component is mixed with the mixed solution of soluble-salt, mix with aqueous slkali and precipitation reaction occurs, again through filtrations, Washing of Filter Cake, drying, high-temperature roasting and shaping, obtain methanation catalyst.The catalytic benefits adopting coprecipitation to obtain is: each component disperses is even, and catalyst strength is high, and by force, under high temperature, catalytic activity is good for heat endurance and anti-sintering property; Shortcoming is: a large amount of active component Ni and Al
2o
3combines closely, make the Ni content being distributed in carrier surface few, thus catalyst poor activity under 260 DEG C of-400 DEG C of low temperature, and catalyst reduction temperature is high, improves difficulty and the cost of reduction.
The material synthesis gas source of coal preparing natural gas comprises catalytic gasification, ground direct gasification, underground gasification etc. are several, the CO content of different makings is different, the technique of coal preparing natural gas is also varied simultaneously, the CO concentration difference of reactor inlet is very large, therefore its hot(test)-spot temperature scope of methanation reaction of different condition is very wide, usually, between 260 DEG C-800 DEG C, need a kind of wide temperature methanation catalyst to meet the demand of this wide temperature range.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the object of the invention is to provide a kind of wide temperature methanation catalyst and preparation method thereof.
The invention provides a kind of preparation method of wide temperature methanation catalyst, wherein said wide temperature methanation catalyst comprises the metal oxide auxiliary agent of the carrier of 5%-75% quality, NiO and the 1%-50% quality as active component of 10%-90% quality, it is characterized in that, described preparation method comprises the following steps:
(A) form according to the quality of described wide temperature methanation catalyst, by mix in water a part of described active component corresponding slaine, with the corresponding slaine of the described carrier of oxide or oxide hydrate form and described metal oxide auxiliary agent, oxide or oxide hydrate, and stir to form mixed liquor, then in described mixed liquor, add precipitating reagent to make the metal ion in described mixed liquor and described precipitating reagent generation precipitation reaction, and obtain sediment;
(B) described sediment is carried out drying and high-temperature calcination, make it change corresponding composite metal oxide into;
(C) by the corresponding dissolving metal salts of the described active component of remainder in water to form solution, then on the described composite metal oxide utilizing infusion process the metal ion load of the described active component in described solution to be obtained in step (B), thus realize second time and introduce described active component; And
(D) composite metal oxide that step (C) obtains carried out drying and calcine again, obtaining finished catalyst.
In a preferred embodiment, in step (A), the mixed liquor that described precipitation reaction obtains, after aging, carry out Separation of Solid and Liquid and washes the solid that obtains with water and obtain sediment.
In a preferred embodiment, in step (B), after described sediment is carried out drying, first carry out precalcining, and then carry out described high-temperature calcination.
In a preferred embodiment, after the sediment compression molding described precalcining obtained, more described high-temperature calcination is carried out.
In a preferred embodiment, described wide temperature methanation catalyst comprises the described metal oxide auxiliary agent of the described carrier of 20%-50% quality, NiO and the 10%-30% quality as active component of 30%-60% quality.
In a preferred embodiment, described carrier is selected from Al
2o
3, TiO
2or ZrO
2.
In a further preferred embodiment, described carrier is Al
2o
3.
In a preferred embodiment, described metal oxide auxiliary agent comprises the oxide of alkaline-earth metal and the oxide of rare earth metal, wherein, described rare earth metal be selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu one or more; Described alkaline-earth metal be selected from Be, Mg, Ca, Sr and Ba one or more.
In a further preferred embodiment, described rare earth metal is La and Ce; Described alkaline-earth metal is Mg.
In a preferred embodiment, the corresponding slaine of described active component is nitrate.
In a preferred embodiment, the corresponding slaine of described metal oxide auxiliary agent is nitrate or chloride.
In a preferred embodiment, described precipitating reagent is selected from sodium carbonate, sodium acid carbonate, NaOH or sodium metaaluminate.
In a further preferred embodiment, described precipitating reagent is sodium metaaluminate.
In a preferred embodiment, the temperature of described precipitation reaction is 20-80 DEG C, and the pH value of precipitation reaction terminal is 9-10.
In a preferred embodiment, the described aging time is 0.5-3h.
In a preferred embodiment, the temperature of the drying in step (B) and step (D) is 90 DEG C-130 DEG C, and the time is 1-6h.
In a preferred embodiment, described precalcining carries out 1-4h at 400 DEG C-600 DEG C.
In a preferred embodiment, described high-temperature calcination carries out 2-12h at 800 DEG C-1000 DEG C.
In a preferred embodiment, in step (C), by flooding the 10%-40% that the active component again introduced is the active component quality total amount of described wide temperature methanation catalyst, dip time is 40-120min.
In a preferred embodiment, in step (D), described calcining again carries out 2-6h at 400 DEG C-600 DEG C.
In a preferred embodiment, described finished catalyst uses after reduction, and the condition of wherein said reduction is: temperature 550 DEG C-750 DEG C, pressure 0.05MPa-0.1MPa, air speed 200h
-1-600h
-1, time 12h-48h.
The wide temperature methanation catalyst prepared by method of the present invention had both possessed the advantage of precipitation method catalyst: under high temperature, active good, thermally-stabilised, anti-caking power is strong, and mechanical strength is high; Possess again the advantage of infusion process catalyst: light-off temperature is low, active good under low temperature.That is, the catalyst synthesized by the inventive method all has good methanation activity, catalyst performance stabilised, long service life in the wide temperature range of 260 DEG C-800 DEG C, is adapted at diversified preparing methane from coal commercial Application, practical.
Detailed description of the invention
For methanation catalyst, Catalyst for Low-Temperature Methanation Ni content is lower, is generally 10%-30%, and high-temperature methanation catalyst Ni content is higher, is generally 20%-75%.Active component Ni is generally combined with catalyst carrier by infusion process or the precipitation method.Methanation reaction is exceedingly fast due to reaction speed, and interior diffusion process is slow, and active constituent nickel should distribute and be advisable on the surface of the catalyst.Adopt the catalyst prepared of infusion process that active constituent Ni be able to be made to be distributed in carrier surface thinly, and Ni is very weak with carrier-bound strength, makes catalyst light-off temperature low, the methanation reaction under applicable low temperature.But the Ni content of gained catalyst is lower, to improve Ni content, need repeatedly flood, production operation is numerous and diverse, and cost is also higher, and catalyst has a large amount of nitrogen oxide to release in preparation process, contaminated environment, and the pore size distribution$ of catalyst is unreasonable, the long-time activity that uses easily reduces, and the heat endurance of catalyst is poor.
The active constituent Ni of the catalyst adopting coprecipitation to obtain can form uniform thing phase with aluminium oxide, is conducive to Ni at Al
2o
3on dispersion.After high-temperature calcination, active component nickel mainly exists with the form of nickel aluminate, makes nickel more and body contacts, and active force is very strong, and thus nickel aluminate reduction temperature is high, and the nickel in catalyst is difficult to Restore All out, causes waste.But after metallic nickel restores from spinelle, General Decentralized is very even, decentralization is high, and grain size is little, active high, is not easy sintering deactivation under the condition of high temperature, high liquid to steam ratio, and anti-caking power is very strong, is applicable to being applied in high-temperature methanation reaction.Meanwhile, the nickel aluminate that reduction phase does not restore also can, along with the carrying out of high-temperature methanation reaction, utilize the reducibility gas in process gas to be reduced into nickel gradually, makes the high activity that catalyst at high temperature can keep for a long time.In addition, nickel aluminate catalytic mechanical intensity is good, is conducive to extending catalyst service life.
Given this, the mode that the present invention adopts the precipitation method and infusion process to combine prepares methanation catalyst.First fix a large amount of active component Ni and other metal promoter by the precipitation method, then by infusion process, second time introduces active component Ni.Gained catalyst, had both possessed the advantage of precipitation method catalyst: active good under high temperature, and by force, mechanical strength is high, possesses again the advantage of infusion process catalyst: light-off temperature is low for heat endurance and anti-sintering property, active good under low temperature.Namely under gained catalyst is applicable to wide temperature, methanation operates, and achieves beyond thought effect.In coal preparing natural gas commercial Application, be not only applicable to the methanation reaction of one section of high temperature height CO concentration, maximum temperature is 600 DEG C-800 DEG C, be applicable to two sections of methanation reactions too, maximum temperature is 500 DEG C-600 DEG C, and three sections of low temperature methanation reactions, temperature range 260 DEG C-400 DEG C.
For this reason, the preparation method of a kind of wide temperature methanation catalyst of the present invention, mainly comprises:
First, quality according to carrier, active component and metal promoter in finished catalyst forms, by the corresponding slaine of the described carrier and described metal oxide auxiliary agent that mix the corresponding slaine of a part of described active component, oxide or oxide hydrate form in water such as deionized water, oxide or oxide hydrate, and stir to form mixed liquor, under liquid-phase condition, carry out precipitation reaction with precipitating reagent to obtain sediment.Then, described sediment is carried out drying and high-temperature calcination, make it change corresponding composite metal oxide into;
Then, by the corresponding dissolving metal salts of the described active component of remainder in water to form solution, then utilize infusion process by the metal ion load of described active component on the described composite metal oxide obtained above, thus realize introducing described active component for the second time; And
Finally, after dipping terminates, drying, then calcine, namely obtain finished catalyst.
In the present invention, described wide temperature methanation catalyst comprises carrier, active component and metal oxide auxiliary agent, and each constituent mass percentage composition is: the carrier of 5%-75%, the NiO as active component of 10%-90%, the metal oxide auxiliary agent of 1%-50%; Preferably, the carrier of 20%-50%, the metal oxide auxiliary agent of the NiO of 30%-60%, 10%-30%.
Support selected from alumina Al
2o
3, titanium oxide TiO
2or zirconia ZrO
2; Be preferably aluminium oxide Al
2o
3.
Metal oxide auxiliary agent comprises the oxide of alkaline-earth metal and the oxide of rare earth metal.Particularly rare earth metal be selected from scandium Sc, yttrium Y, lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, lutetium Lu one or more; Be preferably lanthanum La and cerium Ce; Alkaline-earth metal be selected from beryllium Be, magnesium Mg, calcium Ca, strontium Sr and barium Ba one or more; ; Be preferably magnesium Mg.
More specifically or alternatively, preparation method according to a kind of wide temperature methanation catalyst of a preferred embodiment of the present invention comprises the following steps: the quality according to finished catalyst forms, by dropping into the slaine or oxide that correspond to described carrier, described active component and described metal oxide auxiliary agent in water respectively, form mixed liquor I; According to the alkali number required for mixed liquor I intermediate ion precipitation, be mixed with precipitant solution II; Mixed liquor I and precipitant solution II are carried out precipitation reaction at 20-80 DEG C, and precipitation process fully stirs, and the pH value of precipitation reaction terminal is 9-10, and this is for introducing active component for the first time; After aging for the mixed liquor after precipitation reaction 0.5-3h, carry out Separation of Solid and Liquid and wash with water; By clean after sediment dry 1-6h at 90 DEG C-130 DEG C; Compression molding carry out precalcining 1-4h at 400 DEG C-600 DEG C after; High-temperature calcination 2-12h at 800 DEG C-1000 DEG C again, makes it change corresponding composite metal oxide into; According to the requirement of the required active component content of dipping, by amount of calculation, corresponding activity component metal salt is dissolved in corresponding water, be made into maceration extract III, 40-120min is flooded under normal temperature, by active constituent loading on the composite metal oxide of high-temperature calcination gained, this, for introducing active component for the second time, accounts for the 10%-40% of catalyst activity component total amount; After dipping terminates, dry 1-6h at 90 DEG C-130 DEG C, calcines 2-6h again at 400 DEG C-600 DEG C, obtains finished catalyst.Finished catalyst uses after reduction, and reducing condition is: temperature 550 DEG C-750 DEG C, pressure 0.05MPa-0.1MPa, air speed 200h
-1-600h
-1, time 12h-48h.
Precipitating reagent of the present invention is selected from sodium carbonate, sodium acid carbonate, NaOH or sodium metaaluminate, preferred sodium metaaluminate, reason is when using sodium metaaluminate, introduce the aluminium of a part in precipitating reagent simultaneously, make to be deposited in whole precipitation reaction process and occur equably, the product obtained is more homogeneous, can overcome the fault of construction in high-temperature calcinations step further.The pH value that the present invention controls precipitation reaction terminal is 9-10, and reason under this pH value, is conducive to catalyst activity component nickel precipitation completely, and the alkalescence of this precipitating reagent sodium salt is strong, and easy control ph by nickel precipitation completely.Ageing time 0.5-3h suitable after precipitation reaction is conducive to sedimentary crystallization.
Calcining heat has impact to catalyst structure, such as, about 500 DEG C calcining generate be nickel oxide, and more than 1000 DEG C calcining generate be nickel aluminate.Methanation is a strong exothermic process, generates a large amount of water simultaneously, and this just requires that catalyst has very strong high temperature resistant and resistance to hydration performance.Experimental results demonstrate, through the obtained catalyst of about 500 DEG C calcinings at high temperature carrier there is hydration reaction, structural collapse, catalytic activity sharply declines, and shows only by Al
2o
3it is inadequate that carrier plays stabilization to the dispersion of Ni to active component, needs the nickel aluminate structure having very high stability under high-temperature water heat condition.
Nickel aluminate is in the process of high-temperature calcination, is generally more than 1000 DEG C, and nickel progressively defines a kind of uniform solid by solid phase reaction and diffusion with aluminium oxide, chemical molecular formula is NiAl
2o
4, belong to cubic system.The reduction temperature of nickel aluminate is higher, is more difficultly reduced, illustrate active component and carrier adhesion large.After metallic nickel restores from spinelle, General Decentralized degree is high, and grain size is little, and catalytic activity is good, under the condition of high temperature, high liquid to steam ratio, be not easy sintering deactivation.In addition, nickel aluminate mechanical strength is good, Stability Analysis of Structures, is conducive to the life-span of improving catalyst.
In general the catalyst of more than 1000 DEG C calcinings, just can need be reduced, and the growing amount of nickel aluminate and initial reduction temperature all raises with the rising of calcining heat more than 700 DEG C.From nickel aluminate growing amount, calcining heat is more high better, but from reduction complexity, calcining heat is low more favourable.Therefore consider, high-temperature calcinations step temperature of the present invention controls at 800 DEG C-1000 DEG C.
The preferred catalyst preparing scheme of the present invention one, the step of precalcining is added further after drying precipitate, precalcining 1-4h is carried out at 400 DEG C-600 DEG C, object is that the Substance Transformation in products obtained therefrom is become oxide, can prevent so shaping after catalyst high-temperature calcination crack.
Catalyst promoter of the present invention comprises alkaline earth oxide and rare-earth oxide.The activity of methanation catalyst and stability depend on the decentralization of nickel and anti-caking power to a great extent.Methanation reaction is a strong exothermal reaction, and temperature is higher, and the speed of metallic nickel grain growth is faster.Therefore nickel crystallite is thinner, catalytic activity is higher, and along with the carrying out of methanation reaction, if size of nickel crystallite can be stablized in corresponding maintenance, activity also can keep stable.Alkaline earth oxide and adding of rare-earth oxide make Ni grain refinement, and add the decentralization of Ni on carrier, the crystal grain of Ni diminishes, thus catalytic activity is improved.In catalytic reaction process, unnecessary electric charge can shift to Ni, increases the charge density of Ni, suitably increases the storage of Ni catalyst surface and stays H
2ability, and by electrical feedback, weaken C-O key, make its more easy fracture, promote dissociation and the disproportionation of CO, accelerate the carrying out of methanation reaction; On the other hand, the nickel crystallite that the existence of alkaline-earth metal and rare earth metal can suppress catalyst in use to cause because of the effect of being heated again is grown up and sinters, and catalyst thermal stability is good.
In addition, adding of alkaline-earth metal can affect catalyst surface acidity, effectively prevents the generation of carbon deposition phenomenon in course of reaction.The preferred element magnesium of alkaline-earth metal, owing to defining the structure of magnesium aluminate spinel with aluminium, prevent the generation of structure of similar to thin diaspore, catalyst hydration-resisting is functional.
Therefore, co-catalyst alkaline earth oxide of the present invention and rare-earth oxide adding in methanation catalyst, effective raising nickel dispersity, in suppression course of reaction, nickel crystallite grows up and sinters, make catalyst continue after a long time use to keep high activity and good thermal stability, and catalyst hydration-resisting, anti-carbon are functional.
The present invention has but is not limited to the advantage of following many aspects:
1. the mode adopting the precipitation method and infusion process to combine prepares wide temperature methanation catalyst, and gained catalyst light-off temperature is low, and active good under high temperature, heat endurance is strong, is adapted at applying in the preparing methane from coal industry of diversified wide temperature range.
2., when the precipitating reagent in precipitation reaction uses sodium metaaluminate, in precipitating reagent, introduce the aluminium of a part, precipitation is occurred equably, and product is more homogeneous; The pH value controlling precipitation reaction terminal is 9-10, and active component nickel precipitates pH scope completely just.
3. when first carrying out precalcining after to drying, can prevent shaping after the direct high-temperature calcination of catalyst crack; And high-temperature calcination generating nickel aluminate structure, this construction machine intensity is high, has very strong stability under high hydrothermal condition.
4. add alkaline earth oxide and rare-earth oxide auxiliary agent, add the decentralization of Ni on carrier, resist the nickel crystallite caused that is heated and grow up and sinter, can also effectively prevent carbon distribution and hydration reaction.
In the present invention, have employed following analysis test method:
1. adopt the specific area of U.S. Merck & Co., Inc ASAP2020M device mensuration catalyst, pore volume, aperture;
2. adopt Rigaku D/max-2200PC X-ray diffraction analysis catalyst thing phase;
3. adopt U.S. PE company Optima2100DV inductively coupled plasma spectral emissions instrument analysis of catalyst tenor;
4. adopt U.S. Agilent company 6890N gas chromatographic analysis product composition;
5. adopt ZQJ-II Intelligent testing machine for particle to detect mechanical strength;
6. adopt Merck & Co., Inc of U.S. AUTO CHEMII2920 to carry out Catalyst for CO Characterization of Adsorption;
7. adopt German Nai Chi company STA449F3 thermal analyzer to carry out thermogravimetric analysis.
Below by the mode of embodiment, the present invention will be further described, should be appreciated that to be only preferred embodiment of the present invention below, can not limit scope of the present invention with this.I.e. every change of doing according to the present patent application the scope of the claims and modification, all belongs in scope that patent of the present invention contains.
Embodiment 1
The wide temperature methanation catalyst of following quality composition is prepared: carrier A l by the inventive method
2o
3: 45%; Active component NiO:10%; Metal oxide auxiliary agent: 45% (wherein MgO:15%, CaO:10%, SrO:10%, Nd
2o
3: 4%, Y
2o
3: 6%).
Take the Nickelous nitrate hexahydrate of 28kg, the six nitric hydrate neodymiums of 10.5kg, the six nitric hydrate yttriums of 20.3kg, join in 173L water, abundant stirring is until dissolve completely, drop into 15kg light magnesium oxide, 13.2kg calcium hydroxide, 11.7kg strontium hydroxide, 64.3kg boehmite again, fully stir and form mixed liquor I; Take the NaOH of 16.94kg, by the water-soluble solution of 56L, be mixed with precipitant solution II; Mixed liquor I and precipitant solution II are carried out precipitation reaction at 60 DEG C, and precipitation process fully stirs, and the pH value of precipitation reaction terminal is 9, and this is for introducing active component for the first time; After aging for the mixed liquor after precipitation reaction 2h, carry out Separation of Solid and Liquid and wash with water; By clean after sediment dry 6h at 120 DEG C; Compression molding after precalcining 4h is carried out at 550 DEG C; High-temperature calcination 12h at 800 DEG C again, makes it change corresponding composite metal oxide into; Take 32.67kg Nickelous nitrate hexahydrate, be dissolved in 24.5L water, be made into maceration extract III, flood 90 minutes under normal temperature, by active constituent loading on high-temperature calcination products therefrom, this, for introducing active component for the second time, accounts for 28% of catalyst activity component total amount.After dipping terminates, dry 6h at 130 DEG C, calcines 2h again, namely obtains finished catalyst at 550 DEG C.Finished catalyst uses after reduction, and reducing condition is: temperature 550 DEG C, pressure 0.07MPa, air speed 200h
-1, time 32h.
Embodiment 2
The wide temperature methanation catalyst of following quality composition is prepared: carrier ZrO2:5% by the inventive method; Active component NiO:85%; Metal oxide auxiliary agent: 10% (wherein BaO:8%, Sm
2o
3: 1%, Gd
2o
3: 1%).
Take the Nickelous nitrate hexahydrate of 274.7kg, the six chloride hydrate samariums of 2.0kg, the gadolinium nitrate hexahydrate of 2.4kg, join in 955L water, fully stir until dissolve completely, then drop into 8.0kg barium monoxide, 5.0kg zirconia, fully stir and form mixed liquor I; Take the sodium carbonate of 101.84kg, by the water-soluble solution of 261L, be mixed with precipitant solution II; Mixed liquor I and precipitant solution II are carried out precipitation reaction at 30 DEG C, and precipitation process fully stirs, and the pH value of precipitation reaction terminal is 9.8, and this is for introducing active component for the first time; After aging for the mixed liquor after precipitation reaction 3h, carry out Separation of Solid and Liquid and wash with water; By clean after sediment dry 5h at 90 DEG C; Compression molding after precalcining 1h is carried out at 500 DEG C; High-temperature calcination 2h at 1000 DEG C again, makes it change corresponding composite metal oxide into; Take 168.79kg Nickelous nitrate hexahydrate, be dissolved in 126.6L water, be made into maceration extract III, flood 120 minutes under normal temperature, by active constituent loading on high-temperature calcination products therefrom, this, for introducing active component for the second time, accounts for 17% of catalyst activity component total amount.After dipping terminates, dry 3h at 120 DEG C, calcines 5h again, namely obtains finished catalyst at 400 DEG C.Finished catalyst uses after reduction, and reducing condition is: temperature 600 DEG C, pressure 0.05MPa, air speed 300h
-1, time 48h.
Embodiment 3
The wide temperature methanation catalyst of following quality composition is prepared: carrier A l by the inventive method
2o
3: 69%; Active component NiO:30%; Metal oxide auxiliary agent: 1% (wherein CaO:0.7%, La
2o
3: 0.3%).
Take the Nickelous nitrate hexahydrate of 105.0kg, the lanthanum nitrate hexahydrate of 0.7kg, join in 363L water, fully stir until dissolve completely, then drop into 0.9kg calcium hydroxide, 68.6kg boehmite, fully stir and form mixed liquor I; Take 29,08kg NaOH, 31.95kg boehmite, by the water-soluble solution of 97L, be mixed with sodium metaaluminate precipitant solution II; Mixed liquor I and precipitant solution II are carried out precipitation reaction at 20 DEG C, and precipitation process fully stirs, and the pH value of precipitation reaction terminal is 9.3, and this is for introducing active component for the first time; After aging for the mixed liquor after precipitation reaction 0.5h, carry out Separation of Solid and Liquid and wash with water; By clean after sediment dry 3h at 130 DEG C; Compression molding after precalcining 3h is carried out at 400 DEG C; High-temperature calcination 7h at 900 DEG C again, makes it change corresponding composite metal oxide into; Take 35.0kg Nickelous nitrate hexahydrate, be dissolved in 26.3L water, be made into maceration extract III, flood 50 minutes under normal temperature, by active constituent loading on high-temperature calcination products therefrom, this, for introducing active component for the second time, accounts for 10% of catalyst activity component total amount.After dipping terminates, dry 5h at 90 DEG C, calcines 6h again, namely obtains finished catalyst at 500 DEG C.Finished catalyst uses after reduction, and reducing condition is: temperature 750 DEG C, pressure 0.1MPa, air speed 400h
-1, time 24h.
Embodiment 4
The wide temperature methanation catalyst of following quality composition is prepared: carrier TiO by the inventive method
2: 20%; Active component NiO:55%; Metal oxide auxiliary agent: 25% (wherein MgO:16%, BaO:4%, Ce
2o
3: 5%).
Take the six nitric hydrate ceriums of the Nickelous nitrate hexahydrate of 128.5kg, 12.5kg, join in 471L water, fully stir until dissolve completely, then drop into 16.0kg light magnesium oxide, 4.0kg barium monoxide, 20.0kg titanium oxide, fully stir and form mixed liquor I; Take the sodium acid carbonate of 81.5kg, by the water-soluble solution of 136L, be mixed with precipitant solution II; Mixed liquor I and precipitant solution II are carried out precipitation reaction at 80 DEG C, and precipitation process fully stirs, and the pH value of precipitation reaction terminal is 10, and this is for introducing active component for the first time; After aging for the mixed liquor after precipitation reaction 1.5h, carry out Separation of Solid and Liquid and wash with water; By clean after sediment dry 1h at 100 DEG C; Compression molding after precalcining 3.5h is carried out at 450 DEG C; High-temperature calcination 5h at 850 DEG C again, makes it change corresponding composite metal oxide into; Take 257.0kg Nickelous nitrate hexahydrate, be dissolved in 192.8L water, be made into maceration extract III, flood 40 minutes under normal temperature, by active constituent loading on high-temperature calcination products therefrom, this, for introducing active component for the second time, accounts for 40% of catalyst activity component total amount.After dipping terminates, dry 1h at 100 DEG C, calcines 3h again, namely obtains finished catalyst at 600 DEG C.Finished catalyst uses after reduction, and reducing condition is: temperature 650 DEG C, pressure 0.08MPa, air speed 600h
-1, time 12h.
Embodiment 5
The wide temperature methanation catalyst of following quality composition is prepared: carrier A l by the inventive method
2o
3: 35%; Active component NiO:40%; Metal oxide auxiliary agent: 25% (wherein MgO:19%, La
2o
3: 5%, Ce
2o
3: 1%).
Take the Nickelous nitrate hexahydrate of 124.7kg, the lanthanum nitrate hexahydrate of 13.3kg, the six nitric hydrate ceriums of 2.5kg, join in 465L water, abundant stirring until dissolve completely, then drops into 19kg light magnesium oxide, 10.5kg boehmite, fully stirs and forms mixed liquor I; Take 38.68kg NaOH, 42.51kg boehmite, by the water-soluble solution of 129L, be mixed with sodium metaaluminate precipitant solution II, mixed liquor I and precipitant solution II are carried out precipitation reaction at 40 DEG C, precipitation process fully stirs, the pH value of precipitation reaction terminal is 9.6, and this is for introducing active component for the first time; After aging for the mixed liquor after precipitation reaction 1h, carry out Separation of Solid and Liquid and wash with water; By clean after sediment dry 4h at 110 DEG C; Compression molding after precalcining 2.5h is carried out at 600 DEG C; High-temperature calcination 3h at 950 DEG C again, makes it change corresponding composite metal oxide into; Take 93.53kg Nickelous nitrate hexahydrate, be dissolved in 70.1L water, be made into maceration extract III, flood 60 minutes under normal temperature, by active constituent loading on high-temperature calcination products therefrom, this, for introducing active component for the second time, accounts for 20% of catalyst activity component total amount.After dipping terminates, dry 4h at 110 DEG C, calcines 4h again, namely obtains finished catalyst at 550 DEG C.Finished catalyst uses after reduction, and reducing condition is: temperature 700 DEG C, pressure 0.08MPa, air speed 500h
-1, time 40h.
Comparative example 1
The wide temperature methanation catalyst of following quality composition is prepared: carrier A l by the inventive method
2o
3: 35%; Active component NiO:40%; Metal oxide auxiliary agent: 25% (wherein MgO:19%, La
2o
3: 5%, Ce
2o
3: 1%).This comparative example is distinguished with the preparation method of embodiment 5 and is: only introduced the active component in catalyst by the mode precipitated.
Take the Nickelous nitrate hexahydrate of 155.7kg, the lanthanum nitrate hexahydrate of 13.3kg, the six nitric hydrate ceriums of 2.5kg, join in 572L water, abundant stirring until dissolve completely, then drops into 19.0kg light magnesium oxide, 2.6kg boehmite, fully stirs and forms mixed liquor I; Take 47.21kg NaOH, 51.88kg boehmite, by the water-soluble solution of 157L, be mixed with sodium metaaluminate precipitant solution II, mixed liquor I and precipitant solution II are carried out precipitation reaction at 40 DEG C, precipitation process fully stirs, the pH value of precipitation reaction terminal is 9.6, and this is for uniquely once to introduce active component; After aging for the mixed liquor after precipitation reaction 1h, carry out Separation of Solid and Liquid and wash with water; By clean after sediment dry 4h at 110 DEG C; Compression molding after precalcining 2.5h is carried out at 600 DEG C; High-temperature calcination 3h at 950 DEG C again, makes it change corresponding composite metal oxide into, namely obtains finished catalyst.Finished catalyst uses after reduction, and reducing condition is: temperature 700 DEG C, pressure 0.08MPa, air speed 500h
-1, time 40h.
Comparative example 2
The wide temperature methanation catalyst of following quality composition is prepared: carrier A l by the inventive method
2o
3: 63%; Active component NiO:12%; Metal oxide auxiliary agent: 25% (wherein MgO:19%, La
2o
3: 5%, Ce
2o
3: 1%).This comparative example is distinguished with the preparation method of embodiment 5 and is: only introduced the active component in catalyst by the mode of flooding.
Take the six nitric hydrate ceriums of the lanthanum nitrate hexahydrate of 13.3kg, 2.5kg, join in 36.5L water, fully stir until dissolve completely, then drop into 19kg light magnesium oxide, 85.4kg boehmite, fully stir and form mixed liquor I; Take 4.38kg NaOH, 4.81kg boehmite, by the water-soluble solution of 14.6L, be mixed with sodium metaaluminate precipitant solution II, mixed liquor I and precipitant solution II are carried out precipitation reaction at 40 DEG C, precipitation process fully stirs, and the pH value of precipitation reaction terminal is 9.6; After aging for the mixed liquor after precipitation reaction 1h, carry out Separation of Solid and Liquid and wash with water; By clean after sediment dry 4h at 110 DEG C; Compression molding after precalcining 2.5h is carried out at 600 DEG C; High-temperature calcination 3h at 950 DEG C again, makes it change corresponding composite metal oxide into; Take 140.1kg Nickelous nitrate hexahydrate, be dissolved in 105L water, be made into maceration extract III, flood 60 minutes under normal temperature, by active constituent loading on high-temperature calcination products therefrom, this is for uniquely once to introduce active component, accounts for 100% of catalyst activity component total amount.After dipping terminates, dry 4h at 110 DEG C, calcines 4h again, namely obtains finished catalyst at 550 DEG C.Finished catalyst uses after reduction, and reducing condition is: temperature 700 DEG C, pressure 0.08MPa, air speed 500h
-1, time 40h.
Comparative example 3
The wide temperature methanation catalyst of following quality composition is prepared: carrier A l by the inventive method
2o
3: 35%; Active component NiO:40%; Metal oxide auxiliary agent: 25% (wherein MgO:19%, La
2o
3: 5%, Ce
2o
3: 1%).This comparative example is distinguished with the preparation method of embodiment 5 and is: the catalyst after shaping is without high-temperature calcination.
Take the Nickelous nitrate hexahydrate of 124.7kg, the lanthanum nitrate hexahydrate of 13.3kg, the six nitric hydrate ceriums of 2.5kg, join in 465L water, abundant stirring until dissolve completely, then drops into 19kg light magnesium oxide, 10.5kg boehmite, fully stirs and forms mixed liquor I; Take 38.68kg NaOH, 42.51kg boehmite, by the water-soluble solution of 129L, be mixed with sodium metaaluminate precipitant solution II, mixed liquor I and precipitant solution II are carried out precipitation reaction at 40 DEG C, precipitation process fully stirs, the pH value of precipitation reaction terminal is 9.6, and this is for introducing active component for the first time; After aging for the mixed liquor after precipitation reaction 1h, carry out Separation of Solid and Liquid and wash with water; By clean after sediment dry 4h at 110 DEG C; Compression molding after precalcining 2.5h is carried out at 600 DEG C; Take 93.53kg Nickelous nitrate hexahydrate, be dissolved in 70.1L water, be made into maceration extract III, flood 60 minutes under normal temperature, by active constituent loading on high-temperature calcination products therefrom, this, for introducing active component for the second time, accounts for 20% of catalyst activity component total amount.After dipping terminates, dry 4h at 110 DEG C, calcines 4h again, namely obtains finished catalyst at 550 DEG C.Finished catalyst uses after reduction, and reducing condition is: temperature 700 DEG C, pressure 0.08MPa, air speed 500h
-1, time 40h.
Comparative example 4
The wide temperature methanation catalyst of following quality composition is prepared: carrier A l by the inventive method
2o
3: 47%; Active component NiO:53%.This comparative example is distinguished with the preparation method of embodiment 5 and is: catalyst does not contain the composition of alkaline earth oxide or rare-earth oxide auxiliary agent.
Take the Nickelous nitrate hexahydrate of 165kg, join in 567L water, fully stir until dissolve completely, then drop into 20.2kg boehmite, fully stir and form mixed liquor I; Take 45.39kg NaOH, 49.88kg boehmite, by the water-soluble solution of 151L, be mixed with sodium metaaluminate precipitant solution II, mixed liquor I and precipitant solution II are carried out precipitation reaction at 40 DEG C, precipitation process fully stirs, the pH value of precipitation reaction terminal is 9.6, and this is for introducing active component for the first time; After aging for the mixed liquor after precipitation reaction 1h, carry out Separation of Solid and Liquid and wash with water; By clean after sediment dry 4h at 110 DEG C; Compression molding after precalcining 2.5h is carried out at 600 DEG C; High-temperature calcination 3h at 950 DEG C again, makes it change corresponding composite metal oxide into; Take 123.75kg Nickelous nitrate hexahydrate, be dissolved in 92.8L water, be made into maceration extract III, flood 60 minutes under normal temperature, by active constituent loading on high-temperature calcination products therefrom, this, for introducing active component for the second time, accounts for 20% of catalyst activity component total amount.After dipping terminates, dry 4h at 110 DEG C, calcines 4h again, namely obtains finished catalyst at 550 DEG C.Finished catalyst uses after reduction, and reducing condition is: temperature 700 DEG C, pressure 0.08MPa, air speed 500h
-1, time 40h.
Evaluation test
Each catalyst of embodiment 1-5 and comparative example 1-4 is carried out activity rating, and before and after activity rating, X-ray diffraction (XRD), physical absorption, chemisorbed, mechanical strength and thermogravimetric analysis is carried out to each catalyst.Concrete activity rating method:
Loaded by finished catalyst in fixed bed reactors, after reduction, first carry out low temperature active evaluation, condition is: unstripped gas is oven gas, and inlet temperature is 280 DEG C, and outlet temperature controls at 350 DEG C, and reaction pressure is 2MPa, air speed 6000h
-1, measure CO conversion ratio and CO
2conversion ratio.After low temperature active evaluation continues 50h, carry out high temperature active evaluation, condition is: maintain reaction pressure and air speed constant, controlling outlet temperature is 650 DEG C, continues 450h, measures CO conversion ratio and CO
2conversion ratio.Evaluation and characterization result are as shown in following table 1 and table 2.
It is to be noted that embodiment 5 forms similar to each catalyst of comparative example 1-4, only preparation method is different, and the evaluation of these 5 catalyst and the contrast of characterization result are in table 2.
Table 1
Table 2
The data of above embodiment and comparative example can be found out, catalyst of the present invention have employed the mode that the precipitation method and infusion process combine to be prepared (embodiment 1-5), under low temperature and hot conditions, all there is good activity, and heat endurance and anti-sintering property are by force, and mechanical strength is high.
Investigate from preparation method, under catalyst (comparative example 1) high temperature only adopting the precipitation method to prepare, activity and stability are by force, but low temperature active is poor.Catalyst (comparative example 2) light-off temperature only adopting infusion process to prepare is low, active good under low temperature, but catalyst poor heat stability, easy sintering deactivation.
(embodiment 1-5) is investigated from sintering temperature, sintering temperature is high, in catalyst, nickel aluminate content is just high, high hydrothermal condition stability inferior is stronger, and do not carry out the catalyst (comparative example 2-3) of high-temperature calcination, at high temperature react, easily cause hydration and pulverization, structural collapse, catalytic activity sharply declines.
Investigate from the effect of rare earth metal and base earth metal promoter, with the addition of the catalyst (embodiment 1-5) of metal promoter, auxiliary agent can suppress growing up and sintering of nickel crystallite in course of reaction, effectively can also prevent carbon distribution, keep high activity and the heat endurance of long-lasting catalytic, and do not add the catalyst (comparative example 4) of metal promoter, catalyst generation carbon distribution, simultaneously with activity decrease.
It should be pointed out that the professional and technical personnel for making the art, under the prerequisite not departing from the technology of the present invention principle, is what can realize the multiple amendment of these embodiments, and these amendments also should be considered as in the scope that the present invention should protect.
Claims (17)
1. the preparation method of one kind wide temperature methanation catalyst, wherein said wide temperature methanation catalyst comprises the metal oxide auxiliary agent of the carrier of 20%-50% quality, NiO and the 10%-30% quality as active component of 30%-60% quality, and described wide temperature methanation catalyst has methanation activity in the wide temperature range of 260 DEG C-800 DEG C, it is characterized in that, described preparation method comprises the following steps:
(A) form according to the quality of described wide temperature methanation catalyst, by mix in water a part of described active component corresponding slaine, with the corresponding slaine of the described carrier of oxide or oxide hydrate form and described metal oxide auxiliary agent, oxide or oxide hydrate, and stir to form mixed liquor, then in described mixed liquor, add precipitating reagent to make the metal ion in described mixed liquor and described precipitating reagent generation precipitation reaction, and obtain sediment;
(B) described sediment is carried out drying and high-temperature calcination, make it change corresponding composite metal oxide into;
(C) by the corresponding dissolving metal salts of the described active component of remainder in water to form solution, then on the described composite metal oxide utilizing infusion process the metal ion load of the described active component in described solution to be obtained in step (B), thus realize second time and introduce described active component; And
(D) composite metal oxide that step (C) obtains carried out drying and calcine again, obtaining finished catalyst,
And in step (B), after described sediment is carried out drying, first carry out precalcining, and then carry out described high-temperature calcination, described precalcining carries out 1-4h at 400 DEG C-600 DEG C, and described high-temperature calcination carries out 2-12h at 800 DEG C-1000 DEG C.
2. method according to claim 1, is characterized in that, in step (A), the mixed liquor that described precipitation reaction obtains carries out Separation of Solid and Liquid after aging, and washes the solid that obtains with water and obtain sediment.
3. method according to claim 1, is characterized in that, after the sediment compression molding described precalcining obtained, then carries out described high-temperature calcination.
4. the preparation method according to any one of claim 1-3, is characterized in that, described carrier is selected from Al
2o
3, TiO
2or ZrO
2.
5. the preparation method according to any one of claim 1-3, is characterized in that, described carrier is Al
2o
3.
6. the preparation method according to any one of claim 1-3, it is characterized in that, described metal oxide auxiliary agent comprises the oxide of alkaline-earth metal and the oxide of rare earth metal, wherein, described rare earth metal be selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu one or more; Described alkaline-earth metal be selected from Be, Mg, Ca, Sr and Ba one or more.
7. preparation method according to claim 6, is characterized in that, described rare earth metal is La and Ce; Described alkaline-earth metal is Mg.
8. the preparation method according to any one of claim 1-3, is characterized in that, the corresponding slaine of described active component is nitrate.
9. the preparation method according to any one of claim 1-3, is characterized in that, the corresponding slaine of described metal oxide auxiliary agent is nitrate or chloride.
10. the preparation method according to any one of claim 1-3, is characterized in that, described precipitating reagent is selected from sodium carbonate, sodium acid carbonate, NaOH or sodium metaaluminate.
11. preparation methods according to any one of claim 1-3, it is characterized in that, described precipitating reagent is sodium metaaluminate.
12. preparation methods according to any one of claim 1-3, it is characterized in that, the temperature of described precipitation reaction is 20-80 DEG C, and the pH value of precipitation reaction terminal is 9-10.
13. preparation methods according to claim 2, is characterized in that, the described aging time is 0.5-3h.
14. preparation methods according to any one of claim 1-3, it is characterized in that, the temperature of the drying in step (B) and step (D) is 90 DEG C-130 DEG C, and the time is 1-6h.
15. preparation methods according to any one of claim 1-3, it is characterized in that, in step (C), by flooding the 10%-40% that the active component again introduced is the active component quality total amount of described wide temperature methanation catalyst, dip time is 40-120min.
16. preparation methods according to any one of claim 1-3, it is characterized in that, in step (D), described calcining again carries out 2-6h at 400 DEG C-600 DEG C.
17. preparation methods according to any one of claim 1-3, is characterized in that, described finished catalyst uses after reduction, and the condition of wherein said reduction is: temperature 550 DEG C-750 DEG C, pressure 0.05MPa-0.1MPa, air speed 200h
-1-600h
-1, time 12h-48h.
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| CN104857964A (en) * | 2014-02-26 | 2015-08-26 | 天津大学 | Synthetic gas methanation catalyst and preparation method thereof |
| CN103831109B (en) * | 2014-03-13 | 2015-12-09 | 华烁科技股份有限公司 | A kind of pollution-free preparation process of wide temperature coal preparing natural gas methanation catalyst |
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| CN106732620B (en) * | 2015-11-23 | 2020-02-14 | 中国石油天然气股份有限公司 | Nickel series hydrogenation catalyst and preparation method thereof |
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| CN108620138A (en) * | 2017-03-15 | 2018-10-09 | 单岩崑 | A kind of natural gas catalysis oxidation catalyst for preparing synthesized gas carrier and its method of modifying |
| CN108855129B (en) * | 2017-05-15 | 2021-04-30 | 中国石油天然气股份有限公司 | Nickel-silver hydrogenation catalyst and preparation method thereof |
| CN108855128B (en) * | 2017-05-15 | 2021-04-30 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst and preparation method thereof |
| CN108295857A (en) * | 2018-02-07 | 2018-07-20 | 福州大学 | A kind of Ni-based methanation catalyst of high stability 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 |
| CN110252363A (en) * | 2019-06-25 | 2019-09-20 | 北京三聚环保新材料股份有限公司 | A kind of Ni-based methanation catalyst and preparation method thereof and application |
| CN112517019A (en) * | 2020-12-17 | 2021-03-19 | 大唐国际化工技术研究院有限公司 | By TiO2Methanation catalyst with aerogel as carrier and preparation method and application thereof |
| CN113262790A (en) * | 2021-04-29 | 2021-08-17 | 盘锦迪宝催化剂技术有限公司 | Catalyst for preparing synthesis gas by dry conversion of carbon dioxide and methane and preparation method thereof |
| CN113499780A (en) * | 2021-06-15 | 2021-10-15 | 中石化南京化工研究院有限公司 | Low-nickel high-activity methanation catalyst and preparation method thereof |
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