CN103084174A - Methanation catalyst for carbon oxide removing, preparation method and applications thereof - Google Patents
Methanation catalyst for carbon oxide removing, preparation method and applications thereof Download PDFInfo
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- CN103084174A CN103084174A CN2011103326555A CN201110332655A CN103084174A CN 103084174 A CN103084174 A CN 103084174A CN 2011103326555 A CN2011103326555 A CN 2011103326555A CN 201110332655 A CN201110332655 A CN 201110332655A CN 103084174 A CN103084174 A CN 103084174A
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Abstract
The invention provides a methanation catalyst for carbon oxide removing, a preparation method and applications thereof. According to the present invention, active components of the catalyst are prepared through a microemulsion method, and are loaded on a carrier, and the prepared main active component Ru of the catalyst has characteristics of small particle size, narrow distribution and good dispersion, wherein the particle size is less than 50 nm; the catalyst preparation method has characteristics of simpleness, mild operation condition and easy production; and with application of the catalyst in a methanation reaction for carbon oxide removing, high activity and high selectivity are provided.
Description
Technical field
The present invention relates to a kind of methanation catalyst that removes carbon oxides in gas and its preparation method and application.Be exactly specifically a kind of support type methanation nanocatalyst of microemulsion technology preparation take ruthenium (Ru) as main active component that utilize, this catalyst is used for removing the oxycarbide of gas.
Background technology
Trace amounts of oxycarbide (CO/CO in hydrogen-rich gas
2) to remove be generally to adopt methanation process to realize, namely pass through CO/CO
2Hydrogenation generates CH
4And H
2O and removing.Methanation process is widely used in ethylene unit and synthetic ammonia installation, and the purifying of current fuel cell hydrogen raw material is also one of important research direction of methanation, and purpose is all to remove trace amounts of CO gas in hydrogen-rich gas, for downstream process provides high-purity hydrogen.
US20070253893 discloses a kind of CO and has selected the methanation ruthenium catalyst, and this patent has at length been studied carried metal content, catalyst preparation and preprocess method, the impact of the factors such as carrier.For 3%Ru/Al
2O
3Catalyst is at air speed 13500h
-1, under 240～285 ℃ of conditions of temperature, after reaction, the CO exit concentration is less than 100ppm.
US7560496 discloses a kind of serviceability temperature wide ranges, high selectivity and active CO methanation catalyst, and with Ru, Rh, Ni, Co are active component, carrier is active carbon, is used for the purifying in fuel cell hydrogen source.
Show the characteristics such as quantum size effect, bulk effect, surface and interface effect, quantum size tunnel-effect due to nano particle, nano-particle catalyst shows good characteristic.The method for preparing nano particle mainly comprises steam condensing method, mechanochemical reaction, sol-gel process, the precipitation method, hydro-thermal method, irradiation method, microemulsion method etc.
Microemulsion method is a kind of effective ways that prepare nano particle that grow up the eighties in 20th century, and in microemulsion system, decentralized photo is generally thermodynamic stable system.According to oil-water ratio in system and microstructure thereof, the co-continuous phase microemulsion (W/O/W) that microemulsion can be divided into positive (O/W) microemulsion, two kinds of anti-phase (W/O) microemulsions and intermediate state is the type such as (O/W/O).Generally the preparation nano particle is (W/O) microemulsion.Hybrid films by surfactant and cosurfactant form forms in oil phase in small " pond ", with this reactor as the preparation nano particle.The size of the proportion control water core by regulating microemulsion system water and surfactant.The advantages such as microemulsion method has the experiment condition gentleness, and equipment is simple, and particle diameter is controlled.
Summary of the invention
For the problems of the prior art, the purpose of this invention is to provide a kind of microemulsion technology preparation support type methanation nanocatalyst take ruthenium as main active component and its preparation method and application that utilizes.The catalyst that the method makes has higher activity and selective preferably in the situation that main active component content is lower.
One of the object of the invention is to provide a kind of methanation catalyst that removes oxycarbide, and this catalyst comprises carrier and the active component that is carried on carrier, and the active component of described catalyst is utilize the microemulsion method preparation and get.
Described carrier is Al
2O
3, SiO
2, ZrO
2, TiO
2, V
2O
5, SnO
2, at least a in SiC, kaolin, preferred Al
2O
3, SiO
2, ZrO
2, TiO
2In a kind of; The specific area of described carrier is 1～400m
2/ g, average pore size is 5～300nm, and pore volume is 0.2～1.2ml/g, and its face shaping is that tooth is spherical, granular, spherical, profile of tooth, annular, sheet, strip, clover or bunge bedstraw herb, also can use other special-shaped strip.
Described active component comprises main active component and/or helps active component;
Described main active component is simple substance Ru, and Ru content is the 0.01wt%～7.0wt% of described carrier gross weight, is preferably the 0.05wt%～5wt% of total weight of carrier, more preferably 0.1wt%～the 2.0wt% of total weight of carrier;
The described active component that helps is at least a in Ni, Fe, Ga, Pt, Cu, Sn, Ge, Zn, Cr, rare earth element, alkali metal, and content is the 0.0wt%～20.0wt% of described carrier gross weight, is preferably the 0.0wt%～10.0wt% of total weight of carrier.
The grain diameter of described main active component is less than 50nm;
In catalyst of the present invention, active component is adopt microemulsion method to prepare and get, and is carried on carrier, comprises the following steps:
(1) preparation microemulsion: in water bath with thermostatic control, the water, cosurfactant, the oil phase that are comprised of the salting liquid of non-ionic surface active agent, catalyst activity component mix in proportion, stir the stable w/o type microemulsion system of preparation, the mass ratio of each component is non-ionic surface active agent: cosurfactant: oil phase: salting liquid=1: x: y: z, wherein x is 0.1～5, y is that 0.1～10, z is 0.1～10;
(2) reduction: reducing agent is joined in the microemulsion that step (1) makes, and the mol ratio of reducing agent and salt is (1～10): 1;
(3) load: the catalyst activity component that step (2) reduction is fully obtained loads on carrier;
(4) microemulsion that step (3) is made is dry, roasting obtains catalyst of the present invention.
Wherein said non-ionic surface active agent is at least a in TX-100, Tween85, Tween80, Tween60, Tween20, Span80, Span40, NP-10, NP-4, OP-10; Described cosurfactant is C
3～C
8Alcohols, more preferably a kind of in normal propyl alcohol, n-butanol, n-hexyl alcohol; Described oil phase is selected from C
6～C
12Linear paraffin, cyclic alkane, branched paraffin at least a, more preferably from cyclohexane, n-hexane, normal octane; Described salting liquid is selected from a kind of in described nitrate, sulfate, chloride.
Reduction reaction temperature in step (2) is 0～50 ℃, and mixing time is 0.1～5 hour, and described reducing agent is at least a in hydrazine hydrate, metal hydroboron, hydrogen, sodium hypophosphite, aromatic aldehyde, fatty aldehyde.
The catalyst activity component that above-mentioned reduction is fully obtained loads on carrier by conventional methods such as dipping, sprayings, and more preferably the catalyst activity component of described microemulsion preparation loads on carrier by a step dipping or step impregnation.
The demonstration of transmission electron microscope (TEM) test result, the catalyst that uses microemulsion technology of the present invention to make forms nano particle in microemulsion, and the particle diameter＜5nm of nano particle can be with reference to accompanying drawing 1.In addition, the particle of active component can be controlled by the mode of regulating water/surfactant.
Another object of the present invention is to provide a kind of preparation method who removes the methanation catalyst of oxycarbide.In the method, the aqueous solution of activity component metal salt is dispersed in oil phase through non-ionic surface active agent and cosurfactant parcel, mode by dipping, spraying after the reducing agent reduction loads on carrier, and the metal nanoparticle average diameter that forms in microemulsion is less than 5nm.Specifically comprise the following steps:
(1) preparation microemulsion: in water bath with thermostatic control, the water, cosurfactant, the oil phase that are comprised of the salting liquid of non-ionic surface active agent, catalyst activity component mix in proportion, stir the stable w/o type microemulsion system of preparation, the mass ratio of each component is non-ionic surface active agent: cosurfactant: oil phase: salting liquid=1: x: y: z, wherein x is 0.1～5, y is that 0.1～10, z is 0.1～10;
(2) reduction: reducing agent is joined in the microemulsion that step (1) makes, and the mol ratio of reducing agent and salt is (1～10): 1;
(3) load: the catalyst activity component that step (2) reduction is fully obtained loads on carrier;
(4) microemulsion that step (3) is made is dry, roasting obtains catalyst of the present invention.
The 3rd purpose of the present invention is to provide the application in the oxycarbide reaction of this catalyst in removing gas.
The present invention compared with prior art has the following advantages:
(1) preparation method of the present invention is simple, and is easy to operate, and experiment condition is gentle.
(2) compare with conventional method, the methanation catalyst that removes oxycarbide of the present invention's preparation is because adopting microemulsion method to be prepared from, and its particle diameter is controlled, evenly, and good dispersion, good stability.
(3) although the content of catalyst master active component Ru is low, this catalyst has higher low temperature active.
Description of drawings
Fig. 1 is the distribution of catalyst nanoparticles in microemulsion system
The specific embodiment
The present invention will be further described below in conjunction with specific embodiment, but the present invention is not limited in following embodiment.
Embodiment 1
1. the RuCl of 100mgRu/ml
3Solution 2ml uses deionized water solution to be diluted to 5g.
2. in the water bath with thermostatic control of 20 ℃ in the 100ml volumetric flask with non-ionic surface active agent Tween8010g, cosurfactant normal propyl alcohol 20g, oil phase cyclohexane 20g, the magnetic agitation certain hour is made stable Reverse Microemulsion System.
3. in will 1. adding 2., stir, obtain to contain the microemulsion of Ru ion.
4. stir certain hour, add the reducing agent hydrazine hydrate, added in microemulsion in 1: 7 in molar ratio, carry out reduction reaction, reacted 4 hours.
5. take profile of tooth Al
2O
3Carrier 100g, above-mentioned microemulsion for preparing of dipping on it.
The carrier that 6. will 5. flood above-mentioned microemulsion is through super-dry, roasting, and reduction is prepared into described catalyst, obtains catalyst EM-1, and wherein Ru content is 0.2wt%.
Embodiment 2
With 200mgRu/ml Ru (NO
3)
3Solution 1ml, the Ni (NO of 700mg Ni/ml
3)
2Solution 0.4ml uses deionized water solution to be diluted to 5g, adds non-ionic surface active agent Tween6010g, and n-butanol 20g, normal heptane 20g stir and be prepared into microemulsion.All the other steps obtain catalyst EM-2 all with embodiment 1, and wherein Ru content is 0.2wt%, and Ni content is 0.28wt%.
Embodiment 3
Take the RuCl of 300mg Ru/ml
3Solution 1ml adds the Fe (NO of 100mg Fe/ml
3)
2Solution 0.5ml uses the deionized water dilution to be the 5g aqueous solution, and non-ionic surface active agent is TX-10010g, n-amyl alcohol 10g, normal octane 30g, carrier are SiC, and all the other steps are all with embodiment 1, obtain catalyst EM-3, wherein Ru content is 0.3wt%, and Fe content is 0.05wt%.
Embodiment 4
Take the RuCl of 1gRu/ml
3Solution 0.6ml adds the La (NO of 100mg La/ml
3)
3Solution 2ml uses the deionized water dilution to be the 5g aqueous solution, and non-ionic surface active agent is Tween80-Span8010g, and cosurfactant is normal propyl alcohol 20g, and oil phase is n-decane 20g, and carrier is TiO
2All the other steps obtain catalyst EM-4 all with embodiment 1, and wherein Ru content is 0.6wt%, and La content is 0.2wt%.
Embodiment 5
1. the RuCl of 2gRu/ml
3Solution 0.4ml adds the Pt (NO of 50mgPt/ml
3)
2Solution 1ml uses the deionized water dilution to be the 5g aqueous solution.
2. in the water bath with thermostatic control of 25 ℃ in the 100ml volumetric flask with non-ionic surface active agent (NP-10: NP-4=1: 1 mass ratio) 5g, cosurfactant n-hexyl alcohol 20g, oil phase n-hexane 25g, the magnetic agitation certain hour is made stable microemulsion system.
3. in will 1. adding 2., stir and obtain to contain RuCl
3, Pt (NO
3)
2Microemulsion.
4. stir certain hour, add the borane reducing agent sodium hydride, added in 1: 3 in molar ratio, carry out reduction reaction, reacted 4 hours.
5. take TiO
2Carrier 100g, on it spraying above-mentioned prepare microemulsion.
The carrier of the above-mentioned microemulsion that 6. will 5. spray is through super-dry, roasting, and reduction is prepared into described catalyst.Obtain catalyst EM-5, wherein Ru content is 0.8wt%, and Pt content is 0.05wt%.
Embodiment 6
With non-ionic surface active agent (Tween20: OP-10=2: 1 mass ratio) gross mass is 10g, cosurfactant n-hexyl alcohol 10g, oil phase cyclohexane 30g, the magnetic agitation certain hour is made stable Reverse Microemulsion System.The RuCl of 1gRu/ml
3Solution 0.4ml adds the Cu (NO of 200mgCu/ml
3)
2Solution 0.5ml.Add 100mg Cr/ml Cr (NO
3)
39H
2O 1ml uses the deionized water dilution to be the 5g aqueous solution.Carrier is Al
2O
3, all the other operate all with embodiment 5, obtain catalyst EM-6, and wherein Ru content is 0.4wt%, and Cu content is 0.02wt%, and Cr content is 0.1wt%.
Embodiment 7
With non-ionic surface active agent (Tween85: Span40=1: 1 mass ratio) gross mass is 10g, cosurfactant n-octyl alcohol 10g, the positive nonane 30g of oil phase, the magnetic agitation certain hour is made stable Reverse Microemulsion System.The RuCl of 1gRu/ml
3Solution 1ml adds the KNO solution 0.5ml of 100mgK/ml.Wherein Ru content is 1wt%, and K content is 0.05wt%.
Comparative Examples 1
Adopt the catalyst of infusion process preparation
With reference to patent US20070253893, configure a certain amount of RuCl
3The aqueous solution, dipping γ-Al
2O
3Carrier, 110 ℃ of oven dry 8 hours, 350 ℃ of roastings 5 hours obtain Ru/ γ-Al
2O
3Solid catalyst, Ru content＞3wt%.
Be applied to contain the catalyst of above-described embodiment and Comparative Examples preparation in the hydrogen-rich gas methanation reaction of 0.5%CO, reaction condition is as follows, the 1ml catalyst is packed in the stainless steel tube reactor, after using nitrogen replacement, then individual hour of 180 ℃ of reductase 12s of hydrogen pass into unstripped gas in reactor, and the reactor feed gas volume ratio consists of: methane 5.47%, hydrogen 94.034%, carbon monoxide 0.50%.Raw gas flow is 200ml/min.Can estimate above-mentioned catalyst methane voltinism, each catalyst is deviate from the methanation activity of CO and is listed in table 1 under identical conditions.
The reactivity worth of table 1 catalyst
Experimental result shows, compares with Comparative Examples, and the load capacity of the metal active constituent Ru of the catalyst of the present invention's preparation is low, but shows higher low temperature active in methanation reaction.
Claims (11)
1. a methanation catalyst that is used for removing oxycarbide, comprise carrier and the active component that is carried on carrier, it is characterized in that:
Described carrier is Al
2O
3, SiO
2, ZrO
2, TiO
2, V
2O
5, SnO
2, at least a in SiC, kaolin;
Described active component comprises main active component and/or helps active component;
Described main active component is simple substance Ru, and Ru content is the 0.01wt%～7.0wt% of described carrier gross weight;
The described active component that helps is at least a in Ni, Fe, Ga, Pt, Cu, Sn, Ge, Zn, Cr, rare earth element, alkali metal, and content is the 0.0wt%～20.0wt% of described carrier gross weight;
The grain diameter of described main active component is less than 50nm;
In described catalyst, active component is adopt microemulsion method to prepare and get, and is carried on carrier.
2. the methanation catalyst be used to removing oxycarbide according to claim 1, is characterized in that described Ru content is the 0.05wt%～5wt% of described carrier gross weight.
3. the methanation catalyst be used to removing oxycarbide according to claim 1, is characterized in that described Ru content is the 0.1wt%～2wt% of described carrier gross weight.
4. the methanation catalyst be used to removing oxycarbide according to claim 1, is characterized in that the described active component content that helps is the 0.0wt%～10.0wt% of described carrier gross weight.
5. the methanation catalyst be used to removing oxycarbide according to claim 1, is characterized in that described carrier is Al
2O
3, SiO
2, ZnO, TiO
2, the specific area of carrier is 1～400m
2/ g, average pore size is 5～300nm, pore volume is 0.2～1.2ml/g.
6. the methanation catalyst be used to removing oxycarbide according to claim 1 is characterized in that described catalyst adopts the microemulsion preparation method in preparation process, comprise the following steps:
(1) preparation microemulsion: in water bath with thermostatic control, the water, cosurfactant, the oil phase that are comprised of the salting liquid of non-ionic surface active agent, catalyst activity component mix in proportion, stir the stable w/o type microemulsion system of preparation, the mass ratio of each component is non-ionic surface active agent: cosurfactant: oil phase: salting liquid=1: x: y: z, wherein x is 0.1～5, y is that 0.1～10, z is 0.1～10;
(2) reduction: reducing agent is joined in the microemulsion that step (1) makes, and the mol ratio of reducing agent and salt is (1～10): 1;
(3) load: the catalyst activity component that step (2) reduction is fully obtained loads on carrier;
(4) microemulsion that step (3) is made is dry, roasting obtains the methanation catalyst be used to removing oxycarbide of the present invention.
7. the methanation catalyst be used to removing oxycarbide according to claim 6, it is characterized in that described non-ionic surface active agent is at least a in TX-100, Tween85, Tween80, Tween60, Tween20, Span80, Span40, NP-10, NP-4, OP-10, described cosurfactant is C
3～C
8Alcohols, described oil phase is C
6～C
12Linear paraffin, cyclic alkane, branched paraffin at least a, described salting liquid is at least a in the nitrate, sulfate, chloride of noble metal.
8. the methanation catalyst be used to removing oxycarbide according to claim 6, is characterized in that described cosurfactant is normal propyl alcohol, n-butanol, n-hexyl alcohol, and described oil phase is cyclohexane, n-hexane, normal octane.
9. the methanation catalyst be used to removing oxycarbide according to claim 6, the reduction reaction temperature that it is characterized in that described step (2) is 0～50 ℃, mixing time is 0.1～5 hour, and described reducing agent is at least a in hydrazine hydrate, metal hydroboron, hydrogen, sodium hypophosphite, aromatic aldehyde, fatty aldehyde.
10. the preparation method of the described methanation catalyst be used to removing oxycarbide of one of claim 1-9 comprises the following steps:
(1) preparation microemulsion: in water bath with thermostatic control, the water, cosurfactant, the oil phase that are comprised of the salting liquid of non-ionic surface active agent, catalyst activity component mix in proportion, stir the stable w/o type microemulsion system of preparation, the mass ratio of each component is non-ionic surface active agent: cosurfactant: oil phase: salting liquid=1: x: y: z, wherein x is 0.1～5, y is that 0.1～10, z is 0.1～10;
(2) reduction: reducing agent is joined in the microemulsion that step (1) makes, and the mol ratio of reducing agent and salt is (1～10): 1;
(3) load: the catalyst activity component that step (2) reduction is fully obtained loads on carrier;
(4) microemulsion that step (3) is made is dry, roasting obtains selective hydrogenation catalyst.
11. the described catalyst of claim 1 is applied to remove the methanation reaction of carbon oxides in gas.
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| CN108585017A (en) * | 2018-07-24 | 2018-09-28 | 中铝稀土（江苏）有限公司 | A kind of preparation method of rare earth oxide ceria |
| WO2021152614A1 (en) * | 2020-01-31 | 2021-08-05 | Institute Of Chemical Technology | Catalyst for co2 methanation reaction having high activity and long term stability and process thereof |
| CN114073957A (en) * | 2020-08-14 | 2022-02-22 | 四川大学 | Method for synthesizing double-active-center catalyst by double-microemulsion anti-solvent extraction method |
| CN115121243A (en) * | 2022-07-13 | 2022-09-30 | 南京大学 | Thermocatalytic CO 2 Selective hydrogenation catalyst, preparation method and application thereof |
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| WO2021152614A1 (en) * | 2020-01-31 | 2021-08-05 | Institute Of Chemical Technology | Catalyst for co2 methanation reaction having high activity and long term stability and process thereof |
| GB2605087A (en) * | 2020-01-31 | 2022-09-21 | Institute Of Chemical Tech | Catalyst for Co2 methanation reaction having high activity and long term stability and process thereof |
| CN114073957A (en) * | 2020-08-14 | 2022-02-22 | 四川大学 | Method for synthesizing double-active-center catalyst by double-microemulsion anti-solvent extraction method |
| CN115121243A (en) * | 2022-07-13 | 2022-09-30 | 南京大学 | Thermocatalytic CO 2 Selective hydrogenation catalyst, preparation method and application thereof |
| CN115121243B (en) * | 2022-07-13 | 2023-10-13 | 南京大学 | Thermocatalytic CO 2 Selective hydrogenation catalyst, preparation method and application thereof |
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