CN104511314B - A kind of Catalyst for Low-Temperature Methanation and preparation method thereof - Google Patents
A kind of Catalyst for Low-Temperature Methanation and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Catalyst for Low-Temperature Methanation, comprising: high-molecular organic material carrier, be supported on the thunder damping alloy particle of high-molecular organic material carrier surface, described thunder damping alloy contains the nickel of 30 60wt%, the ferrum of 0.01 5wt%, the chromium of 0.01 5wt%, the lanthanum of 0.01 5wt% and the aluminum of 30 60wt%.This catalyst has activity advantages of higher in low temperature methanation reaction.
Description
Technical field
The present invention relates to catalytic field, in particular, relate to a kind of for low temperature methanation removing hydrogen
The catalyst of middle trace amounts of oxycarbide.
Background technology
In catalytic field, " Lei Nifa " is the preparation method of a kind of active metal catalyst, the method
It is first to prepare the above alloy of the binary containing active metal, then by least one METAL EXTRACTION out, surplus
Under the metal with loose structure there is higher catalytic activity.This method is also referred to as " activation ".Example
As, Raney's nickel catalyst (the Industrial and Engineering invented by U.S. M.Raney the earliest
Chemistry, 1940, Vol.32,1199), it first prepares nickel alumin(i)um alloy, is then dissolved by strong base solution
Aluminium element in alloy, remaining nickel metal has loose structure, has the highest catalysis activity.
Methanation catalyst is mainly used in ethylene unit or synthetic ammonia installation trace carbon oxidation in thick hydrogen
The deep removal of thing (mainly CO), typically requires that the oxycarbide in thick hydrogen is through methanator
Must be removed to less than 5ppm.
Methanation catalyst mainly includes Ru series catalysts and Ni series catalysts.Owing to Ru metal is expensive,
So the application of industry is little.The methanation catalyst being widely used at present is mainly support type Ni
Catalyst.Supported Ni catalyst is also divided into high temperature catalyst and low temperature catalyst.In ethylene unit,
High temperature catalyst operation temperature is generally 280-350 DEG C, and low temperature catalyst operation temperature is generally
150-200℃.Catalyst for Low-Temperature Methanation has energy-saving and environmental protection, safe, economic advantage, high temperature
Methanation process will gradually be replaced by low temperature methanation process.
Catalyst activity is required the highest, in order to obtain low temperature high activity, typically by low temperature methanation process
Needing to prepare the catalyst that Ni load capacity is the highest, traditional method prepares the operation of high Ni load capacity catalyst
Complexity, processing cost is high, and conventional methanation catalyst needs high-temperature roasting, and high-temperature roasting certainly will cause
Considerable metallic particles sinters so that the utilization rate of active metal is low, so the reactivity of catalyst
The highest.
In sum, in the prior art, traditional method its operation of Catalyst for Low-Temperature Methanation is prepared multiple
Miscellaneous, processing cost is high, and catalyst activity is relatively low, and therefore a kind of preparation method of exploitation is simple and has
Higher active Catalyst for Low-Temperature Methanation is had to have great importance for methanation process.
Summary of the invention
It is an object of the invention to provide a kind of Catalyst for Low-Temperature Methanation, this method for preparing catalyst letter
Easily, the load capacity of active metal is high, and the utilization rate of active metal is the highest, for low temperature methanation reaction
There is very high activity.
Catalyst for Low-Temperature Methanation of the present invention, comprising: high-molecular organic material carrier, load
At the thunder damping alloy particle of high-molecular organic material carrier surface, described thunder damping alloy include nickel, ferrum,
Chromium, lanthanum and aluminum.
Preferably, in described thunder damping alloy contains, nickel is 30-60wt%, ferrum is 0.01-5wt%, chromium
For 0.01-5wt%, lanthanum be 0.01-5wt%'s and aluminum be 30-60wt%.
Preferably, the thunder damping alloy particle in Catalyst for Low-Temperature Methanation is to be partially submerged into organic polymer material
Form in material carrier is supported on carrier surface, and " thunder damping alloy particle fraction embeds high-molecular organic material
In carrier " some embeds in carrier to refer to each thunder damping alloy particle.Described thunder damping alloy
Particle fraction embed in organic polymeric carrier material be by under carrier processing and forming temperature conditions or
Under conditions of uncured sizing, mold what the carrier being coated with by thunder damping alloy particle reached.
Under the dual function of heat and pressure, high-molecular organic material carrier produces softening transform, Lei Nihe
In the carrier that gold particle is softened by part press-in, while particle fraction is pressed into, the carrier of softening can be
Particle periphery overflows, and the carrier of spilling not only acts as the effect firmly fixing particle, and in spilling
Can be pressed into again other particles on carrier surface, the most repeatedly, making that the press-in of thunder damping alloy particle fraction is all can
In the carrier surface that can be pressed into.As it has been described above, the present invention effectively make use of overall surface area so that
The active metallic content of catalyst load is the highest.Additionally, due to thunder damping alloy particle fraction embeds in carrier,
The carrier of particle periphery, as firmly fixing thing, makes catalyst have good stability.
Preferably, the mean diameter of described thunder damping alloy particle is generally 0.1～1000 micron, preferably
It it is 10～100 microns.
In order to improve catalyst activity or selectivity, thunder damping alloy may be incorporated into accelerator, accelerator
At least one in Mo, Ti, Ru, Pd, Pt and Rh, forms the thunder damping alloy of multicomponent mixture,
The amount of accelerator is the 0.01～5wt% of thunder damping alloy total amount.
The preferred plastics of described high-molecular organic material or its modified product, plastics include thermosetting plastics and
Thermoplastic.Concrete plastics include: polyolefin, poly-4-methyl isophthalic acid amylene, polyamide are (such as Buddhist nun
Dragon-5, PA-12, nylon-6/6, nylon-6/10, nylon-11), polycarbonate resin, homopolymerization and
/ or copolymerized methanal, monounsaturated dicarboxylic acid and dihydroxylic alcohols by polycondensation reaction prepare linear polyester, aromatic ring high score
Son (polymer that aromatic ring macromolecule i.e. molecule is only made up of aromatic ring and linking group, as polyphenyl, polyphenylene oxide,
Polyphenylene sulfide, polyarylsulfone (PAS), poly aryl ketone.Aromatic polyester, aromatic polyamides), heterocyclic polymer (heterocycle
On macromolecule i.e. molecular backbone in addition to aromatic ring also have heterocycle macromolecular material, such as polybenzimidazoles), contain
Fluoropolymer, acrylic resin, mephenesin Carbamate, epoxy resin, phenolic resin, Lauxite, three
Melamine-formaldehyde resin etc..Preferred polyolefm resin, polyamide, polystyrene, epoxy resin and
At least one in phenolic resin, more preferably polypropylene, nylon-6, nylon-66, polystyrene, phenolic aldehyde
At least one in resin and epoxy resin.
Modifying plastics product refers to the modified product using existing modifying plastics method to obtain.Modifying plastics
Method is including, but not limited to following methods: polarity or non-polar monomer or the graft modification of its polymer；
By with inorganic or organic reinforcing, toughening material, the firm material of increasing, increase the material such as heat-resisting material
Melt blending modified etc..
Invention further provides the preparation method of above-mentioned Catalyst for Low-Temperature Methanation.
The preparation method of the Catalyst for Low-Temperature Methanation of the present invention, comprising: become at high-molecular organic material
Under the conditions of type processing temperature or under conditions of uncured sizing, mold pressing is organic by thunder damping alloy particle cladding
Macromolecular material.
For different high-molecular organic material carriers, concrete preparation method is slightly different.
When carrier uses organic thermoplastic polymer material, can specifically select () or () with the following method
Preparation:
Method ():
(1) thermoplastic carrier is processed into meet needed for fixed bde catalyst or fluid catalyst big
The granule of little any shape；
(2) being placed in by above-mentioned carrier granular in thunder damping alloy particle, i.e. carrier is completely by thunder damping alloy grain
Attached bag is covered；
(3) under corresponding thermoplastic carrier's processing and forming temperature conditions, mold and be placed in thunder damping alloy grain
Thermoplastic carrier in son, by thunder damping alloy particle fraction press-in thermoplastic carrier's granule so that Lei Nihe
Gold particle is supported on thermoplastic carrier's particle surface and is partially submerged in carrier, cooling, sieves, obtains
Granular Catalyst for Low-Temperature Methanation.
The size of graininess Catalyst for Low-Temperature Methanation is can meet fixed bde catalyst or stream
Needed for change bed catalyst on the basis of particle size.The shape of granule can be any irregularly shaped, spherical
Body, hemispherical mass, cylinder, semi-cylindrical body, prism-shaped body, cube, cuboid, ring-type
Body, half-annuli, hollow cylinder, profile of tooth or the combination etc. of above shape, the most spherical, annular,
Profile of tooth, cylinder or the combination of above shape.Thermoplastic carrier's granule can be by raw material processing molding, also
Can directly use thermoplastic carrier's granule of commercial molding.
Or method ():
(1) thermoplastic carrier is processed into fixed bde catalyst or fluid catalyst desired thickness
Sheet material；
(2) by the surface of thunder damping alloy uniform particle cladding resulting vehicle sheet material；
(3) under the conventional processing and forming temperature conditions of corresponding thermoplastic carrier, to by thunder damping alloy grain
The sheet material that attached bag is covered molds, and thunder damping alloy particle, by part press-in support sheet, uses after cooling
Any available process equipment, has thunder by cutting, cutting, punching press or the method such as broken by area load
The support sheet of damping alloy particle is processed into the granule of required shapes and sizes, the most also obtains granule
The Catalyst for Low-Temperature Methanation of shape.
Thermoplastic carrier described in method () or method () can add such as antioxidant, help
Antioxidant, heat stabilizer, light stabilizer, ozone stabilizers, processing aid, plasticizer, softening agent,
Anti-blocking agent, foaming agent, dyestuff, pigment, wax, extender, organic acid, fire retardant and coupling agent
Deng auxiliary agent conventional in plastic processes.Adjuvant used consumption is conventional amount used, or according to actual feelings
The requirement of condition is adjusted.
When carrier uses thermosetting high-molecular organic material carrier, can specifically select () with the following method
Or prepared by ():
Method ():
(1) it is configured to suitable curing system, liquid body according to the conventional curing formula of thermoset carrier
System can directly stir；Pulverized solid system can directly be blended uniformly；Granulated solid system can recruitment
Any disintegrating apparatus conventional in industry is blended uniformly after pulverizing.
(2) particle size any needed for can meeting fixed bde catalyst or fluid catalyst
It is initially charged thunder damping alloy powder in the mould of cavity shape, adds the uncured thermosetting prepared organic
Macromolecular material, then adds thunder damping alloy powder, and it is partially cured fixed to carry out under conventional condition of cure
Type, is then coated with any available the having of pelleted substrate of thunder damping alloy powder to partially cured sizing
Machine processing of high molecular material equipment proceeds molded curing, after completion of cure, sieves, and i.e. obtains granule
Shape loaded catalyst；
Or method ():
(1) it is configured to suitable firming body according to the conventional curing formula of thermosetting high-molecular organic material
System, liquid system can directly stir；Pulverized solid system can directly be blended uniformly；Granulated solid
System can be blended uniformly after pulverizing with industrial conventional any disintegrating apparatus.
(2) the thermosetting high-molecular organic material system that will prepare, under conventional condition of cure,
Molding in flakes with any available equipment, not fully cured, thickness is by fixed bde catalyst or fluid bed
Catalyst size determines, upper and lower surface is uniformly coated with thunder damping alloy powder, continues to mold to being fully cured, thunder
In damping alloy pruinescence part press-in thermoset carrier, the surface of thermoset carrier sheet material is by thunder damping alloy powder institute
Load, i.e. obtains Catalyst for Low-Temperature Methanation.
(3) by Catalyst for Low-Temperature Methanation obtained above, any available organic polymer material is used
Material process equipment, by cutting, cutting, punching press or crush etc. method be processed into fixed bed or fluid bed
The granule that reaction can use, the size of granule is can meet fixed bde catalyst or fluid bed
Needed for catalyst on the basis of particle size, the shape of granule can be any irregularly shaped, spheroid,
Hemispherical mass, cylinder, semi-cylindrical body, prism-shaped body, cube, cuboid, ring bodies,
Half-annuli, hollow cylinder, profile of tooth or the combination etc. of above shape, the most spherical, annular, profile of tooth,
Cylinder or the combination of above shape.
Prepare at the thermosetting high-molecular organic material curing system described in method () or method ()
During, optional one or more can be added selected from following additive: curing accelerator, dyestuff,
Pigment, coloring agent, antioxidant, stabilizer, plasticizer, lubricant, flow ability modifying agent or auxiliary agent,
Fire retardant, dripping inhibitor, anti-caking agent, adhesion promoter, conductive agent, polyvalent metal ion, impact modifying agent,
Demolding aids, nucleator etc..Additive therefor consumption is conventional amount used, or wanting according to practical situation
Ask and be adjusted.
The catalyst that the present invention obtains can be easy to be activated, and activation condition is usually: at 25 DEG C
～95 DEG C, use 0.5-30%(weight) at least one in aluminum, zinc and silicon of the aqueous slkali dissolution of concentration,
Alkali liquor is preferably with NaOH or KOH, about 5 minutes～72 hours base extraction time.
By controlling the addition of thunder damping alloy in catalyst preparation process and/or controlling the activation of catalyst
Degree, such that it is able to control the load capacity of Raney metal in catalyst easily, such as, can obtain thunder
Buddhist nun's content of metal is 1～90%(weight) support type of the activation of (being in terms of 100% by overall catalyst weight)
Catalyst, preferably Raney metal load capacity are 10～80%(weight) the loaded catalyst of activation,
More preferably Raney metal load capacity is 40～80%(weight).
Inorganic oxide carrier metal supported catalyst prepared by traditional employing infusion process, needs repeatedly to soak
Stain, repeated calcination, process is complicated, and the load capacity of metal is difficult to more than 40%(weight) (with catalyst
Gross weight is 100% meter), and owing to the high-temperature roasting in preparation process causes considerable metallic particles to burn
Knot so that the utilization rate of active metal is relatively low, thus catalyst activity is relatively low.Catalyst of the present invention is not only
More active metal can be loaded, and preparation process does not has high-temperature process, so the profit of active metal
The highest by rate, thus catalyst activity is high.
Catalyst prepared by the present invention may be used for the adding of trace amounts of oxycarbide in low temperature removing hydrogen-rich gas
Hydrogen reacts, and reaction condition can be carried out according to known low temperature methanation reaction condition.
The preparation method of catalyst of the present invention is simple, and cost is relatively low, and the catalyst obtained is in low temperature methanation
Reaction has very high activity.
Detailed description of the invention
The present invention is described further for example below, but not thereby limiting the invention.
Embodiment 1
Prepared by the catalyst of macromolecular material load:
(1) polypropylene powder (Maoming Petrochemical, F280M) is extruded and chopped into double screw extruder
Φ 3mm × 3～5mm granule；
(2) weighing 100g PP GRANULES to be placed among thunder damping alloy powder body, in thunder damping alloy, Ni contains
Amount is 48%(weight), Fe tenor is 1.5%(weight), Cr tenor is 1.5%(weight),
La tenor is 1.0%(weight), Al tenor 48%(weight), with compression molding instrument in temperature
Spend 200 DEG C, mold 10min under conditions of pressure 7MPa, take out cooling, sieve, sift out spherical
Grain, particle surface is covered by thunder damping alloy powder completely, i.e. obtains catalyst, be weighed as 380g；
(3) configure 20%NaOH aqueous solution 400g with deionized water, add the catalysis of step (2) gained
Agent 40g, keeps temperature 85 DEG C, filters out solution after 4 hours, i.e. obtains the catalyst of activation, finally
In catalyst, nickel content of metal is about 53%(weight), washing to close to after neutrality, deposit in from
In sub-water standby.
Embodiment 2
Prepared by the catalyst of macromolecular material load:
(1) polypropylene powder (Maoming Petrochemical, F280M) is extruded and chopped into double screw extruder
Φ 3mm × 3～5mm granule；
(2) weighing 100g PP GRANULES to be placed among thunder damping alloy powder body, in thunder damping alloy, Ni contains
Amount is 40%(weight), Fe tenor is 1.5%(weight), Cr tenor is 1.5%(weight),
La tenor is 1.0%(weight), Al tenor 56%(weight), with compression molding instrument in temperature
Spend 200 DEG C, mold 10min under conditions of pressure 7MPa, take out cooling, sieve, sift out spherical
Grain, particle surface is covered by thunder damping alloy powder completely, i.e. obtains catalyst, be weighed as 380g；
(3) configure 20%NaOH aqueous solution 400g with deionized water, add the catalysis of step (2) gained
Agent 40g, keeps temperature 85 DEG C, filters out solution after 4 hours, i.e. obtains the catalyst of activation, finally
In catalyst, nickel content of metal is about 48%(weight), washing to close to after neutrality, deposit in from
In sub-water standby.
Embodiment 3
Prepared by the catalyst of macromolecular material load:
(1) polypropylene powder (Maoming Petrochemical, F280M) is extruded and chopped into double screw extruder
Φ 3mm × 3～5mm granule；
(2) weighing 100g PP GRANULES to be placed among thunder damping alloy powder body, in thunder damping alloy, Ni contains
Amount is 60%(weight), Fe tenor is 1.5%(weight), Cr tenor is 1.5%(weight),
La tenor is 1.0%(weight), Al tenor 36%(weight), with compression molding instrument in temperature
Spend 200 DEG C, mold 10min under conditions of pressure 7MPa, take out cooling, sieve, sift out spherical
Grain, particle surface is covered by thunder damping alloy powder completely, i.e. obtains catalyst, be weighed as 380g；
(3) configure 20%NaOH aqueous solution 400g with deionized water, add the catalysis of step (2) gained
Agent 40g, keeps temperature 65 DEG C, filters out solution after 1 hour, i.e. obtains the catalyst of activation, finally
In catalyst, nickel content of metal is about 68%(weight), washing to close to after neutrality, deposit in from
In sub-water standby.
Embodiment 4
(1) polypropylene powder (Maoming Petrochemical, F280M) is extruded and chopped into double screw extruder
Φ 3mm × 3～5mm granule；
(2) weighing 100g PP GRANULES to be placed among nickel alumin(i)um alloy powder body, in nickel alumin(i)um alloy, Ni contains
Amount is 48%(weight), Fe tenor is 1.5%(weight), Cr tenor is 1.5%(weight),
La tenor is 1.0%(weight), Al tenor 48%(weight), with compression molding instrument in temperature
Spend 220 DEG C, mold 10min under conditions of pressure 7MPa, take out cooling, sieve, sift out spherical
Grain, particle surface is covered by thunder damping alloy powder completely, i.e. obtains catalyst, be weighed as 420g；
(3) configure 20%NaOH aqueous solution 400g with deionized water, add the catalysis of step (2) gained
Agent 40g, keeps temperature 85 DEG C, filters out solution after 8 hours, i.e. obtains the catalyst of activation, finally
In catalyst, nickel content of metal is about 60%(weight), washing to close to after neutrality, deposit in from
In sub-water standby.
Comparative example
The preparation of alumina load nickel-metal catalyst:
Alumina load Ni catalyst uses infusion process to prepare.Preparation process is as follows: first by carrier molding
For 3-5mm granular size, forming process needs the steps such as kneading, extrusion, dry, high-temperature roasting；
Nickel nitrate is configured to certain concentration solution again, sprays on alumina support, dry 24 hours for 150 DEG C,
400 DEG C of roastings 4 hours, obtain reducing procatalyst；In order to obtain high metal content catalyst, need
Want repeat the above steps repeatedly；Last catalyst needs reduction activation in hydrogen, reduction temperature 400 DEG C,
24 hours recovery times.With reference to said method, repeat the above steps 7 times, preparing Ni tenor is
58%(weight) alumina load catalyst, trace amounts of CO in low temperature methanation removing hydrogen
Reaction.
Embodiment 5
CO methanation reaction performance test:
Measuring 6ml catalyst and load rustless steel fixed bed reactors, be passed through high pure nitrogen, flow is 300
Ml/min, is heated to 150 DEG C, keeps 2 hours；Then switch to unstripped gas reaction, in thick hydrogen
Containing 0.5%CO(volume).After reaction, gas composition uses gas chromatographic analysis, and chromatographic detector is FID,
CO content can be as accurate as 1ppm.Table 1 gives detailed assessment result.
According to above-mentioned evaluation methodology, to embodiment 1, embodiment 2, embodiment 3, embodiment 4 and contrast
Example has carried out reaction evaluating respectively, and table 1 gives detailed assessment result.Outlet CO content (ppm)
The least, show that the activity of catalyst is the highest.
Table 1 methanation reaction evaluation result
From table 1 result, the outlet CO content of the embodiment of the present invention is far below comparative example, shows this
Invention catalyst has more preferable low temperature methanation activity.
Claims (9)
1. a Catalyst for Low-Temperature Methanation, comprising: high-molecular organic material carrier, be supported on the thunder damping alloy particle of high-molecular organic material carrier surface, described thunder damping alloy includes nickel, ferrum, chromium, lanthanum and aluminum；In some organic polymeric carrier material of embedding of each thunder damping alloy particle.
Catalyst the most according to claim 1, wherein thunder damping alloy particle fraction is by under the processing and forming temperature conditions of carrier or under conditions of uncured sizing in embedding carrier, molds what the carrier being coated with by thunder damping alloy particle reached.
Catalyst the most according to claim 1, wherein in described thunder damping alloy, nickel is 30-60wt%, ferrum is 0.01-5wt%, chromium is 0.01-5wt%, lanthanum is 0.01-5wt%, aluminum is 30-60wt%.
Catalyst the most according to claim 1, wherein in described thunder damping alloy, also includes the accelerator of at least one in Mo, Ti, Ru, Pd, Pt and Rh, and accelerator is the 0.01～5wt% of thunder damping alloy gross weight.
Catalyst the most according to claim 1, wherein said high-molecular organic material is plastics or modified plastics.
Catalyst the most according to claim 5, at least one in vistanex, polyamide, polystyrene, epoxy resin and phenolic resin of wherein said plastics.
Catalyst the most according to claim 1, catalyst shape is spherical, annular, profile of tooth, cylinder, cuboid or the combination of above shape.
8. the method preparing catalyst as described in one of claim 1～7, comprising: under high-molecular organic material processing and forming temperature conditions or under conditions of uncured sizing, mold by the high-molecular organic material of thunder damping alloy particle cladding.
9. the catalyst that one of claim 1～7 is described low temperature methanation elimination reaction of trace amounts of CO in hydrogen.
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| CN106497619A (en) * | 2015-09-06 | 2017-03-15 | 中国石油化工股份有限公司 | A kind of method that Raney alloy catalyst is applied to synthesis gas preparing natural gas by methanation |
| CN106492864B (en) * | 2015-09-06 | 2019-12-24 | 中国石油化工股份有限公司 | Catalyst for methanation of synthesis gas and preparation method and application thereof |
| CN107008328B (en) * | 2017-03-15 | 2019-10-22 | 中国科学院上海高等研究院 | A kind of high load amount catalyst and its preparation method and application for methane tri-reforming |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58112087A (en) * | 1981-12-24 | 1983-07-04 | Chiyoda Chem Eng & Constr Co Ltd | Catalyst for purification of waste water |
| CN1037283A (en) * | 1988-04-14 | 1989-11-22 | 格雷斯公司 | The catalyst of moulding and preparation method |
| CN101356004A (en) * | 2005-11-14 | 2009-01-28 | 新加坡科技研究局 | Highly dispersed metal catalysts |
-
2013
- 2013-09-30 CN CN201310461181.3A patent/CN104511314B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58112087A (en) * | 1981-12-24 | 1983-07-04 | Chiyoda Chem Eng & Constr Co Ltd | Catalyst for purification of waste water |
| CN1037283A (en) * | 1988-04-14 | 1989-11-22 | 格雷斯公司 | The catalyst of moulding and preparation method |
| CN101356004A (en) * | 2005-11-14 | 2009-01-28 | 新加坡科技研究局 | Highly dispersed metal catalysts |
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