CN104512864B - A kind of method that low temperature removes trace amounts of oxycarbide - Google Patents
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Abstract
The invention discloses a kind of method that low temperature removes trace amounts of oxycarbide, it is characterized in that, in fixed bed reactors, the hydrogen-rich gas containing oxycarbide is contacted with a kind of loaded catalyst, is less than 6000h in 90 125 DEG C of reaction temperature, the 7.0MPa of pressure 0.1, gas space velocity‑1, entrance CO concentration be less than 3000ppm under conditions of carry out methanation reaction.Trace amounts of CO in hydrogen-rich gas can be removed to below 5ppm by this method.
Description
Technical field
The present invention relates to field of gas purification, relate more specifically to the low temperature methanation of micro CO in hydrogen-rich gas
Removing.
Background technology
In catalytic field, " Lei Nifa " is a kind of preparation method of active metal catalyst, and this method is first to prepare to contain
The binary above alloy of active metal, then comes out at least one METAL EXTRACTION, the remaining metal with loose structure
With higher catalytic activity.This method also referred to as " is activated ".For example, the raney ni catalysis invented earliest by U.S. M.Raney
Agent（Industrial and Engineering Chemistry,1940,Vol.32,1199）, it first prepares nickel alumin(i)um alloy, so
The aluminium element in alloy is dissolved by strong base solution afterwards, remaining nickel metal has loose structure, with very high catalytic activity.
Methanation catalyst is mainly used in ethylene unit or synthetic ammonia installation trace amounts of oxycarbide in thick hydrogen（Mainly
CO）Deep removal, typically require that the oxycarbide in thick hydrogen must be removed to less than 5ppm through methanator.
Methanation catalyst mainly includes Ru catalyst and Ni catalyst.Because Ru metals are expensive, so the application of industry
Seldom.The methanation catalyst being widely used at present is mainly Ni catalyst.Ni catalyst be also divided into high temperature catalyst and
Low temperature catalyst.In ethylene unit, high temperature catalyst operation temperature is generally 280-350 DEG C, low temperature catalyst operation temperature
Generally 150-200 DEG C.Catalyst for Low-Temperature Methanation has energy-saving and environmental protection, safe, economic advantage, therefore, high-temperature methanation
Technique gradually will be replaced by low temperature methanation process.
The reaction temperature of existing Catalyst for Low-Temperature Methanation is all higher than 150 DEG C.Because the reaction less than 150 DEG C is to catalyst
Active pharmaceutical is high, and conventional methanation catalyst needs high-temperature roasting in preparation process, and high-temperature roasting causes considerable gold
Metal particles are sintered so that the utilization rate reduction of active metal, the reactivity for ultimately resulting in catalyst is low, so as to can not meet low
In 150 DEG C of methanation reaction.
Therefore, for low temperature methanation reaction, exploitation is a kind of at lower temperatures（Less than 150 DEG C）Still with high activity
Catalyst has great importance for methanation process.
The content of the invention
It is an object of the invention to provide the method for trace amounts of oxycarbide in a kind of low temperature removing hydrogen-rich gas.This method makes
With a kind of high polymer material supported catalyst still at low temperature with high activity, realize hydrogen-rich gas at 90-125 DEG C
In trace amounts of CO be removed to below 5ppm.
The method that a kind of low temperature of the present invention removes trace amounts of oxycarbide, it is characterised in that in fixed bed reactors
In, the hydrogen-rich gas containing CO is contacted with a kind of loaded catalyst, in 90-125 DEG C of reaction temperature, pressure 0.1-
7.0MPa, gas space velocity are less than 6000h-1, entrance CO concentration be less than 3000ppm under conditions of carry out methanation reaction；It is preferred that
Reaction temperature is 90-125 DEG C, and pressure 2.0-4.0MPa, gas space velocity is less than 3000h-1, entrance CO concentration is less than 3000ppm
Under the conditions of carry out methanation reaction.
Wherein described loaded catalyst includes organic polymeric carrier material and is supported on high-molecular organic material load
The Raney alloy particle in body surface face, the element that described Raney alloy includes Raney metal nickel and can be leached.
Preferably, shape of the Raney alloy particle to be partially submerged into high-molecular organic material carrier in loaded catalyst
Formula is supported on carrier surface, and " Raney alloy particle fraction is embedded in organic polymeric carrier material " refers to each Raney alloy
In particle all some insertion carriers.It is to pass through that described Raney alloy particle fraction, which is embedded in organic polymeric carrier material,
Under carrier processing and forming temperature conditionss or under conditions of uncured sizing, it is molded the carrier coated by Raney alloy particle and reaches
's.Under heat and the double action of pressure, high-molecular organic material carrier produces softening transform, and Raney alloy particle is partly pressed
In the carrier for entering softening, while particle fraction is pressed into, the carrier of softening can overflow in particle periphery, and the carrier of spilling is not only
Play a part of firmly fixing particle, and other particles can be pressed into again on the carrier surface of spilling, so repeatedly, make thunder
The press-in of damping alloy particle fraction is possible in the carrier surface of press-in.As described above, the present invention effectively make use of carrier table
Face region so that the active metallic content of catalyst load is very high.Further, since in Raney alloy particle fraction insertion carrier,
The carrier of particle periphery makes catalyst have good stability as thing is firmly fixed.
Described Raney alloy includes Raney metal and the element that can be leached, and " Raney metal " refers to be activated with Lei Nifa
When insoluble metal, most typical Raney metal is nickel." element that can be leached " can be dissolved when referring to be activated with Lei Nifa
Element, the element that can be leached is generally at least one of aluminium, zinc and silicon.
It is of the invention that Raney alloy particle size and Raney alloy constituent content are not required, commercially available Raney alloy
To use, the average grain diameter of Raney alloy particle is generally 0.1~1000 micron, preferably 10~100 microns.Preferably, thunder
Content of Buddhist nun's metallic nickel in Raney alloy is 55~80wt%.In order to improve catalyst activity or selectivity, Raney alloy is also
Accelerator can be introduced, accelerator is selected from least one of Mo, Cr, Ti, Fe, Pt, Pd, Rh, Ru, forms the thunder of multicomponent mixture
Damping alloy, the amount of accelerator is 0.01~5wt% of Raney alloy total amount.
The preferred plastics of described high-molecular organic material or its modified product, plastics include thermosetting plastics and thermoplasticity is moulded
Material.Specific plastics include：Polyolefin, poly- 4- methyl isophthalic acids amylene, polyamide（Such as nylon -5, Nylon-12, nylon-6/6, Buddhist nun
Dragon -6/10, nylon-11）, polycarbonate resin, homopolymerization and/or copolymerized methanal, monounsaturated dicarboxylic acid and dihydric alcohol it is anti-by polycondensation
Should obtained linear polyester, aromatic ring macromolecule（Aromatic ring macromolecule is the polymer that molecule is only made up of aromatic ring and linking group, such as
Polyphenyl, polyphenylene oxide, polyphenylene sulfide, polyarylsulfone (PAS), poly aryl ketone.Aromatic polyester, aromatic polyamides）, heterocyclic polymer（Heterocyclic polymer
There are the high polymer material of heterocycle, such as polybenzimidazoles i.e. on molecular backbone in addition to aromatic ring）, fluoropolymer, acrylic acid series tree
Fat, mephenesin Carbamate, epoxy resin, phenolic resin, Lauxite, melamine resin etc..Preferred polyolefm resin, polyamides
It is at least one of polyimide resin, polystyrene, epoxy resin and phenolic resin, more preferably polypropylene, nylon-6, nylon -66, poly-
At least one of styrene, phenolic resin and epoxy resin.
Modifying plastics product refers to the modified product obtained using existing modifying plastics method.Modifying plastics method includes
But it is not limited to following methods：The graft modification of polarity or non-polar monomer or its polymer；By with inorganic or organic enhancing
Melt blending modifications of material such as material, toughening material, the firm material of increasing, increase heat-resisting material etc..
Invention further provides the preparation method of above-mentioned catalyst.
The preparation method of catalyst of the present invention, it includes：Under high-molecular organic material processing and forming temperature conditionss or not
Under conditions of solidifying and setting, the high-molecular organic material coated by Raney alloy particle is molded.
For different high-molecular organic material carriers, specific preparation method is slightly different.
When carrier uses organic thermoplastic polymer material, can specifically it select with the following method（ⅰ）Or（ⅱ）Prepare：
Method（ⅰ）：
（1）Thermoplastic carrier is processed into any shape of size needed for meeting fixed bed catalyst or fluid catalyst
The particle of shape；
（2）Above-mentioned carrier granular is placed in Raney alloy particle, i.e., carrier is coated by Raney alloy particle completely；
（3）Under corresponding thermoplastic carrier's processing and forming temperature conditionss, molding is placed in thermoplasticity in Raney alloy particle
Carrier, Raney alloy particle fraction is pressed into thermoplastic carrier's particle so that Raney alloy particle is supported on thermoplastic carrier
Particle surface is simultaneously partially submerged into carrier, is cooled down, and sieving obtains granular Catalyst for Low-Temperature Methanation.
The particle size of pellet type catalyst is can meet particle needed for fixed bed catalyst or fluid catalyst
On the basis of size.The shape of particle can be any irregular shape, orbicule, hemispherical mass, cylinder, semi-cylindrical
Body, prism-shaped body, cube, cuboid, ring bodies, half-annuli, hollow cylinder, tooth form or more combination of shape etc.,
It is preferred that the combination of spherical, annular, tooth form, cylinder or more shape.Thermoplastic carrier's particle can be molded by raw material processing,
The thermoplastic carrier's particle being molded purchased in market can directly be used.
Or method（ⅱ）：
（1）The sheet material of thickness needed for thermoplastic carrier is processed into fixed bed catalyst or fluid catalyst；
（2）Raney alloy uniform particle is coated to the surface of resulting vehicle sheet material；
（3）Under the conventional processing and forming temperature conditionss of corresponding thermoplastic carrier, to the piece coated by Raney alloy particle
Material is molded, and Raney alloy particle is used any available process equipment, passed through by part press-in support sheet after cooling
Cutting, cut, the support sheet that area load has Raney alloy particle is processed into required shape by punching press or the method such as broken
The particle of shape and size, finally also obtains pellet type catalyst.
Method（ⅰ）Or method（ⅱ）Described in thermoplastic carrier can add such as antioxidant, help antioxidant, heat steady
Determine agent, light stabilizer, ozone stabilizers, processing aid, plasticizer, softening agent, anti-blocking agent, foaming agent, dyestuff, pigment, wax,
The auxiliary agent commonly used in the plastic processes such as extender, organic acid, fire retardant and coupling agent.Adjuvant used consumption is routine
Consumption, or be adjusted according to the requirement of actual conditions.
When carrier uses thermosetting high-molecular organic material carrier, can specifically it select with the following method（ⅲ）Or（ⅳ）System
It is standby：
Method（ⅲ）：
（1）Suitable curing system is configured to according to the conventional curing formula of thermoset carrier, liquid system can be stirred directly
Mix uniform；Pulverized solid system can directly be blended uniformly；The available any disintegrating apparatus industrially commonly used of granulated solid system
It is blended after crushing uniform.
（2）Any cavity shape of particle size needed for it can meet fixed bed catalyst or fluid catalyst
Raney alloy powder is first added in mould, the uncured thermosetting high-molecular organic material prepared is added, then adds
Raney alloy powder, carries out partially cured sizing under conventional condition of cure, is then coated with thunder Buddhist nun to partially cured sizing
The pelleted substrate of alloyed powder proceeds molded curing, completion of cure with any available high-molecular organic material process equipment
Afterwards, sieve, that is, obtain particulate supported type catalyst；
Or method（ⅳ）：
（1）Suitable curing system, liquid body are configured to according to the conventional curing formula of thermosetting high-molecular organic material
System can directly stir；Pulverized solid system can directly be blended uniformly；Available times industrially commonly used of granulated solid system
What disintegrating apparatus is blended uniform after crushing.
（2）By the thermosetting high-molecular organic material system prepared, under conventional condition of cure, with any available
Equipment molding is in blocks, and not fully cured, thickness determines that upper and lower surface is equal by fixed bed catalyst or fluid catalyst size
Even cladding Raney alloy powder, continues to be molded to being fully cured, Raney alloy powder is by part press-in thermoset carrier, and thermosetting is carried
The surface of body sheet material is loaded by Raney alloy powder, that is, obtains catalyst.
（3）By catalyst obtained above, using any available high-molecular organic material process equipment, by cutting,
Cut, the particle that fixed bed or fluidized-bed reaction can be used, the particle size of particle are processed into punching press or the method such as broken
On the basis of it can meet particle size needed for fixed bed catalyst or fluid catalyst, the shape of particle can be any
Irregular shape, orbicule, hemispherical mass, cylinder, semi-cylindrical body, prism-shaped body, cube, cuboid, ring bodies,
Combination of half-annuli, hollow cylinder, tooth form or more shape etc., preferably spherical, annular, tooth form, cylinder or more shape
The combination of shape, it is more preferably spherical..
In method（ⅲ）Or method（ⅳ）, can be with described thermosetting high-molecular organic material curing system preparation process
Add optional one or more and be selected from following additive：It is curing accelerator, dyestuff, pigment, colouring agent, antioxidant, steady
Determine agent, plasticizer, lubricant, flow ability modifying agent or auxiliary agent, fire retardant, dripping inhibitor, anti-caking agent, adhesion promoter, conductive agent, multivalence
Metal ion, impact modifying agent, demolding aids, nucleator etc..Additive therefor consumption is conventional amount used, or according to actual feelings
The requirement of condition is adjusted.
The catalyst that the present invention is obtained can be easy to be activated, and activation condition is usually：At 25 DEG C~95 DEG C, 0.5- is used
30%（Weight）The aqueous slkali dissolution of concentration is selected from least one of aluminium, zinc and silicon, and alkali lye is preferably with NaOH or KOH, alkali lye
About 5 minutes~72 hours processing time.
By controlling the activation degree of the addition of Raney alloy and/or control catalyst in catalyst preparation process, from
And the load capacity of Raney metal in catalyst can be easily controlled, it is 1~90% that can for example obtain Raney metal load capacity
（Weight）（Counted using overall catalyst weight as 100%）Activation loaded catalyst, preferably Raney metal load capacity be 10~80%
（Weight）Activation loaded catalyst, more preferably Raney metal load capacity be 40~80%（Weight）.
Inorganic oxide carrier metal supported catalyst prepared by traditional use infusion process is, it is necessary to repeatedly impregnate, repeatedly
Roasting, process is complicated, and the load capacity of metal is difficult more than 40%（Weight）（Counted using overall catalyst weight as 100%）, and due to system
High-temperature roasting during standby causes considerable metallic particles to sinter so that the utilization rate of active metal is relatively low, thus catalysis
Agent activity is relatively low.Catalyst of the present invention can not only load more active metals, and not have high-temperature process, institute in preparation process
It is very high with the utilization rate of active metal, thus catalyst activity is high.
Compared with prior art, the method for removing trace amounts of oxycarbide of the invention has advantages below：
1. method for preparing catalyst is simple in method of the present invention, and cost is relatively low.
2. it is high that the catalyst that high polymer material is loaded in method of the present invention overcomes traditional inorganic oxide carrier
Temperature roasting causes considerable metallic particles Sintering Problem so that the utilization rate of active metal is high, so the reaction of catalyst is lived
Property it is high, realize at 90-125 DEG C and the trace amounts of CO in hydrogen-rich gas be removed to below 5ppm.
Embodiment
The present invention is described further for example below, but not thereby limiting the invention.
Embodiment 1
1st, the catalyst preparation of high polymer material load
（1）By polypropylene powder（Maoming Petrochemical, F280M）Φ 3mm × 3~5mm is extruded and chopped into double screw extruder
Particle；
（2）Weigh 100g PP GRANULESs to be placed among nickel alumin(i)um alloy powder, Ni contents are 48% in nickel alumin(i)um alloy（Weight
Amount）, aluminium weight content 52%（Weight）, 10min is molded under conditions of 200 DEG C of temperature, pressure 7MPa with compression molding instrument, is taken
Go out cooling, sieving sifts out spherical particle, particle surface is covered by Nickel Aluminium Alloy Powder completely, that is, is obtained loaded catalyst, weighed
For 380g；
（3）20%NaOH aqueous solution 400g are configured with deionized water, step is added（2）Gained catalyst 40g, keeping temperature
Filter out solution after 85 DEG C, 4 hours, that is, the catalyst activated, nickel content of metal is about 56% in final catalyst（Weight
Amount）, after washing to close neutrality, deposit in standby in deionized water.
2nd, fixed bed reaction evaluation
Measure 10ml catalyst and load stainless steel fixed bed reactors, be passed through high pure nitrogen, nitrogen flow is 300ml/
Min, is heated to 120 DEG C, is kept for 2 hours；Then switch to contain CO1000ppm in raw material solid/liquid/gas reactions, unstripped gas, other tools
Precursor reactant condition is listed in Table 1 below.Gas composition uses gas chromatographic analysis after reaction, and chromatographic detector is FID, and CO contents can be with
It is accurate to 1ppm.Table 1 gives detailed assessment result.Export CO contents（ppm）It is smaller, show that the activity of catalyst is higher.
The catalyst reaction evaluation result of 1 embodiment of table 1
Embodiment 2
1st, the catalyst preparation of high polymer material load
（1）By polypropylene powder（Maoming Petrochemical, F280M）Φ 3mm × 3~5mm is extruded and chopped into double screw extruder
Particle；
（2）Weigh 100g PP GRANULESs to be placed among nickel alumin(i)um alloy powder, Ni contents are 48% in nickel alumin(i)um alloy（Weight
Amount）, aluminium weight content 52%（Weight）, 10min is molded under conditions of 200 DEG C of temperature, pressure 7MPa with compression molding instrument, is taken
Go out cooling, sieving sifts out spherical particle, particle surface is covered by Nickel Aluminium Alloy Powder completely, that is, is obtained loaded catalyst, weighed
For 420g；
（3）20%NaOH aqueous solution 400g are configured with deionized water, step is added（2）Gained catalyst 40g, keeping temperature
Filter out solution after 85 DEG C, 8 hours, that is, the catalyst activated, nickel content of metal is about 63% in final catalyst（Weight
Amount）, after washing to close neutrality, deposit in standby in deionized water.
2nd, fixed bed reaction evaluation
Measure 10ml catalyst and load stainless steel fixed bed reactors, be passed through high pure nitrogen, nitrogen flow is 300ml/
Min, is heated to 120 DEG C, is kept for 2 hours；Then switch to contain CO2000ppm in raw material solid/liquid/gas reactions, unstripped gas, other tools
Precursor reactant condition is listed in Table 2 below.Gas composition uses gas chromatographic analysis after reaction, and chromatographic detector is FID, and CO contents can be with
It is accurate to 1ppm.Table 2 gives detailed assessment result.Export CO contents（ppm）It is smaller, show that the activity of catalyst is higher.
The catalyst reaction evaluation result of 2 embodiment of table 2
Comparative example 1
1st, the preparation of conventional aluminium oxide supported ni catalyst
The nickel-metal catalyst of alumina load is prepared by pressed disc method.First by 1kg basic nickel carbonates NiCO3·2Ni
(OH)2·4H2After O and a certain amount of boehmite kneading, sieve as little particle, 160 DEG C dry 24 hours, 400 DEG C of roastings 4
Hour, compression molding is Φ 3mm × 3mm cylindrical catalyst particles, and 450 DEG C of hydrogen reducings 24 hours obtain containing 56%（Weight）
The alumina load catalyst of nickel metal, for fixed bed hydrogenation reaction.
2nd, fixed bed reaction evaluation,
Measure 10ml catalyst and load stainless steel fixed bed reactors, first remove catalyst with hydrogen reducing at 240 DEG C
The oxide on surface, the recovery time is 2 hours；Then switch to contain CO1000ppm in raw material solid/liquid/gas reactions, unstripped gas, other tools
Precursor reactant condition is listed in Table 3 below.Gas composition uses gas chromatographic analysis after reaction, and chromatographic detector is FID, and CO contents can be with
It is accurate to 1ppm.Table 1 gives detailed assessment result.Export CO contents（ppm）It is smaller, show that the activity of catalyst is higher.
The catalyst reaction evaluation result of 3 comparative example of table 1
The evaluation result of comparative example 1,2 and comparative example 1 can be seen that can be with using the Ni catalyst of macromolecule loading
Realize at 90-125 DEG C（Trace amounts of CO is removed to less than 1ppm, and the catalyst of comparative example 1 is substantially less than reality in 90-125 DEG C of activity
Apply example 1,2 catalyst, it is impossible to realize CO purification removing purpose.
Embodiment 3
1st, the catalyst preparation of high polymer material load
（1）By polypropylene powder（Maoming Petrochemical, F280M）Φ 3mm × 3~5mm is extruded and chopped into double screw extruder
Particle；
（2）Weigh 100g PP GRANULESs to be placed among nickel alumin(i)um alloy powder, Ni contents are 48% in nickel alumin(i)um alloy（Weight
Amount）, aluminium weight content 52%（Weight）, 10min is molded under conditions of 200 DEG C of temperature, pressure 7MPa with compression molding instrument, is taken
Go out cooling, sieving sifts out spherical particle, particle surface is covered by Nickel Aluminium Alloy Powder completely, that is, is obtained loaded catalyst, weighed
For 420g；
（3）20%NaOH aqueous solution 400g are configured with deionized water, step is added（2）Gained catalyst 40g, keeping temperature
Filter out solution after 85 DEG C, 8 hours, that is, the catalyst activated, nickel content of metal is about 63% in final catalyst（Weight
Amount）, after washing to close neutrality, deposit in standby in deionized water.
2nd, fixed bed reaction evaluation
Measure 10ml catalyst and load stainless steel fixed bed reactors, be passed through high pure nitrogen, nitrogen flow is 300ml/
Min, is heated to 120 DEG C, is kept for 2 hours；Then switch to contain CO1000ppm in raw material solid/liquid/gas reactions, unstripped gas, reaction temperature
125 DEG C of degree, reaction pressure 3.5MPa, gas space velocity 6000h-1,.Gas composition uses gas chromatographic analysis, chromatogram inspection after reaction
Survey device is FID, and CO contents can be as accurate as 1ppm.Reaction result：Outlet CO is 2ppm.
Embodiment 4
1st, the catalyst preparation of high polymer material load
（1）By polypropylene powder（Maoming Petrochemical, F280M）Φ 3mm × 3~5mm is extruded and chopped into double screw extruder
Particle；
（2）Weigh 100g PP GRANULESs to be placed among nickel alumin(i)um alloy powder, Ni contents are 48% in nickel alumin(i)um alloy（Weight
Amount）, aluminium weight content 52%（Weight）, 10min is molded under conditions of 200 DEG C of temperature, pressure 7MPa with compression molding instrument, is taken
Go out cooling, sieving sifts out spherical particle, particle surface is covered by Nickel Aluminium Alloy Powder completely, that is, is obtained loaded catalyst, weighed
For 420g；
（3）20%NaOH aqueous solution 400g are configured with deionized water, step is added（2）Gained catalyst 40g, keeping temperature
Filter out solution after 85 DEG C, 8 hours, that is, the catalyst activated, nickel content of metal is about 63% in final catalyst（Weight
Amount）, after washing to close neutrality, deposit in standby in deionized water.
2nd, fixed bed reaction evaluation
Measure 10ml catalyst and load stainless steel fixed bed reactors, be passed through high pure nitrogen, nitrogen flow is 300ml/
Min, is heated to 120 DEG C, is kept for 2 hours；Then switch to contain CO3000ppm in raw material solid/liquid/gas reactions, unstripped gas, reaction temperature
125 DEG C of degree, reaction pressure 3.5MPa, gas space velocity 1000h-1,.Gas composition uses gas chromatographic analysis, chromatogram inspection after reaction
Survey device is FID, and CO contents can be as accurate as 1ppm.Reaction result：Export CO and be less than 1ppm.
Claims (10)
1. a kind of method that low temperature removes trace amounts of oxycarbide, it is characterised in that in fixed bed reactors, oxidation of coal will be contained
The hydrogen-rich gas of thing is contacted with a kind of loaded catalyst, in 90-125 DEG C of reaction temperature, pressure 0.1-7.0MPa, gas space velocity
Less than 6000h-1, entrance CO concentration be less than 3000ppm under conditions of carry out methanation reaction；
Wherein described loaded catalyst includes organic polymeric carrier material and is supported on high-molecular organic material carrier table
The Raney alloy particle in face, the element that described Raney alloy includes Raney metal nickel and can be leached, described is leached
Element be selected from least one of aluminium, zinc and silicon；
In described loaded catalyst in some organic polymeric carrier material of insertion of each Raney alloy particle.
2. according to the method described in claim 1, wherein Raney alloy particle fraction insertion carrier in be by carrier into
Under the conditions of type processing temperature or under conditions of uncured sizing, it is molded what the carrier coated by Raney alloy particle reached.
3. according to the method described in claim 1, wherein in described Raney alloy, Raney metal nickel is Raney alloy gross weight
55~80wt%.
4. according to the method described in claim 1, wherein in described Raney alloy, in addition to selected from Mo, Cr, Ti, Fe,
At least one of Pt, Pd, Rh, Ru accelerator, accelerator are 0.01~5wt% of Raney alloy gross weight.
5. according to the method described in claim 1, wherein described high-molecular organic material is plastics.
6. method according to claim 5, wherein described plastics are selected from vistanex, polyamide, asphalt mixtures modified by epoxy resin
At least one of fat and phenolic resin.
7. method according to claim 6, wherein described plastics are selected from polypropylene, nylon-6, nylon -66 and polyphenyl second
At least one of alkene.
8. according to the method described in claim 1, catalyst shape is spherical, annular, tooth form, cylinder, cuboid or more
The combination of shape.
9. method according to claim 8, catalyst shape is spherical.
10. according to the method described in claim 1, wherein reaction temperature is 90-125 DEG C, pressure 2.0-4.0MPa, gas space velocity
Less than 3000h-1, entrance CO concentration is less than 3000ppm.
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| CN101934229B (en) * | 2010-05-07 | 2012-11-21 | 重庆工商大学 | Catalyst for oxidative removal of CO in hydrogen-rich gas and preparation and application thereof |
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