CN104415767B - Palladium and/or platinum-containing catalyst and method for removing H2 in CO raw material - Google Patents
Palladium and/or platinum-containing catalyst and method for removing H2 in CO raw material Download PDFInfo
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Abstract
The invention provides a palladium and/or platinum-containing catalyst. The palladium and/or platinum-containing catalyst contains a magnetic carrier and palladium and/or platinum which accounts for 0.1-3 weight percent of the palladium and/or platinum-containing catalyst and is loaded on the magnetic carrier. The invention further provides a method for removing H2 in a CO raw material. The method comprises the following steps: in a magnetically stabilized bed reactor, making the CO raw material be contact with the palladium and/or platinum-containing catalyst under the condition of a methanation reaction, wherein the palladium and/or platinum-containing catalyst is the palladium and/or platinum-containing catalyst provided by the invention. The method for removing H2 in the CO raw material, provided by the invention, can be used for rapidly reducing the content of H2 in the CO raw material to below 90ppm because the palladium and/or platinum-containing catalyst and the magnetically stabilized bed reactor are adopted.
Description
Technical field
The present invention relates to a kind of catalyst containing palladium and/or platinum, and contain the catalyst removal co of palladium and/or platinum using this
H in raw material2Method.
Background technology
Replace oil ethylene with coal or natural gas through oxalate synthesizing glycol technology, be recognized be current raw material route
Science, the utilization of resources are the most reasonable, be substantially better than the synthesizing glycol technology of petroleum path.According to measuring and calculating, if whole world oil
The 2 of ethylene production, 2,000,000 tons of ethylene glycol are all produced with this technology, are equivalent to one annual output 5,500 of success newly developed
The Daqing oil field of the above oil of ten thousand tons of scales, nearly 2,00,000,000,000 yuan of its output value.Relatively rich in conjunction with China's oil starvation, few gas, coal resources
Rich current resources situation, developing the technology preparing ethylene glycol from coal has great economic and social benefit.If this skill
Art can be able to popularization and application at home, will greatly alleviate the current oil of China, ethylene and the ethylene glycol quilt that supply falls short of demand
Dynamic situation, promotes the technological progress of the energy and Coal Chemical Industry, and then the coordination of promotion national economy, health, stable development, ensures me
The energy of state and national defense safety.
Existing coal-ethylene glycol industrialized unit mostly adopts oxalate technique, and this process route mainly has three reaction steps
Rapid: 1. coal water gas separate through pressure-variable adsorption and obtain co unstripped gas；2. co catalytic coupling synthesis of oxalate；3. oxalic acid ester catalysis
Hydrogenation preparing ethylene glycol.The process of wherein co catalytic coupling synthesis of oxalate needs the co unstripped gas of a large amount of high purifications, and by water
Coal gas pressure-variable adsorption separates or cryogenics separate the industrial co unstrpped gas obtaining and unavoidably carry a certain amount of h2Remnants,
Affect follow-up carbongl group synthesis reaction.Research work shows, for oxo process step pd series catalysts in h2Content is higher
In the case of exist face hydrogen deactivation prob.(the h such as Li Zhenhua2Deactivation mechanism to the reaction of co gas-phase catalytic coupling ethyl oxalate,
Journal of Chemical Industry and Engineering, 2003,54(1): 59-63) to h2The shadow to catalyst in the reaction of co gas-phase catalytic coupling ethyl oxalate
Sound is inquired into, and finds under same reaction temperature, h in synthesis gas2Content is higher, and the activity of catalyst is lower, oxalic acid diethyl
The selectivity of ester and space time yield are lower, even if 1% about h2Remnants also can have a strong impact on the property of synthetic catalyst in step 2
Energy.Therefore, how to facilitate and economically remove a small amount of h in industrial co gas2Thus obtaining the co gas meeting subsequent reactions requirement
It is an important technology difficult problem of development oxo process industry.
It is used for both at home and abroad at present removing a small amount of h in co gas2Technique and catalyst report seldom, compare typical method
It is to add a small amount of o in unstripped gas2It is selectively oxidized reaction to remove hydrogen, catalyst is then catalyzed for carried noble metal
Agent.
Cn102284286a discloses a small amount of h in a kind of selective oxidation removal industry co synthesis gas2Collosol and gel pd/
a12o3Catalyst, wherein, active component palladium content is 0.1-0.5%.This reaction adopts fixed bed reactors, containing a small amount of h2's
Co unstripped gas is with 2000-8000h-1Air speed pass through bed, be additionally passed through o2Air speed be 10-100h-1, in pressure 0.1-
1mpa, reacts under conditions of temperature 100-300 DEG C, h in the co gas after making except hydrogen purification2Content is less than 100ppm.Using this
Method, in reaction end gas, the content of hydrogen can drop to 90ppm.Although adopting the method, in reaction end gas, the content of hydrogen can
To drop to 90ppm, but it is 2000h that embodiment only gives feed space velocity-1Experiment number when (catalyst amount is 10 milliliters)
According to.This air speed is less, and reaction efficiency is relatively low.
Cn102649568a discloses a kind of method that co mixed gas gating catalytic oxidation removes hydrogen, and platinum metal is
The catalyst of active component, in the pretreatment gas atmosphere for 1-100% for the oxygen content, is 100-400 DEG C in temperature, volume
Air speed is 100-10000h-1, under conditions of pressure is 0-2.0mpa, process 0.0l-40 hour；Then, it is big with hydrogen content
It is raw material in the co mixed gas of 0-10%, in oxygen and raw material, the mol ratio of hydrogen is 0.5-5:1, and reaction temperature is 100-
300 DEG C, volume space velocity is 100-10000h-1, under conditions of reaction pressure is -0.08-5.0mpa, raw material passes through equipped with platinum group gold
Belong to and contacting with catalyst for active constituent catalyst reactor.In described catalyst, preferred platinum or palladium are active component, and platinum
Be the content of active component be 0.05-1%, carrier is silicon oxide, at least one in aluminium oxide or molecular sieve.Although adopt should
Method, in reaction end gas, the content of hydrogen can drop to below 5ppm, but the method operation is more complicated, needs catalyst is entered
The special pretreatment of row；And the applicable volume space velocity of the method is less, gives highest volume space velocity and be only in embodiment
7800h-1When (270 DEG C of temperature, pressure be -0.04mpa) experimental data.This air speed is less, and reaction efficiency is relatively low.
Cn101993073a discloses a kind of method that co mixed gas selective oxidation removes hydrogen, adopts the co with hydrogen
Gas be raw material, reaction temperature be 80-260 DEG C, volume space velocity be 100-10,000h-1, oxygen/hydrogen mol ratio be 0.5-
Under conditions of 10:1, reaction pressure are -0.08-5.0mpa, raw material is contacted with noble metal catalyst, and the hydrogen in raw material is oxidized
For water, wherein noble metal catalyst includes lamellar composite carrier, active component and auxiliary agent, by weight percentage, catalyst bag
Include following component: at least one that (a) is selected from platinum metal is active component；(b) be selected from alkali metal, alkaline-earth metal, ib,
At least one in iib, vb, viib, viii, iiia, iva or lanthanide compound is auxiliary agent；C () is by a kind of inert carrier
Kernel and be incorporated on core porous coating material shell composition lamellar composite carrier.Although adopting the method, reaction
In tail gas, the content of hydrogen can drop to below 1ppm, but the catalyst composition that the method adopts is complex, even and if
Under greater catalytic agent consumption (10 milliliters), the highest volume space velocity that embodiment is given is 8800h-1.This air speed is still less, instead
Should be less efficient.
Therefore, explore a kind of new more efficient, more economical remove in industrial co gas the Technology of a small amount of hydrogen and
Efficient catalyst is significant.
Content of the invention
It is an object of the invention to provide a kind of new catalyst containing palladium and/or platinum and contain palladium and/or platinum using this
H in catalyst removal co raw material2Method, the method can be by h in co raw material under higher space velocity2Content be reduced to 90ppm
Below.
The present inventor finds through substantial amounts of experiment, the catalyst containing palladium and/or platinum being provided using the present invention
With magnetically stabilized bed reactor, can be fast and effeciently by h in co raw material2Content (in co raw material, hydrogen content can be 0.01-
2 volumes %) it is reduced to below 90ppm.
To achieve these goals, the invention provides a kind of catalyst containing palladium and/or platinum, wherein, described containing palladium and/
Or the catalyst of platinum contains magnetic carrier and being supported on and accounts for the described catalyst 0.1- containing palladium and/or platinum on described magnetic carrier
The palladium of 3 weight % and/or platinum.
Present invention also offers h in a kind of removing co raw material2Method, wherein, the method includes, in magnetic stablizing bed reaction
In device, co raw material is contacted under the conditions of methanation reaction with the catalyst containing palladium and/or platinum；Described urging containing palladium and/or platinum
Agent catalyst containing palladium and/or platinum for above-mentioned offer.
The present invention mainly passes through using the catalyst containing palladium and/or platinum and magnetically stabilized bed reactor, has quick dehydrogenation
Effect.The method that the present invention provides volume space velocity of co raw material when processing co raw material can reach 50000h-1, with prior art
Compare hence it is evident that improve production efficiency.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of catalyst containing palladium and/or platinum, wherein, the described catalyst containing palladium and/or platinum contains
Magnetic carrier and being supported on account on described magnetic carrier the described palladium of catalyst 0.1-3 weight % containing palladium and/or platinum and/or
Platinum.The content of described magnetic carrier is 97-99.9 weight %.It should be noted that heretofore described urging containing palladium and/or platinum
In agent, the content of each component is all calculated with charged material weight.In the described catalyst containing palladium and/or platinum, the element of palladium and/or platinum
Content be palladium and/or platinum input amount account for magnetic carrier and palladium and/or platinum total input amount percentage ratio.
The catalyst being provided according to the present invention, described magnetic carrier does not specially require, and can be able to produce for any one
The material of magnetisation.Under preferable case, described magnetic carrier can contain aluminium oxide and magnetic-particle, and described magnetic-particle is permissible
It is made up of the silicon dioxide of iron compound and this iron compound of cladding.
The catalyst being provided according to the present invention, as long as described magnetic carrier contains aluminium oxide and magnetic-particle, and makes containing palladium
And/or the catalyst of platinum has superparamagnetism, the content of aluminium oxide and magnetic carrier is not specially required.Preferably feelings
Under condition, based on the gross weight of described magnetic carrier, the content of described magnetic-particle is 1-50 weight %, balance of aluminium oxide.
The catalyst being provided according to the present invention, described magnetic-particle is by the titanium dioxide of iron compound and this iron compound of cladding
Silicon forms.In described magnetic-particle, the content of silicon dioxide and iron compound does not specially require, as long as silicon dioxide can wrap
Cover iron compound.Under preferable case, in described magnetic-particle, the weight of silicon dioxide and iron compound is than for 0.3-4:
1, more preferably 1-3:1.The two is capable of silicon dioxide and preferably coats iron compound in this proportion.This
The magnetic-particle that bright employing coated with silica iron compound is formed, can avoid iron compound with oxide contact at high temperature
Form hercynite, it is to avoid the permanent deactivation containing palladium and/or the catalyst of platinum.In addition, the magnetic carrier that the present invention provides
There is good heat stability and corrosion resistance.
The catalyst being provided according to the present invention, the present invention do not specially require to the species of iron compound, as long as can be containing
The catalyst of palladium and/or platinum brings magnetic.That is, except containing can be containing palladium and/or platinum in described iron compound
Catalyst bring beyond the ferrum of the magnetic being stable in the presence of in magnetically stabilized bed reactor, other components can be impurity.
For example, described iron compound can be iron slag and other magnetisable material, in order to improve the catalysis containing palladium and/or platinum further
The superparamagnetism of agent, under preferable case, the ferrum containing 50-100 weight % in described iron compound.In the case of more preferably, described contain
Iron substance is fe3o4, fe and γ-fe2o3One or more of.It should be noted that selecting fe3o4As iron compound preparation
During magnetic carrier, in preparation process, part fe3o4It is transformed into γ-fe2o3But, the throwing of each component when calculating magnetic carrier
Material weight is than still with fe3o4Calculate, that is, ignore this conversion process.
The catalyst being provided according to the present invention, the present invention does not specially require to the particle diameter of iron compound, under preferable case,
The particle diameter of described iron compound is 3-30nm.When described iron compound particle diameter within the range when, be conducive to magnetic stablizing bed
Middle formation chained operations state, reactor bed is more stable.
According to the present invention, the preparation method of described magnetic carrier does not specially require.Under preferable case, described magnetic carrier
Can be prepared as follows:
By na2sio3·9h2O is dissolved in distilled water, is slowly added dropwise hcl solution under agitation, by the ph of solution
Value is adjusted to 10-13, standby after filtration.
Fecl is added in the stirred tank equipped with distilled water3·6h2O and/or fecl2·4h2O, is warming up to 85-90 DEG C,
Nh is added in high-speed agitating process3·h2O solution, after high-speed stirred 3-60 minute, isolates black fe using magnetic separator3o4
Granular product.By the precipitated product ultrasonic disperse after cleaning in above-mentioned pretreated na2sio3In solution, then move into stirring
In kettle, it is warming up to 85-100 DEG C, under nitrogen protection and stirring condition, be slowly added dropwise concentration about hcl solution in solution, in 3-
In 6 hours, the ph value of solution is down to 4-6 by 10-13.Obtain white sio2Cladding fe3o4The magnetic-particle of granule.
By alcl3·6h2O is dissolved in deionized water, adds high-purity aluminum foil, keeps 60-72 hour at 80-100 DEG C,
After so that aluminium foil is completely dissolved in solution, liquor capacity heating is concentrated into 300-600ml, obtains clarifying translucent hydrogen-oxygen
Change Alumina gel.
At 10-30 DEG C, aluminum hydroxide sol is mixed with Amine Solutions (containing hexamethylenetetramine and carbamide), stirring
Uniformly, add magnetic-particle, pour into after being sufficiently stirred for and fill the sulfonated kerosene (surfactant containing 0.05 volume %
Span80 in stirred tank).At 15-25 DEG C, it is uniformly dispersed under the rotating speed of 500-700rpm, form water-in-oil emulsion,
Subsequently system is warming up to 85-90 DEG C, after keeping 15-60 minute, cools down, isolate product, obtain the spherical al of magnetic (oh)3.
By spherical for above-mentioned magnetic al (oh)3Product loads in the autoclave filling sulfonated kerosene medium, under nitrogen protection
In 180-240 DEG C of hydrothermal treatment consists 2-6 hour, after product cleaning oil removing, subsequently in 80-100 in ph value is for the weak ammonia of 10-12
DEG C ageing 4-10 hour to remove wherein partial impurities, through 60-100 DEG C dry after, can get the magnetic ball of boehmite structure
Shape al (oh)3Product.The spherical al of this magnetic (oh)3Product sinters 2-10 hour through 580-700 DEG C of air atmosphere, can be contained
sio2Cladding γ-fe2o3Spherical gamma-the al of magnetic kernel2o3Carrier.
The catalyst being provided according to the present invention, described catalyst preferably by magnetic carrier and is supported on described magnetic carrier
On palladium and/or platinum composition.Further preferably described catalyst by magnetic carrier and is supported on the palladium on described magnetic carrier
With platinum composition.In described catalyst, the ratio of palladium and platinum does not specially require, as long as in described catalyst containing palladium and platinum being
Can.Under preferable case, the weight of palladium and platinum is than for 2-8:1.
The catalyst being provided according to the present invention, the particle diameter of described catalyst does not specially require, and under preferable case, described urges
The particle diameter of agent is 50 μm of -1mm.So in the case of the utilization ratio realizing catalyst as far as possible, make catalyst with raw material
The flow losses of air-flow few as far as possible.
According to the present invention, the preparation method of described catalyst does not specially require, can according to those skilled in the art
The preparation method of any one catalyst known is carried out, for example infusion process, the sedimentation method etc..
Present invention also offers h in a kind of removing co raw material2Method, wherein, the method includes, in magnetic stablizing bed reaction
In device, co raw material is contacted under the conditions of methanation reaction with the catalyst containing palladium and/or platinum；Described urging containing palladium and/or platinum
Agent catalyst containing palladium and/or platinum for above-mentioned offer.
The method being provided according to the present invention, described magnetically stabilized bed reactor can be well known by persons skilled in the art any
A kind of magnetically stabilized bed reactor, the present invention does not specially require.Under preferable case, magnetically stabilized bed reactor of the present invention is permissible
It is made up of reactor and externally-applied magnetic field.As long as reactor and reactor other part are made up of the good material of magnetic permeability, along instead
Device is answered axially to add uniform and stable magnetic field, uniform magnetic field can be by DC source and the Helmholtz coaxial with reactor
Coil or uniform high-density solenoid provide.The magnetically stabilized bed reactor that the present invention adopts is with magnetic retention granule as solid phase, equal
Form special bed under even magnetic field, not only have fixed bed and the advantage of fluid bed concurrently, significantly can strengthen course of reaction, and make
Standby process is simple, the size of magnetically stabilized bed reactor and magnetic field intensity flexibly can select according to practical situation, for extensive work
Industry application provides great convenience.
The method being provided according to the present invention, in the preferred case, the magnetic field intensity that described magnetically stabilized bed reactor produces can
Think 20-400ka/m.This magnetic field intensity can select according to the volume space velocity of co raw material, generally, the body of co raw material
Long-pending air speed is bigger, and magnetic field intensity is bigger, in order to avoid the catalyst containing palladium and/or platinum is taken away by co raw material, it is to avoid containing palladium and/or platinum
The loss of catalyst.
The method being provided according to the present invention, in the preferred case, described methanation reaction condition includes: temperature is 100-
300 DEG C, pressure is 0.1-5mpa, preferably 0.1-3mpa.
The method being provided according to the present invention, the catalyst by co raw material and containing palladium and/or platinum is under the conditions of methanation reaction
Can be with 1000-50000h-1Volume space velocity contact.Although using the method for the present invention in relatively low-speed (as 1000-
10000h-1) under can be completely by the h in co raw material2Content is reduced to lower loading, but air speed is relatively low to be unfavorable for improving reaction
Efficiency, therefore, in the preferred case, can be using the volume space velocity of the co raw material being far longer than prior art, will co raw material
With the catalyst containing palladium and/or platinum under the conditions of methanation reaction with 15000-50000h-1Volume space velocity contact, remain able to
Obtain h in co raw material2Content be reduced to the effect of below 90ppm, substantially increase production efficiency.
The method being provided according to the present invention, described co raw material can be the synthesis gas of petroleum and natural gas conversion, coal controlling the water circulation
Coal gas and semiwater gas, steel plant's tail gas etc. separate, through pressure-variable adsorption, the co unstripped gas obtaining, and these co of industrial preparation are former
The h of 0.01-2 volume % is usually contained in material gas2.Using the method for the present invention, not only h in co unstripped gas2Volume content is relatively low
When can drop to lower loading and even remove the h in co unstripped gas completely2But, h in co unstripped gas2Volume content is higher (such as
Up to 2 volumes %) when, still can obtain h2Content be reduced to the co raw material of below 90ppm.
By the way of embodiment, the present invention is described in further detail below.
In following examples, grain diameter adopts sieve method to select.
Hereinafter raw material used or reagent unless stated otherwise, are commercial goods, and identical reagent source phase
With.
Embodiment 1
(1) magnetic-particle preparation
By 189g na2sio3·9h2O is dissolved in 1000ml distilled water, is slowly added dropwise 3mol/l under agitation
Hcl solution, the ph value of solution is adjusted to 13, standby after filtration.
42.2g fecl is added in the 3l stirred tank equipped with 1200ml distilled water3·6h2O and 20.6gfecl2·4h2O,
It is warming up to 85 DEG C, high-speed agitating process adds the nh of 60ml25%3·h2O solution, high-speed stirred, after 3 minutes, is divided using magnetic
Isolate black fe from device3o4Granule (grain diameter is 3-30nm).By the black fe after cleaning3o4Granule ultrasonic disperse is upper
State pretreated na2sio3In solution, then move in 3l stirred tank, be warming up to 85 DEG C, in nitrogen protection and stirring condition
Under, the hcl solution of Deca concentration 2mol/l in solution, in 3 hours, the ph value of solution is down to 6 by 13, is filtrated to get
60g white sio2Cladding fe3o4Magnetic-particle (wherein, the fe of granule3o4Weight about 20g, is coated on fe3o4The sio on surface2About
40g, silicon dioxide and fe3o4Weight than for 2:1).Through vibrating specimen magnetometer (vsm) (purchased from U.S. quantum design
Company) detect that the hysteresis curve obtaining shows, magnetic-particle has superparamagnetism.
(2) magnetic carrier preparation
Weigh alcl3·6h2O80g, is dissolved in 600ml deionized water, adds 44g high-purity aluminum foil, keeps at 80 DEG C
72 hours, after so that aluminium foil is completely dissolved in solution, liquor capacity heating is concentrated into 300ml, obtains clarifying translucent
Aluminum hydroxide sol.
At 10 DEG C, measure 100ml aluminum hydroxide sol, the Amine Solutions (300g/ containing hexamethylenetetramine with 90ml
L and carbamide 150g/l) mixing, stir, add 7.3g magnetic-particle, pour into after being sufficiently stirred for and fill 1600ml sulfonated coal
In the 3l stirred tank of oily (the surfactant span80 containing 0.05 volume %).At 25 DEG C, disperse under the rotating speed of 700rpm
Uniformly, form water-in-oil emulsion, subsequently system is warming up to 90 DEG C, after keeping 15 minutes, cool down, isolate product, obtain
The spherical al of magnetic (oh)3.
By spherical for above-mentioned magnetic al (oh)3Load in the 1l autoclave filling 0.7l sulfonated kerosene medium, under nitrogen protection
180 DEG C of hydrothermal treatment consists 2 hours, after product cleaning oil removing, subsequently in ph value is for 10 weak ammonia in 80 DEG C of ageings 5 hours to go
Remove wherein partial impurities, after drying through 60 DEG C, can get the spherical al of magnetic (oh)3Product.The spherical al of this magnetic (oh)3Product by
al(oh)3、fe3o4With γ-fe2o3(xrd spectrogram proves there is part fe3o4It is oxidized to γ-fe2o3) and sio2Composition.
The spherical al (oh) of above-mentioned magnetic3Product sinters 2 hours through 580 DEG C of air atmospheres, can obtain about 45g magnetic spherical
γ-al2o3(wherein, the charged material weight ratio of each component is carrier: fe3o4: sio2: al2o3=6:12:82.Aoxidize in magnetic carrier
The content of aluminum is 82 weight %).The mean diameter of this carrier is about 200 μm.
(3) preparation of catalyst
By 0.168g pdcl2It is dissolved in 1.0ml2mol/l dilute hydrochloric acid, adjusting solution ph is 3, will using infusion process
The solution of preparation is mixed with above-mentioned 10g magnetic carrier.Dry 8 hours at 120 DEG C after being sufficiently impregnated with, then again at 500 DEG C
Roasting 8 hours is obtained the %(charged material weight ratio of weight containing pd1) catalyst cat-1.The particle diameter of catalyst cat-1 is 200 μm.
Embodiment 2
(1) magnetic-particle preparation
By 28.4g na2sio3·9h2O is dissolved in 1000ml distilled water, is slowly added dropwise 3mol/l under agitation
Hcl solution, the ph value of solution is adjusted to 13, standby after filtration.
46.7g fecl is added in the 2l stirred tank equipped with 1200ml distilled water3·6h2O and 17.2gfecl2·4h2O,
It is warming up to 90 DEG C, high-speed agitating process adds the naoh solution of 160ml6mol/l, high-speed stirred, after 3 minutes, is divided using magnetic
Isolate black fe from device3o4Granule (grain diameter is 3-30nm).By the black fe after cleaning3o4Granule ultrasonic disperse is upper
State pretreated na2sio3In solution, then move in 2l stirred tank, be warming up to 85 DEG C, in nitrogen protection and stirring condition
Under, the hcl solution of Deca concentration 2mol/l in solution, in 3 hours, the ph value of solution is down to 6 by 13.Obtain 26g white
Color sio2Cladding fe3o4Magnetic-particle (wherein, the fe of granule3o4Weight about 20g, is coated on fe3o4The sio on surface2About 6g, dioxy
SiClx and fe3o4Weight than for 0.3:1).Show through the hysteresis curve that vibrating specimen magnetometer (vsm) detection obtains, magnetic
Grain has superparamagnetism.
(2) magnetic carrier preparation
Weigh alcl3·6h2O75.1g, is dissolved in 600ml deionized water, adds 44.6g high-purity aluminum foil, at 90 DEG C
Keep 70 hours, after so that aluminium foil is completely dissolved in solution, liquor capacity heating is concentrated into 300ml, obtains clarifying translucent
The aluminum hydroxide sol of shape.
At 10 DEG C, measure 100ml aluminum hydroxide sol, the Amine Solutions (300g/ containing hexamethylenetetramine with 90ml
L and carbamide 150g/l) mixing, stir, add 21.3g magnetic-particle, pour into after being sufficiently stirred for and fill 1600ml sulfonation
In the 3l stirred tank of kerosene (the surfactant span80 containing 0.05 volume %).At 25 DEG C, in lower point of the rotating speed of 500rpm
Dissipate uniformly, form water-in-oil emulsion, subsequently system is warming up to 90 DEG C, after keeping 15 minutes, cool down, isolate product, obtain
To the spherical al of magnetic (oh)3.
By spherical for above-mentioned magnetic al (oh)3Load in the 1l autoclave filling 0.7l sulfonated kerosene medium, under nitrogen protection
180 DEG C of hydrothermal treatment consists 2 hours, after product cleaning oil removing, subsequently in ph value is for 10 weak ammonia in 80 DEG C of ageings 4 hours to go
Remove wherein partial impurities, after drying through 90 DEG C, can get the spherical al of magnetic (oh)3Product.The spherical al of this magnetic (oh)3Product by
al(oh)3、fe3o4With γ-fe2o3(xrd spectrogram proves there is part fe3o4It is oxidized to γ-fe2o3) and sio2Composition.
The spherical al (oh) of above-mentioned magnetic3Product sinters 2 hours through 580 DEG C of air atmospheres, can obtain about 65g magnetic spherical
γ-al2o3(wherein, the charged material weight ratio of each component is carrier: fe3o4: sio2: al2o3=30:9:61.Aoxidize in magnetic carrier
The content of aluminum is 61 weight %).The mean diameter of this carrier is about 1mm.
(3) preparation of catalyst
By 0.136g ptcl2It is dissolved in 0.8ml2mol/l dilute hydrochloric acid, adjusting solution ph is 3.0, using infusion process
The solution of preparation is mixed with above-mentioned 10g magnetic carrier.Dry 8 hours at 120 DEG C after being sufficiently impregnated with, then again at 500 DEG C
Lower roasting 8 hours is obtained pt1 weight %(charged material weight ratio) catalyst cat-2.The particle diameter of catalyst cat-2 is 1mm.
Embodiment 3
(1) magnetic-particle preparation
By 189g na2sio3·9h2O is dissolved in 1000ml distilled water, is slowly added dropwise 3mol/l under agitation
Hcl solution, the ph value of solution is adjusted to 13, standby after filtration.
By 14.54g black iron powder (grain diameter is 3-30nm) granule ultrasonic disperse in above-mentioned pretreated na2sio3
In solution, then move in 3l stirred tank, be warming up to 85 DEG C, under nitrogen protection and stirring condition, the Deca concentration in solution
The hcl solution of 2mol/l, in 3 hours, the ph value of solution is down to 6 by 13, is filtrated to get 60g white sio2Cladding iron powder
(wherein, iron powder weight about 20g, is coated on the sio on iron powder surface to the magnetic-particle of granule2About 40g, silicon dioxide and iron powder
Weight is than for 2:1).Show, magnetic-particle has superparamagnetic through the hysteresis curve that vibrating specimen magnetometer (vsm) detection obtains
Property.
(2) magnetic carrier preparation
Weigh alcl3·6h2O80g, is dissolved in 600ml deionized water, adds 44g high-purity aluminum foil, keeps at 90 DEG C
72 hours, after so that aluminium foil is completely dissolved in solution, liquor capacity heating is concentrated into 300ml, obtains clarifying translucent
Aluminum hydroxide sol.
At 10 DEG C, measure 100ml aluminum hydroxide sol, the Amine Solutions (300g/ containing hexamethylenetetramine with 90ml
L and carbamide 150g/l) mixing, stir, add 7.3g magnetic-particle, pour into after being sufficiently stirred for and fill 1600ml sulfonated coal
In the 3l stirred tank of oily (the surfactant span80 containing 0.05 volume %).At 20 DEG C, disperse under the rotating speed of 700rpm
Uniformly, form water-in-oil emulsion, subsequently system is warming up to 90 DEG C, after keeping 15 minutes, cool down, isolate product, obtain
The spherical al of magnetic (oh)3.
By spherical for above-mentioned magnetic al (oh)3Load in the 1l autoclave filling 0.7l sulfonated kerosene medium, under nitrogen protection
180 DEG C of hydrothermal treatment consists 2 hours, after product cleaning oil removing, subsequently in ph value is for 10 weak ammonia in 80 DEG C of ageings 5 hours to go
Remove wherein partial impurities, after drying through 60 DEG C, can get the spherical al of magnetic (oh)3Product.The spherical al of this magnetic (oh)3Product by
al(oh)3、fe3o4With γ-fe2o3(xrd spectrogram proves there is part fe3o4It is oxidized to γ-fe2o3) and sio2Composition.
The spherical al (oh) of above-mentioned magnetic3Product sinters 2 hours through 600 DEG C of air atmospheres, can obtain about 45g magnetic spherical
γ-al2o3(wherein, the charged material weight ratio of each component is carrier: iron powder: sio2: al2o3=6:12:82.Aluminium oxide in magnetic carrier
Content be 82 weight %).The mean diameter of this carrier is about 200 μm.
(3) preparation of catalyst
By 0.168g pdcl2With 0.027g ptcl2It is dissolved in 1.0ml2mol/l dilute hydrochloric acid, adjusting solution ph is
3.0, using infusion process, the solution prepared is mixed with above-mentioned 10g magnetic carrier.Dry 8 hours at 100 DEG C after being sufficiently impregnated with,
Then at 500 DEG C, roasting 8 hours is obtained the % of weight containing pd1.0 and pt0.2 weight %(charged material weight ratio again) catalyst
cat-3.The particle diameter of catalyst cat-3 is 200 μm.
Embodiment 4
Catalyst is prepared using the method for embodiment 3, except for the difference that, adjusts pdcl2And ptcl2Input amount so that made
The catalyst cat-4 obtaining contains the pd of the 0.2 weight % and pt of 0.2 weight %.
Embodiment 5
Catalyst is prepared using the method for embodiment 2, except for the difference that, adjusts ptcl2Input amount so that obtained urges
Agent cat-5 contains the pt of 2 weight %.
Embodiment 6
Catalyst is prepared using the method for embodiment 2, except for the difference that, adjusts ptcl2Input amount so that obtained urges
Agent cat-6 contains the pt of 3 weight %.
Embodiment 7
Catalyst is prepared using the method for embodiment 2, except for the difference that, adjusts ptcl2Input amount so that obtained urges
Agent cat-7 contains the pt of 0.5 weight %.
Embodiment 8
Method preparation using embodiment 2 contains the catalyst of palladium and/or platinum, except for the difference that, when preparing magnetic-particle, two
Silicon oxide and fe3o4Weight than for 0.1:1.
It is cat-8 that the obtained catalyst containing palladium and/or platinum is numbered.
Comparative example 1
Catalyst is prepared using the method for embodiment 2, except for the difference that, adjusts ptcl2Input amount so that obtained urges
Agent d1 contains the pt of 3.5 weight %.
Testing example 1
1ml is contained palladium and/or the catalyst sample cat-1 of platinum inserts magnetic stablizing bed micro anti-evaluation device (this device reaction
Device is made up of reaction tube, distributor and additional coil, and reaction tube is the 1cr18ni9ti stainless steel tube of φ 8mm, and length is
700mm；Distributor is made up of the stainless steel cloth of multilamellar 300-400 mesh, and this distributor is located at the feed end of reaction tube；Additional
The uniform coiling of 4 coil flat copper wire forms, each internal coil diameter 65mm, external diameter 160mm, thickness 60mm, the number of turn 400, peace
Adjacent windings centre-to-centre spacing 70mm during dress) in, it is passed through mixed gas (volume content: co:98.0%, h2: 0.3%；o2: 0.16%, surplus
For n2), h in product2By the analysis of gas chromatogram on-line checking, (detection of gas chromatograph is limited to 0.1ppm to concentration, below
Identical).H in reaction velocity, magnetic field intensity, reaction temperature and reaction pressure and product2Concentration is as shown in table 1.
Table 1
Testing example 2
Respectively 1ml is contained palladium and/or the catalyst sample cat-2 to cat-8 of platinum inserts magnetic stablizing bed micro anti-evaluation device
In, it is passed through mixed gas (volume content: co:98.0%, h2: 0.3%；o2: 0.16%, balance of n2), h in product2Concentration
Analyzed by gas chromatogram on-line checking.Catalyst, reaction velocity, magnetic field intensity, reaction temperature and reaction pressure and reaction
H in product2Concentration is as shown in table 2.
Test comparison example 2
Using the method for testing example 2, except for the difference that, d1 selected by catalyst.
H in reaction velocity, magnetic field intensity, reaction temperature and reaction pressure and product2Concentration is as shown in table 2.
Table 2
Testing example 3
The catalyst sample cat-1 that 1ml is contained palladium and/or platinum inserts in magnetic stablizing bed micro anti-evaluation device, be passed through containing
The mixed gas of co, hydrogen and oxygen, h in product2Concentration is analyzed by gas chromatogram on-line checking.Reaction temperature is
300 DEG C, pressure is 3mpa, and air speed is 20000h-1, magnetic field intensity is 300ka/m.H in mixed gas2Content, product
Middle h2Concentration is as shown in table 3.
Test comparison example 3
Using the method for testing example 3, except for the difference that, d1 selected by catalyst.
H in mixed gas2Content, h in product2Concentration is as shown in table 3.
Table 3
From table 1-3 it is apparent that the method providing using the present invention, reach 50000h in air speed-1When, can instead
The content answering hydrogen in product is reduced to below 90ppm.In addition, containing 3.5 weights catalyst d1 from table 2 and 3 as can be seen that working as
During the pt of amount %, the catalysis activity of catalyst d1 does not significantly increase, on the contrary due to tenor because of the increase of platinum content
Exceed certain numerical value, metal ion, in surface aggregation, leads to activity to be decreased obviously.Therefore.In the catalyst containing palladium and/or platinum
In, as long as having appropriate palladium and/or platinum, catalyst can have higher catalysis activity.And work as the present invention containing palladium and/or
When the catalyst of platinum contains palladium and/or the platinum of 0.1-3 weight %, not only there is higher catalysis activity, and significantly reduce life
Produce cost.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to various can
The compound mode of energy no longer separately illustrates.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it equally should be considered as content disclosed in this invention.
Claims (11)
1. h in a kind of removing co raw material2Method it is characterised in that the method includes, in magnetically stabilized bed reactor, co is former
Material is contacted under the conditions of methanation reaction with the catalyst containing palladium and/or platinum；The described catalyst containing palladium and/or platinum is carried by magnetic
Body and being supported on accounts for the described palladium of catalyst 0.1-3 weight % containing palladium and/or platinum and/or platinum group on described magnetic carrier
Become；
Described magnetic carrier contains aluminium oxide and magnetic-particle, and described magnetic-particle by iron compound and coats this iron compound
Silicon dioxide forms.
2. method according to claim 1, wherein, based on the gross weight of described magnetic carrier, the containing of described magnetic-particle
Measure as 1-50 weight %, balance of aluminium oxide.
3. method according to claim 1, wherein, in described magnetic-particle, the weight of silicon dioxide and iron compound
Than for 0.3-4:1.
4. the method according to any one in claim 1-3, wherein, described iron compound is fe3o4, fe and γ-fe2o3
One or more of.
5. the method according to any one in claim 1-3, wherein, the particle diameter of described iron compound is 3-30nm.
6. method according to claim 1, wherein, in described catalyst, the weight of palladium and platinum is than for 2-8:1.
7. the method according to any one in claim 1-3, wherein, the particle diameter of described catalyst is 50 μm of -1mm.
8. method according to claim 1, wherein, the magnetic field intensity that described magnetically stabilized bed reactor produces is 20-
400ka/m.
9. method according to claim 1, wherein, described methanation reaction condition includes: temperature is 100-300 DEG C, pressure
Power is 0.1-5mpa.
10. method according to claim 1, wherein, by co raw material with the catalyst containing palladium and/or platinum in methanation reaction
Under the conditions of with 1000-50000h-1Volume space velocity contact.
11. methods according to claim 1, wherein, h in described co raw material2Volumn concentration be 0.01-2%.
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| CN1541766A (en) * | 2003-04-29 | 2004-11-03 | 中国石油化工股份有限公司 | Precious metal carrying hydrogenation catalyst |
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