CN104415767A - 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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- CN104415767A CN104415767A CN201310397810.0A CN201310397810A CN104415767A CN 104415767 A CN104415767 A CN 104415767A CN 201310397810 A CN201310397810 A CN 201310397810A CN 104415767 A CN104415767 A CN 104415767A
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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 use this to contain H in the catalyst removal CO raw material of palladium and/or platinum
2method.
Background technology
Replace oil ethene through oxalate synthesizing glycol technology with coal or natural gas, being recognized is the synthesizing glycol technology that current raw material route is most scientific, the utilization of resources the most rationally, is obviously better than petroleum path.According to measuring and calculating, if the whole world 2,2,000,000 tons of ethylene glycol of oil ethylene production are all produced by this technology, be just equivalent to the Daqing oil field that 5,5,000,000 tons of above oil of scale are produced in success newly developed per year, its output value nearly 2,00,000,000,000 yuan.In conjunction with the current resources situation of China's oil starvation, weak breath, coal resources relative abundance, developing the technology preparing ethylene glycol from coal has great economic and social benefit.If this technology can be applied at home, greatly will alleviate the current oil of China, ethene and the ethylene glycol passive situation that supply falls short of demand, promote the technological progress of the energy and Coal Chemical Industry, and then promote the coordination of national economy, health, stable development, ensure the energy and the national defense safety of China.
Existing coal-ethylene glycol industrialized unit mostly adopts oxalate technique, and this process route mainly contains three reactions steps: 1. coal water gas is separated through pressure-variable adsorption and obtains CO unstripped gas; 2. CO catalytic coupling synthesis of oxalate; 3. oxalate catalytic hydrogenation preparing ethylene glycol.The wherein CO unstripped gas of a large amount of high purification of the process need of CO catalytic coupling synthesis of oxalate, and to be separated by water-gas pressure-variable adsorption or cryogenics is separated the industrial CO unstrpped gas that obtains unavoidably with a certain amount of H
2remnants, affect follow-up carbongl group synthesis reaction.Research work shows, for the Pd series catalysts of carbonylation synthesis step at H
2exist when content is higher and face hydrogen deactivation prob.(the H such as Li Zhenhua
2to the deactivation mechanism of CO gas-phase catalytic coupling diethy-aceto oxalate reaction, Journal of Chemical Industry and Engineering, 2003,54(1): 59-63) to H
2in the reaction of CO gas-phase catalytic coupling diethy-aceto oxalate, the impact of catalyst is inquired into, find under same reaction temperature, H in synthesis gas
2content is higher, and the activity of catalyst is lower, and the selective and space time yield of diethy-aceto oxalate is lower, even if the H of about 1%
2the remaining performance that also can have a strong impact on synthetic catalyst in step 2.Therefore, how to facilitate and remove a small amount of H in industrial CO gas economically
2thus obtain the important technology difficult problem that the CO gas meeting subsequent reactions requirement is the industry of development carbonylation synthesis.
Domestic and international for removing a small amount of H in CO gas at present
2technique and catalyst report seldom, comparing typical method is in unstripped gas, add a small amount of O
2carry out selective oxidation reaction to remove hydrogen, catalyst is then loaded noble metal catalyst.
CN102284286A discloses a small amount of H in a kind of selective oxidation removal industry CO synthesis gas
2collosol and gel Pd/A1
2o
3catalyst, wherein, active component palladium content is 0.1-0.5%.This reaction adopts fixed bed reactors, containing a small amount of H
2cO unstripped gas with 2000-8000h
-1air speed by bed, additionally pass into O
2air speed be 10-100h
-1, react under the condition of pressure 0.1-1MPa, temperature 100-300 DEG C, make H in the CO gas after except hydrogen purification
2content is less than 100ppm.Adopt the method, in reaction end gas, the content of hydrogen can drop to 90ppm.Although employing the method, in reaction end gas, the content of hydrogen can drop to 90ppm, and it is 2000h that embodiment only gives feed space velocity
-1experimental data time (catalyst amount is 10 milliliters).This air speed is less, and reaction efficiency is lower.
CN102649568A discloses the method for a kind of CO mist gating catalytic oxidation except hydrogen, be the catalyst of active component by platinum metal, be in the pretreatment gas atmosphere of 1-100% at oxygen content, be 100-400 DEG C in temperature, volume space velocity is 100-10000h
-1, pressure is under the condition of 0-2.0MPa, process 0.0l-40 hour; Then, with hydrogen content be greater than 0-10% CO mist for raw material, in oxygen and raw material, the mol ratio of hydrogen is 0.5-5:1, and reaction temperature is 100-300 DEG C, and volume space velocity is 100-10000h
-1, reaction pressure is under the condition of-0.08-5.0MPa, and raw material is active constituent catalyst reactor and catalyst exposure by being equipped with platinum metal.In described catalyst, preferred platinum or palladium are active component, and the content of platinum group active component is 0.05-1%, and carrier is at least one in silica, aluminium oxide or molecular sieve.Although employing the method, in reaction end gas, the content of hydrogen can drop to below 5ppm, and the method operation is more complicated, needs to carry out special pretreatment to catalyst; And the volume space velocity that the method is suitable for is less, gives the highest volume space velocity and be only 7800h in embodiment
-1time (temperature 270 DEG C, pressure is-0.04MPa) experimental data.This air speed is less, and reaction efficiency is lower.
CN101993073A discloses the selective oxidation of a kind of CO mist except the method for hydrogen, adopts with the CO gas of hydrogen for raw material, reaction temperature be 80-260 DEG C, volume space velocity is 100-10,000h
-1, oxygen/hydrogen mol ratio is 0.5-10:1, reaction pressure is under the condition of-0.08-5.0MPa, raw material contacts with noble metal catalyst, hydrogen in raw material is oxidized to water, wherein noble metal catalyst comprises lamellar composite carrier, active component and auxiliary agent, by weight percentage, catalyst comprises following component: (a) at least one be selected from platinum metal is active component; B () at least one be selected from alkali metal, alkaline-earth metal, IB, IIB, VB, VIIB, VIII, IIIA, IVA or lanthanide compound is auxiliary agent; (c) by a kind of inert carrier kernel and be combined in the lamellar composite carrier that the porous coating material shell on kernel forms.Although employing the method, in reaction end gas, the content of hydrogen can drop to below 1ppm, and the catalyst composition that the method adopts is comparatively complicated, even and if under greater catalytic agent consumption (10 milliliters), the highest volume space velocity that embodiment provides is 8800h
-1.This air speed is still less, and reaction efficiency is lower.
Therefore, explore technology and the efficient catalyst of a small amount of hydrogen in a kind of more efficient, more economical removing industrial CO gas newly, significant.
Summary of the invention
The object of this invention is to provide a kind of new catalyst containing palladium and/or platinum and use this to contain H in the catalyst removal CO raw material of palladium and/or platinum
2method, the method can by H in CO raw material under higher space velocity
2content be reduced to below 90ppm.
The present inventor finds through a large amount of experiments, adopts the catalyst and the magnetically stabilized bed reactor that contain palladium and/or platinum provided by the invention, can fast and effeciently by H in CO raw material
2content (in CO raw material hydrogen content can for 0.01-2 volume %) be reduced to below 90ppm.
To achieve these goals, the invention provides a kind of catalyst containing palladium and/or platinum, wherein, the described catalyst containing palladium and/or platinum contains palladium and/or the platinum that magnetic carrier and load account for the described catalyst 0.1-3 % by weight containing palladium and/or platinum on described magnetic carrier.
Present invention also offers one and remove H in CO raw material
2method, wherein, the method comprises, and in magnetically stabilized bed reactor, is contacted by CO raw material with the catalyst containing palladium and/or platinum under methanation reaction condition; The described catalyst containing palladium and/or platinum is the above-mentioned catalyst containing palladium and/or platinum provided.
The present invention, mainly through adopting the catalyst and magnetically stabilized bed reactor that contain palladium and/or platinum, has the effect of quick dehydrogenation.The volume space velocity of method provided by the invention CO raw material when processing CO raw material can reach 50000h
-1, compared with prior art, significantly improve production efficiency.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of 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 load accounts for the described palladium and/or the platinum that contain the catalyst 0.1-3 % by weight of palladium and/or platinum on described magnetic carrier.The content of described magnetic carrier is 97-99.9 % by weight.It should be noted that, the content containing each component in the catalyst of palladium and/or platinum described in the present invention all calculates with charged material weight.Described containing in the catalyst of palladium and/or platinum, the constituent content of palladium and/or platinum is the percentage that the input amount of palladium and/or platinum accounts for total input amount of magnetic carrier and palladium and/or platinum.
According to catalyst provided by the invention, described magnetic carrier does not specially require, and can produce the material of magnetic for any one.Under preferable case, described magnetic carrier can contain aluminium oxide and magnetic-particle, and described magnetic-particle can be made up of the silica of iron compound and this iron compound coated.
According to catalyst provided by the invention, as long as described magnetic carrier is containing aluminium oxide and magnetic-particle, and make the catalyst containing palladium and/or platinum have superparamagnetism, the content of aluminium oxide and magnetic carrier is not specially required.Under preferable case, based on the gross weight of described magnetic carrier, the content of described magnetic-particle is 1-50 % by weight, and surplus is aluminium oxide.
According to catalyst provided by the invention, described magnetic-particle is made up of the silica of iron compound and this iron compound coated.In described magnetic-particle, the content of silica and iron compound does not specially require, as long as silica can coated iron compound.Under preferable case, in described magnetic-particle, the weight ratio of silica and iron compound is 0.3-4:1, is more preferably 1-3:1.The two can realize the good coated iron compound of silica in this proportion.The magnetic-particle that the present invention adopts coated with silica iron compound to be formed, can avoid iron compound and oxide contact at high temperature to form hercynite, avoids the permanent deactivation of the catalyst containing palladium and/or platinum.In addition, magnetic carrier provided by the invention has good heat endurance and corrosion resistance.
According to catalyst provided by the invention, the kind of the present invention to iron compound does not specially require, as long as can for bringing magnetic containing the catalyst of palladium and/or platinum.That is, can for bring except the iron of the magnetic of stable existence in magnetically stabilized bed reactor containing the catalyst of palladium and/or platinum except containing in described iron compound, other components can be impurity.Such as, described iron compound can be iron slag and other magnetisable material, in order to improve the superparamagnetism of the catalyst containing palladium and/or platinum further, under preferable case, and the iron containing 50-100 % by weight in described iron compound.More preferably, in situation, described iron compound is Fe
3o
4, Fe and γ-Fe
2o
3in one or more.It should be noted that, select Fe
3o
4when preparing magnetic carrier as iron compound, in preparation process, part Fe
3o
4be transformed into γ-Fe
2o
3but the charged material weight ratio of each component is still with Fe when calculating magnetic carrier
3o
4calculate, namely ignore this conversion process.
According to catalyst provided by the invention, the particle diameter of the present invention to iron compound does not specially require, and under preferable case, the particle diameter of described iron compound is 3-30nm.When the particle diameter of described iron compound is within the scope of this, be conducive in 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 Na
2siO
39H
2o is dissolved in distilled water, slowly drips HCl solution under agitation, the pH value of solution is adjusted to 10-13, for subsequent use after filtering.
FeCl is added in the stirred tank that distilled water is housed
36H
2o and/or FeCl
24H
2o, is warming up to 85-90 DEG C, in high-speed agitating process, add NH
3h
2o solution, after high-speed stirred 3-60 minute, adopts magnetic separator to isolate black Fe
3o
4granular product.By the precipitated product ultrasonic disperse after cleaning at above-mentioned pretreated Na
2siO
3in solution, then move in stirred tank, be warming up to 85-100 DEG C, under nitrogen protection and stirring condition, in solution, slowly drip concentration be about HCl solution, in 3-6 hour, the pH value of solution is down to 4-6 by 10-13.Obtain white SiO
2coated Fe
3o
4the magnetic-particle of particle.
By AlCl
36H
2o is dissolved in deionized water, adds high-purity aluminum foil, at 80-100 DEG C, keep 60-72 hour, and aluminium foil is fully dissolved in after in solution, and liquor capacity heating is concentrated into 300-600mL, obtains clarifying translucent aluminum hydroxide sol.
At 10-30 DEG C, aluminum hydroxide sol is mixed with By Amine Solutions (containing hexamethylenetetramine and urea), stir, then add magnetic-particle, pour in the stirred tank filling sulfonated kerosene (the surfactant Span80 containing 0.05 volume %) after fully stirring.At 15-25 DEG C, be uniformly dispersed under the rotating speed of 500-700rpm, form water-in-oil emulsion, subsequently system is warming up to 85-90 DEG C, keeps after 15-60 minute, cool, isolate product, obtain the spherical Al of magnetic (OH)
3.
By spherical for above-mentioned magnetic Al (OH)
3product loading fills in the autoclave of sulfonated kerosene medium; under nitrogen protection in 180-240 DEG C of hydrothermal treatment consists 2-6 hour; after product cleaning oil removing; in pH value be subsequently in the weak aqua ammonia of 10-12 in 80-100 DEG C of ageing 4-10 hour to remove wherein partial impurities; after drying through 60-100 DEG C, the spherical Al of magnetic (OH) of boehmite structure can be obtained
3product.The spherical Al of this magnetic (OH)
3product, through 580-700 DEG C of air atmosphere sintering 2-10 hour, can obtain containing SiO
2coated γ-Fe
2o
3spherical gamma-the Al of magnetic kernel
2o
3carrier.
According to catalyst provided by the invention, described catalyst is preferably made up of palladium on described magnetic carrier of magnetic carrier and load and/or platinum.Further preferred described catalyst is made up of palladium on described magnetic carrier of magnetic carrier and load and platinum.In described catalyst, the ratio of palladium and platinum does not specially require, as long as containing palladium and platinum in described catalyst.Under preferable case, the weight ratio of palladium and platinum is 2-8:1.
According to catalyst provided by the invention, the particle diameter of described catalyst does not specially require, and under preferable case, the particle diameter of described catalyst is 50 μm of-1mm.Like this when realizing the utilization ratio of catalyst as far as possible, make few as much as possible with the flow losses of flow of feed gas of catalyst.
According to the present invention, the preparation method of described catalyst does not specially require, and can carry out, such as infusion process, the precipitation method etc. according to the preparation method of any one catalyst well known by persons skilled in the art.
Present invention also offers one and remove H in CO raw material
2method, wherein, the method comprises, and in magnetically stabilized bed reactor, is contacted by CO raw material with the catalyst containing palladium and/or platinum under methanation reaction condition; The described catalyst containing palladium and/or platinum is the above-mentioned catalyst containing palladium and/or platinum provided.
According to method provided by the invention, described magnetically stabilized bed reactor can be any one magnetically stabilized bed reactor well known by persons skilled in the art, and the present invention does not specially require.Under preferable case, magnetically stabilized bed reactor of the present invention can be made up of reactor and externally-applied magnetic field.As long as reactor and other parts of reactor are made up of the material that magnetic permeability is good, axially add uniform and stable magnetic field along reactor, uniform magnetic field can by dc source and coaxial helmholtz coil or even high-density solenoid provide with reactor.The magnetically stabilized bed reactor that the present invention adopts is solid phase with magnetic retention particle, under uniform magnetic field, forms special bed, not only have the advantage of fixed bed and fluid bed concurrently, greatly can strengthen course of reaction, and preparation technology is simple, the size of magnetically stabilized bed reactor and magnetic field intensity can be selected flexibly according to actual conditions, for large-scale industrial application provides great convenience.
According to method provided by the invention, in the preferred case, the magnetic field intensity that described magnetically stabilized bed reactor produces can be 20-400kA/m.This magnetic field intensity can be selected according to the volume space velocity of CO raw material, and generally, the volume space velocity of CO raw material is larger, and magnetic field intensity is larger, in order to avoid taken away by CO raw material containing the catalyst of palladium and/or platinum, avoids the loss of the catalyst containing palladium and/or platinum.
According to method provided by the invention, in the preferred case, described methanation reaction condition comprises: temperature is 100-300 DEG C, and pressure is 0.1-5MPa, is preferably 0.1-3MPa.
According to method provided by the invention, can with 1000-50000h under methanation reaction condition by CO raw material and the catalyst containing palladium and/or platinum
-1volume space velocity contact.Although adopt method of the present invention at comparatively low-speed (as 1000-10000h
-1) under can completely by the H in CO raw material
2content is reduced to more low content, but air speed lower being unfavorable for improves reaction efficiency, therefore, in the preferred case, the volume space velocity of the CO raw material being far longer than prior art can be adopted, by CO raw material and the catalyst containing palladium and/or platinum under methanation reaction condition with 15000-50000h
-1volume space velocity contact, still can obtain H in CO raw material
2content be reduced to the effect of below 90ppm, substantially increase production efficiency.
According to method provided by the invention, the synthesis gas that described CO raw material can transform for petroleum and natural gas, coal water gas and semiwater gas, steel plant's tail gas etc. are separated through pressure-variable adsorption the CO unstripped gas obtained, the H usually containing 0.01-2 volume % in these CO unstripped gas of industrial preparation
2.Adopt method of the present invention, not only H in CO unstripped gas
2more low content can be dropped to when volume content is lower and remove the H in CO unstripped gas even completely
2but, H in CO unstripped gas
2during volume content higher (as up to 2 volume %), still H can be obtained
2content be reduced to the CO raw material of below 90ppm.
The mode of embodiment is adopted to be described in further detail the present invention below.
In following examples, grain diameter adopts sieve method to select.
Raw material hereinafter used or reagent unless stated otherwise, are commercial goods, and identical reagent source is identical.
Embodiment 1
(1) magnetic-particle preparation
By 189g Na
2siO
39H
2o is dissolved in 1000mL distilled water, slowly drips 3mol/L HCl solution under agitation, the pH value of solution is adjusted to 13, for subsequent use after filtering.
42.2g FeCl is added in the 3L stirred tank that 1200mL distilled water is housed
36H
2o and 20.6gFeCl
24H
2o, is warming up to 85 DEG C, adds the NH of 60mL25% in high-speed agitating process
3h
2o solution, high-speed stirred, after 3 minutes, adopts magnetic separator to isolate black Fe
3o
4particle (grain diameter is 3-30nm).By the black Fe after cleaning
3o
4particle ultrasonic disperse is at above-mentioned pretreated Na
2siO
3in solution, then move in 3L stirred tank, be warming up to 85 DEG C, under nitrogen protection and stirring condition, in solution, drip the HCl solution of concentration 2mol/L, in 3 hours, the pH value of solution is down to 6 by 13, filter and obtain 60g white SiO
2coated Fe
3o
4magnetic-particle (wherein, the Fe of particle
3o
4weight is about 20g, is coated on Fe
3o
4the SiO on surface
2about 40g, silica and Fe
3o
4weight ratio be 2:1).Detect the hysteresis curve display obtained through vibrating specimen magnetometer (VSM) (purchased from American Quantum Design company), magnetic-particle has superparamagnetism.
(2) magnetic carrier preparation
Take AlCl
36H
2o80g, is dissolved in 600mL deionized water, adds 44g high-purity aluminum foil, keeps 72 hours, aluminium foil is fully dissolved in after in solution at 80 DEG C, and liquor capacity heating is concentrated into 300mL, obtains clarifying translucent aluminum hydroxide sol.
At 10 DEG C, measure 100mL aluminum hydroxide sol, mix with the By Amine Solutions (containing hexamethylenetetramine 300g/L and urea 150g/L) of 90mL, stir, add 7.3g magnetic-particle again, pour in the 3L stirred tank filling 1600mL sulfonated kerosene (the surfactant Span80 containing 0.05 volume %) after fully stirring.At 25 DEG C, be uniformly dispersed under the rotating speed of 700rpm, form water-in-oil emulsion, subsequently system is warming up to 90 DEG C, keeps after 15 minutes, cool, isolate product, obtain the spherical Al of magnetic (OH)
3.
By spherical for above-mentioned magnetic Al (OH)
3loading fills in the 1L autoclave of 0.7L sulfonated kerosene medium; the lower 180 DEG C of hydrothermal treatment consists of nitrogen protection 2 hours, after product cleaning oil removing, in pH value be subsequently in the weak aqua ammonia of 10 in 80 DEG C of ageings 5 hours to remove wherein partial impurities; after drying through 60 DEG C, the spherical Al of magnetic (OH) can be obtained
3product.The spherical Al of this magnetic (OH)
3product is by Al (OH)
3, Fe
3o
4with γ-Fe
2o
3(XRD spectra proves, has part Fe
3o
4be oxidized to γ-Fe
2o
3) and SiO
2composition.
The spherical Al of above-mentioned magnetic (OH)
3product sinters 2 hours through 580 DEG C of air atmospheres, can obtain about 45g magnetic spherical gamma-Al
2o
3(wherein, the charged material weight ratio of each component is carrier: Fe
3o
4: SiO
2: Al
2o
3=6:12:82.In magnetic carrier, the content of aluminium oxide is 82 % by weight).The average grain diameter of this carrier is about 200 μm.
(3) preparation of catalyst
By 0.168g PdCl
2be dissolved in 1.0mL2mol/L watery hydrochloric acid, regulate solution ph to be 3, adopt infusion process to be mixed with above-mentioned 10g magnetic carrier by the solution of preparation.Dry 8 hours at 120 DEG C after abundant dipping, and then namely roasting obtains the catalyst CAT-1 containing Pd1 % by weight (charged material weight ratio) for 8 hours at 500 DEG C.The particle diameter of catalyst CAT-1 is 200 μm.
Embodiment 2
(1) magnetic-particle preparation
By 28.4g Na
2siO
39H
2o is dissolved in 1000mL distilled water, slowly drips 3mol/L HCl solution under agitation, the pH value of solution is adjusted to 13, for subsequent use after filtering.
46.7g FeCl is added in the 2L stirred tank that 1200mL distilled water is housed
36H
2o and 17.2gFeCl
24H
2o, is warming up to 90 DEG C, adds the NaOH solution of 160mL6mol/L in high-speed agitating process, and high-speed stirred, after 3 minutes, adopts magnetic separator to isolate black Fe
3o
4particle (grain diameter is 3-30nm).By the black Fe after cleaning
3o
4particle ultrasonic disperse is at above-mentioned pretreated Na
2siO
3in solution, then move in 2L stirred tank, be warming up to 85 DEG C, under nitrogen protection and stirring condition, in solution, drip the HCl solution of concentration 2mol/L, in 3 hours, the pH value of solution is down to 6 by 13.Obtain 26g white SiO
2coated Fe
3o
4magnetic-particle (wherein, the Fe of particle
3o
4weight is about 20g, is coated on Fe
3o
4the SiO on surface
2about 6g, silica and Fe
3o
4weight ratio be 0.3:1).Detect the hysteresis curve display obtained through vibrating specimen magnetometer (VSM), magnetic-particle has superparamagnetism.
(2) magnetic carrier preparation
Take AlCl
36H
2o75.1g, is dissolved in 600mL deionized water, adds 44.6g high-purity aluminum foil, keeps 70 hours, aluminium foil is fully dissolved in after in solution at 90 DEG C, and liquor capacity heating is concentrated into 300mL, obtains clarifying translucent aluminum hydroxide sol.
At 10 DEG C, measure 100mL aluminum hydroxide sol, mix with the By Amine Solutions (containing hexamethylenetetramine 300g/L and urea 150g/L) of 90mL, stir, add 21.3g magnetic-particle again, pour in the 3L stirred tank filling 1600mL sulfonated kerosene (the surfactant Span80 containing 0.05 volume %) after fully stirring.At 25 DEG C, be uniformly dispersed under the rotating speed of 500rpm, form water-in-oil emulsion, subsequently system is warming up to 90 DEG C, keeps after 15 minutes, cool, isolate product, obtain the spherical Al of magnetic (OH)
3.
By spherical for above-mentioned magnetic Al (OH)
3loading fills in the 1L autoclave of 0.7L sulfonated kerosene medium; the lower 180 DEG C of hydrothermal treatment consists of nitrogen protection 2 hours, after product cleaning oil removing, in pH value be subsequently in the weak aqua ammonia of 10 in 80 DEG C of ageings 4 hours to remove wherein partial impurities; after drying through 90 DEG C, the spherical Al of magnetic (OH) can be obtained
3product.The spherical Al of this magnetic (OH)
3product is by Al (OH)
3, Fe
3o
4with γ-Fe
2o
3(XRD spectra proves, has part Fe
3o
4be oxidized to γ-Fe
2o
3) and SiO
2composition.
The spherical Al of above-mentioned magnetic (OH)
3product sinters 2 hours through 580 DEG C of air atmospheres, can obtain about 65g magnetic spherical gamma-Al
2o
3(wherein, the charged material weight ratio of each component is carrier: Fe
3o
4: SiO
2: Al
2o
3=30:9:61.In magnetic carrier, the content of aluminium oxide is 61 % by weight).The average grain diameter of this carrier is about 1mm.
(3) preparation of catalyst
By 0.136g PtCl
2be dissolved in 0.8mL2mol/L watery hydrochloric acid, regulate solution ph to be 3.0, adopt infusion process to be mixed with above-mentioned 10g magnetic carrier by the solution of preparation.Dry 8 hours at 120 DEG C after abundant dipping, and then namely roasting obtains the catalyst CAT-2 of Pt1 % by weight (charged material weight ratio) for 8 hours at 500 DEG C.The particle diameter of catalyst CAT-2 is 1mm.
Embodiment 3
(1) magnetic-particle preparation
By 189g Na
2siO
39H
2o is dissolved in 1000mL distilled water, slowly drips 3mol/L HCl solution under agitation, the pH value of solution is adjusted to 13, for subsequent use after filtering.
By 14.54g black iron powder (grain diameter is 3-30nm) particle ultrasonic disperse at above-mentioned pretreated Na
2siO
3in solution, then move in 3L stirred tank, be warming up to 85 DEG C, under nitrogen protection and stirring condition, in solution, drip the HCl solution of concentration 2mol/L, in 3 hours, the pH value of solution is down to 6 by 13, filter and obtain 60g white SiO
2(wherein, iron powder weight is about 20g to the magnetic-particle of cladding iron powder particle, is coated on the SiO on iron powder surface
2about 40g, the weight ratio of silica and iron powder is 2:1).Detect the hysteresis curve display obtained through vibrating specimen magnetometer (VSM), magnetic-particle has superparamagnetism.
(2) magnetic carrier preparation
Take AlCl
36H
2o80g, is dissolved in 600mL deionized water, adds 44g high-purity aluminum foil, keeps 72 hours, aluminium foil is fully dissolved in after in solution at 90 DEG C, and liquor capacity heating is concentrated into 300mL, obtains clarifying translucent aluminum hydroxide sol.
At 10 DEG C, measure 100mL aluminum hydroxide sol, mix with the By Amine Solutions (containing hexamethylenetetramine 300g/L and urea 150g/L) of 90mL, stir, add 7.3g magnetic-particle again, pour in the 3L stirred tank filling 1600mL sulfonated kerosene (the surfactant Span80 containing 0.05 volume %) after fully stirring.At 20 DEG C, be uniformly dispersed under the rotating speed of 700rpm, form water-in-oil emulsion, subsequently system is warming up to 90 DEG C, keeps after 15 minutes, cool, isolate product, obtain the spherical Al of magnetic (OH)
3.
By spherical for above-mentioned magnetic Al (OH)
3loading fills in the 1L autoclave of 0.7L sulfonated kerosene medium; the lower 180 DEG C of hydrothermal treatment consists of nitrogen protection 2 hours, after product cleaning oil removing, in pH value be subsequently in the weak aqua ammonia of 10 in 80 DEG C of ageings 5 hours to remove wherein partial impurities; after drying through 60 DEG C, the spherical Al of magnetic (OH) can be obtained
3product.The spherical Al of this magnetic (OH)
3product is by Al (OH)
3, Fe
3o
4with γ-Fe
2o
3(XRD spectra proves, has part Fe
3o
4be oxidized to γ-Fe
2o
3) and SiO
2composition.
The spherical Al of above-mentioned magnetic (OH)
3product sinters 2 hours through 600 DEG C of air atmospheres, can obtain about 45g magnetic spherical gamma-Al
2o
3(wherein, the charged material weight ratio of each component is carrier: iron powder: SiO
2: Al
2o
3=6:12:82.In magnetic carrier, the content of aluminium oxide is 82 % by weight).The average grain diameter of this carrier is about 200 μm.
(3) preparation of catalyst
By 0.168g PdCl
2with 0.027g PtCl
2be dissolved in 1.0mL2mol/L watery hydrochloric acid, regulate solution ph to be 3.0, adopt infusion process to be mixed with above-mentioned 10g magnetic carrier by the solution of preparation.Dry 8 hours at 100 DEG C after abundant dipping, and then namely roasting obtains the catalyst CAT-3 containing Pd1.0 % by weight and Pt0.2 % by weight (charged material weight ratio) for 8 hours at 500 DEG C.The particle diameter of catalyst CAT-3 is 200 μm.
Embodiment 4
Adopt the method Kaolinite Preparation of Catalyst of embodiment 3, unlike, adjustment PdCl
2and PtCl
2input amount, make obtained catalyst CAT-4 contain the Pd of the 0.2 % by weight and Pt of 0.2 % by weight.
Embodiment 5
Adopt the method Kaolinite Preparation of Catalyst of embodiment 2, unlike, adjustment PtCl
2input amount, make obtained catalyst CAT-5 contain the Pt of 2 % by weight.
Embodiment 6
Adopt the method Kaolinite Preparation of Catalyst of embodiment 2, unlike, adjustment PtCl
2input amount, make obtained catalyst CAT-6 contain the Pt of 3 % by weight.
Embodiment 7
Adopt the method Kaolinite Preparation of Catalyst of embodiment 2, unlike, adjustment PtCl
2input amount, make obtained catalyst CAT-7 contain the Pt of 0.5 % by weight.
Embodiment 8
The method preparation of embodiment 2 is adopted to contain the catalyst of palladium and/or platinum, unlike, when preparing magnetic-particle, silica and Fe
3o
4weight ratio be 0.1:1.
The obtained catalyst containing palladium and/or platinum is numbered CAT-8.
Comparative example 1
Adopt the method Kaolinite Preparation of Catalyst of embodiment 2, unlike, adjustment PtCl
2input amount, make obtained catalyst D1 contain the Pt of 3.5 % by weight.
Testing example 1
Catalyst sample CAT-1 1mL being contained palladium and/or platinum inserts magnetic stablizing bed micro anti-evaluation device, and (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 multilayer 300-400 object stainless steel cloth, and this distributor is positioned at the feed end of reaction tube; 4 additional even coilings of coil flat copper wire form, each internal coil diameter 65mm, external diameter 160mm, thickness 60mm, the number of turn 400, adjacent windings centre-to-centre spacing 70mm during installation) in, pass into mist (volume content: CO:98.0%, H
2: 0.3%; O
2: 0.16%, surplus is N
2), H in product
2concentration analyzes (detection of gas chromatograph is limited to 0.1ppm, identical below) by gas-chromatography on-line checkingi.H in reaction velocity, magnetic field intensity, reaction temperature and reaction pressure and product
2concentration is as shown in table 1.
Table 1
Testing example 2
Respectively 1mL is inserted in magnetic stablizing bed micro anti-evaluation device containing the catalyst sample CAT-2 to CAT-8 of palladium and/or platinum, pass into mist (volume content: CO:98.0%, H
2: 0.3%; O
2: 0.16%, surplus is N
2), H in product
2concentration is analyzed by gas-chromatography on-line checkingi.H in catalyst, reaction velocity, magnetic field intensity, reaction temperature and reaction pressure and product
2concentration is as shown in table 2.
Test comparison example 2
Adopt the method for testing example 2, unlike, D1 selected by catalyst.
H in reaction velocity, magnetic field intensity, reaction temperature and reaction pressure and product
2concentration is as shown in table 2.
Table 2
Testing example 3
1mL is inserted in magnetic stablizing bed micro anti-evaluation device containing the catalyst sample CAT-1 of palladium and/or platinum, passes into the mist containing CO, hydrogen and oxygen, H in product
2concentration is analyzed by gas-chromatography on-line checkingi.Reaction temperature is 300 DEG C, and pressure is 3MPa, and air speed is 20000h
-1, magnetic field intensity is 300kA/m.H in mist
2content, H in product
2concentration is as shown in table 3.
Test comparison example 3
Adopt the method for testing example 3, unlike, D1 selected by catalyst.
H in mist
2content, H in product
2concentration is as shown in table 3.
Table 3
As apparent from table 1-3 can, adopt method provided by the invention, reach 50000h in air speed
-1time, the content of hydrogen in product can be reduced to below 90ppm.In addition, as can be seen from table 2 and 3, when containing the Pt of 3.5 % by weight in catalyst D1, the catalytic activity of catalyst D1 does not enlarge markedly because of the increase of platinum content, on the contrary because tenor exceedes certain numerical value, metal ion, at surface aggregation, causes active obviously decline.Therefore.In the catalyst containing palladium and/or platinum, as long as have appropriate palladium and/or platinum, catalyst just can have higher catalytic activity.And when the catalyst containing palladium and/or platinum of the present invention contains palladium and/or the platinum of 0.1-3 % by weight, not only there is higher catalytic activity, and significantly reduce production cost.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (14)
1. contain a catalyst for palladium and/or platinum, it is characterized in that, the described catalyst containing palladium and/or platinum contains magnetic carrier and load accounts for the described palladium and/or the platinum that contain the catalyst 0.1-3 % by weight of palladium and/or platinum on described magnetic carrier.
2. catalyst according to claim 1, wherein, described magnetic carrier contains aluminium oxide and magnetic-particle, and described magnetic-particle is made up of the silica of iron compound and this iron compound coated.
3. catalyst according to claim 2, wherein, based on the gross weight of described magnetic carrier, the content of described magnetic-particle is 1-50 % by weight, and surplus is aluminium oxide.
4. catalyst according to claim 2, wherein, in described magnetic-particle, the weight ratio of silica and iron compound is 0.3-4:1.
5. according to the catalyst in claim 2-4 described in any one, wherein, described iron compound is Fe
3o
4, Fe and γ-Fe
2o
3in one or more.
6. according to the catalyst in claim 2-5 described in any one, wherein, the particle diameter of described iron compound is 3-30nm.
7. catalyst according to claim 1, wherein, described catalyst is made up of palladium on described magnetic carrier of magnetic carrier and load and/or platinum.
8. catalyst according to claim 7, wherein, in described catalyst, the weight ratio of palladium and platinum is 2-8:1.
9. according to the catalyst in claim 1-8 described in any one, wherein, the particle diameter of described catalyst is 50 μm of-1mm.
10. one kind removes H in CO raw material
2method, it is characterized in that, the method comprises, and in magnetically stabilized bed reactor, is contacted by CO raw material with the catalyst containing palladium and/or platinum under methanation reaction condition; The described catalyst containing palladium and/or platinum is the catalyst containing palladium and/or platinum in claim 1-9 described in any one.
11. methods according to claim 10, wherein, the magnetic field intensity that described magnetically stabilized bed reactor produces is 20-400kA/m.
12. methods according to claim 10, wherein, described methanation reaction condition comprises: temperature is 100-300 DEG C, and pressure is 0.1-5MPa.
13. methods according to claim 10, wherein, by CO raw material and the catalyst containing palladium and/or platinum under methanation reaction condition with 1000-50000h
-1volume space velocity contact.
14. methods according to claim 10, wherein, H in described CO raw material
2volumn concentration be 0.01-2%.
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