CN103394354A - Catalyst loaded on carbon sphere and preparation method of catalyst - Google Patents
Catalyst loaded on carbon sphere and preparation method of catalyst Download PDFInfo
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- CN103394354A CN103394354A CN2013103683424A CN201310368342A CN103394354A CN 103394354 A CN103394354 A CN 103394354A CN 2013103683424 A CN2013103683424 A CN 2013103683424A CN 201310368342 A CN201310368342 A CN 201310368342A CN 103394354 A CN103394354 A CN 103394354A
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Abstract
The invention discloses a catalyst loaded on a carbon sphere and a preparation method of the catalyst. A carbon sphere carrier is a carbonized ion exchange resin microsphere. Effective compositions and/or an auxiliary or precursors of the effective compositions and/or the auxiliary of the catalyst are subjected to ion exchange, adsorption, sedimentation and/or dipping and are uniformly loaded on the surface and/or in pore channels of the ion exchange resin microsphere before carbonization of an ion exchange resin. The preparation method of the catalyst is simple in operation and convenient to control, obtain catalyst particles are good in spherical degree and high in mechanical strength, and higher catalytic activity and excellent low carbon olefin selectivity are presented in a syngas conversion reaction process.
Description
Technical field
The present invention relates to a kind of catalyst that loads on the carbon ball, particularly, relate to a kind of catalyst that loads on the carbon ball that precursor is ion exchange resin.
Background technology
In the preparation method of loaded catalyst, spray drying process and infusion process are two kinds of the most frequently used preparation methods.Although but loaded catalyst particle good sphericity prepared by spray drying process, preparation method's complexity, although loaded catalyst preparation process prepared by infusion process is relatively simple, the particle sphericity of catalyst is bad.Find that a kind of preparation process is simple, particle good sphericity, method for preparing catalyst that granule strength is large be one of task of catalyst preparation field researcher all the time.
Through research for many years, Many researchers is found: the catalytic performance quality of loaded catalyst not only depends on the composition of catalyst itself, the for example kind of the active principle of catalyst, auxiliary agent and carrier and content, different preparation method also depends on method for preparing catalyst, because may cause the mixing dispersing mode between the different active principles of catalyst different with uniformity.So, usually there will be the huge situation of catalyst catalytic performance difference that finally obtains when identical catalyst adopts different preparation methods to prepare that forms.
Usually, it is believed that: the active principle of catalyst and/or auxiliary agent disperse or mix more even, the catalytic activity of catalyst is just better, the active principle of catalyst and/or auxiliary agent distribute more even in carrier, the performance of catalyst is also just better, has so just determined to guarantee that active principle and/or auxiliary agent are uniformly dispersed and guarantee that it is the key of producing high-performance supported type catalyst that active principle and/or auxiliary agent are evenly distributed in carrier.
Also have, for loaded catalyst, the compatibility of catalyst active principle and/or auxiliary agent and carrier and the cooperative effect between them are also to obtain the key factor of high-performance supported type catalyst.
In recent years, the carbon ball of usining is increasing as the research of the catalyst of carrier, and for example, CN10269875A discloses a kind of nano-sized iron oxide/carbon ball composite catalyst, preparation method and application.Wherein, ferric oxide nanometer particle loads on carbon ball surface equably.Its preparation method is to utilize Fenton reaction, the strong oxidizing property while namely utilizing hydrogen peroxide and ferrous ion to coexist to modify carbon ball surface, thereby make nano level iron oxide particles distribute equably or load on carbon ball surface, thereby obtaining nano-sized iron oxide/carbon ball composite catalyst.The disclosed method of this patent documentation has solved the problems such as the serious reunion of nano level ferric oxide catalyst particle, and resulting catalyst can be used as efficient burning catalyst, the agent of light degradation catalytic organism and petroleum cracking catalyst.
The carbon ball carrier common intensity that above-mentioned catalyst uses is lower, by nanometer ferro oxide or its presoma when the Fenton reaction load is on carbon ball surface, need the long-time described carbon ball that stirs, like this, just likely carbon ball carrier is caused damage, thereby it is damaged to a certain extent that it is occurred, and this likely has influence on the sphericity of final catalyst granules.
CN102125844A discloses a kind of method and application thereof for preparing iron charcoal micron ball material, this iron charcoal micron ball material is under hydrothermal condition, by single step reaction, to make with the aqueous solution of molysite containing sugar, wherein, the ferriferous oxide nano particle is evenly dispersed in the carbon ball of micron-scale, this iron charcoal micron ball material can be used as the catalyst of Fischer-Tropsch synthesis, and it has higher C than existing not modified iron catalyst
5The advantage such as+hydrocarbon-selective and stability.
During the preparation method of the iron charcoal micron ball material of putting down in writing in the document is actually and just the iron component is incorporated into to the raw material for preparing carbon ball presoma in carbon ball presoma preparation process, thereby, in the carbon ball presoma that forms, be uniform-distribution with the presoma of ferriferous oxide nano particle, by carbonization or roasting, form the unique texture in the carbon ball that the ferriferous oxide nano particle is evenly dispersed in micron-scale, but such preparation method be difficult to guarantee to make most of ferriferous oxide distribution of particles the surface of carbon ball and or duct in.
Above-mentioned disclosed carbon ball material or carbon ball carrier material ubiquity the shortcoming of the not high and preparation process complexity of mechanical strength.How to overcome above-mentioned shortcoming and find that a kind of process is simple, the end product good sphericity, mechanical strength is large and to specific reaction or product have better catalytic activity and optionally the preparation method of carbon sphere catalyst be very urgent.
The present invention is intended to the better preparation method who solves above-mentioned technical barrier and make every effort to find a kind of catalyst take the carbon ball as carrier, thereby, make the catalyst that makes show higher catalytic activity and selectivity of product, better catalyst granules sphericity and larger catalyst granules intensity.
Summary of the invention
According to a first aspect of the invention, a kind of catalyst that loads on the carbon ball is provided, it is characterized in that: this carbon ball carrier is the ion exchange resin of carbonization, and the active principle of described catalyst and/or auxiliary agent or their precursor are loaded in the surface and/or duct of ion exchange resin equably through ion-exchange, absorption, precipitation and/or dipping before described ion exchange resin carbonization.
Usually, described ion exchange resin is highly basic or weak basic anion exchange resin microballoon or strong acid or Weak-acid cation exchange resin microballoon, for example, described ion exchange resin is further macroporous type highly basic or weak basic anion exchange resin microballoon or macroporous type strong acid or Weak-acid cation exchange resin microballoon.
As the exemplary and nonrestrictive example of above-mentioned catalyst, but oxide and/or the carbide of the active principle iron content of above-mentioned catalyst; The precursor of the active principle of described catalyst can thermal decomposition be the water-soluble salt solution of the oxide of iron; But the oxide of auxiliary agent copper, potassium, cobalt, nickel and/or the manganese of described catalyst, the precursor of the auxiliary agent of described catalyst can thermal decomposition be the water-soluble salt solution of the oxide of copper, potassium, cobalt, nickel and/or manganese.Particularly, the precursor of the active principle of above-mentioned catalyst is further anion state metal complex or the cationic slaine of iron that contains iron ion.
Equally, as the exemplary and nonrestrictive example of above-mentioned catalyst, but the catalyst of above-mentioned catalyst synthesis gas one step producing light olefins catalyst, fischer-tropsch synthetic catalyst, methanation catalyst prepared by synthetic gas or while co-producing light olefins, light oil and methane.
According to second aspect present invention, a kind of preparation method who loads on the catalyst on the carbon ball is provided, comprise the following steps:
(1) described ion exchange resin microballoon is put into to the active principle of described catalyst and/or the aqueous solution of auxiliary agent or their precursor, carry out sufficient Agitation and mixing, so that the active principle of catalyst and/or auxiliary agent or their precursor and described ion exchange resin carry out sufficient ion-exchange, absorption, precipitation and/or dipping.Thereby loaded on equably in the surface and/or duct of described ion exchange resin;
(2) the described ion exchange resin microballoon after cleaning above-mentioned steps (1), to remove unnecessary catalyst active principle and/or auxiliary agent or their precursor, then, carry out drying, to remove moisture;
(3) under inert atmosphere, described ion exchange resin microballoon after roasting above-mentioned steps (2), in order to make the carbonization of described ion exchange resin microballoon become the carbon ball, simultaneously, the active principle of described catalyst and/or the precursor of auxiliary agent are thermal decomposited active principle and/or the auxiliary agent into described catalyst, thereby, obtain active principle and/or auxiliary agent and loaded on equably the catalyst in carbon ball surface and/or duct.
Preferably, in step (1), the Agitation and mixing time can be 8-24 hour; In step (2), baking temperature can be 80-150 ℃, can be 2-24 hour drying time; In step (3), sintering temperature can be 300-650 ℃,, but roasting time 2-8 hour.
In above-mentioned preparation method, preferably, the particle diameter of described ion exchange resin microballoon is the 0.2-1.0 millimeter, the precursor of the active principle of described catalyst is to carry out with described ion exchange resin microballoon the Organic Iron salting liquid of ion-exchange, such as the potassium ferricyanide, ammonium ferric oxalate, ferric ammonium sulfate and/or ferric citrate etc.; Or ironic citrate, iron chloride, ferric nitrate, ferric sulfate, ferrous sulfate, ferric oxalate, ferric acetate, iron pentacarbonyl.
The accompanying drawing explanation
Fig. 1 is the scanning electron photo of the catalyst for preparing of preparation method of the present invention;
The specific embodiment
By the description below with reference to accompanying drawing, be further explained in detail the present invention, but following description is only be used to making the general technical staff of the technical field of the invention can more be expressly understood principle of the present invention and marrow, and do not mean that the present invention is carried out to any type of restriction.
Material with carbon element has wide application in a lot of fields, the carbon ball is as a kind of special shape of material with carbon element, because of its special spherical structure and good surface modificability, be used as gradually the carrier material of electrode material, energy storage hydrogen storage material, sorbing material, lubricant material and some high performance catalysts.Simultaneously, itself also possesses certain catalytic activity the carbon ball, and under certain conditions, can bring into play the effect of catalyst promoter, when the carbon ball is used as catalyst carrier, in some cases, it can bring into play multiple action, particularly, and when its carrier as the oxide catalyst of oxide catalyst, for example iron, itself and oxide catalyst active principle show extraordinary compatibility and synergy, are the desirable carrier materials of oxide catalyst.
Usually, the carbon ball can be by organic carbon hydrate preparation, for example, by glucose, as carbon source, through Hydrothermal Synthesis, prepares the carbon ball; Or prepare hollow carbon balls by organic carbon sources such as sulfonated polystyrene microballoon, furancarbinol and phenolic resins.Most typical carbon ball preparation method's a example is as follows:
1) prepare the uniform polystyrene microsphere template of diameter; 2) polystyrene moulding is added to sulfonation in the concentrated sulfuric acid, by controlling the sulfonation time, obtain the different polystyrene moulding of sulfonation degree; 3) utilize phenolic resins and sulfonated polystyrene micro ball template to prepare polystyrene/phenolic resin composite balls; 4), by the composite balls carbonization, obtain the carbon ball.
Carbon ball prepared by said method can be used as electrode material, energy storage hydrogen storage material, sorbing material and lubricant, also useful as catalysts carrier.
Generally speaking, carbon ball preparation method can comprise chemical vapour deposition technique, solvent-thermal method and template etc., and these methods cut both ways, but the most frequently used be template, mostly carbon source is the organic carbon hydrate.Usually, the carbon ball can be divided into nanoscale, submicron order, micron order and grade carbon ball, and nanoscale and submicron order carbon ball be due to little, the easy reunion of size, so less stable, usually, be micron order and grade carbon ball as the carbon ball of catalyst carrier.
The carbon ball of various sizes not only can be used to build various multi-functional dopant materials, and itself also can be used for catalysis, medicine carrying, nano-device etc.Yet these application but depend on size and the dispersiveness of carbon ball to a great extent.Therefore, prepare good dispersion, the high-quality carbon ball of moderate dimensions just seems particularly important.At present, generally acknowledge that in the world preparing carbon ball most effectual way is the phenolic resins polymerization.The method preparation easily, Heat stability is good, easily change into the carbon ball.But raw material-phenol and formaldehyde that the method is used have high carcinogenic.Therefore, adopt the carbon ball of the synthetic heat endurance of low toxicity raw material and favorable dispersibility to have very large meaning to its practical application.
Some patent documentations also disclose some carbonaceous materials, the particularly preparation method of carbon ball, for example, CN1480397A discloses a kind of preparation method of high-strength resin-based spheric active carbon, it is take spherical resin as raw material, through swelling, degree of depth sulfonation, gradient concentration acid elution, pass through again high temperature cabonization and steam activation, obtain spherical activated carbon.
CN102247819A discloses a kind of preparation method of magnetic carbonized resin microspheres, it comprises potassium ferricyanide solution is mixed with anion exchange resin, so that they carry out ion-exchange, afterwards, again the resin of drying is carried out to carbonization, obtain the be magnetic carbon ball of particle of load, this magnetic carbon sphere is used as sorbent material, the COD value of leather waste water can be effectively reduced, and sulphur, chromium content in leather waste water can be reduced.
CN102643513A discloses a kind of preparation method of m-aminophenyl resinox ball and the preparation method of carbon ball.Wherein, make m-aminophenol and formaldehyde carry out polymerisation under ammoniacal liquor and/or ethylene glycol catalytic action, in course of reaction, form micella, m-aminophenol and formaldehyde carry out polymerisation in micella, form m-aminophenyl resinox ball, resulting m-aminophenyl resinox ball has higher monodispersity and dimensional controllability, after this m-aminophenyl resinox ball roasting, can obtain corresponding carbon ball, the carbon ball also has higher monodispersity.This carbon ball can be used as the decorative material of electrode after loaded metal platinum, for the reduction of oxygen and the catalytic oxidation of methyl alcohol.
For micron and/or grade carbon ball as catalyst carrier, except sphericity, particle diameter and the dispersiveness of carbon ball itself, the active ingredient of catalyst and auxiliary agent distribution situation and the dispersing uniformity on carbon ball carrier is also most important to final catalyst performance.
Therefore, finding a kind of method that makes active ingredient and/or the auxiliary agent high degree of dispersion of catalyst and be evenly distributed in and duct surperficial as the carbon ball of catalyst carrier is the key that preparation loads on the high-quality catalyst on the carbon ball.
Clearly, the method by simple dipping or precipitation can't and be evenly distributed in carbon ball surface and duct the active ingredient of catalyst and/or auxiliary agent high degree of dispersion.
As mentioned above, organic resin, for example phenolic resins can be used as preparing the carbon source material of carbon ball as organic carbon source, if the active ingredient of above-mentioned catalyst and/or auxiliary agent can by certain technological means be dispersed in the carbon ball presoma, be in carbon source material, after the carbonization of carbon ball presoma, they just can be realized high degree of dispersion and be evenly distributed in the surface and duct of carbon ball.
According to this thinking, the inventor is through repeatedly studying and testing, find that ion exchange resin can be used as the presoma of above-mentioned carbon ball, is carbon source material, and preferably, the active ingredient of above-mentioned catalyst and/or the presoma of auxiliary agent are to carry out with above-mentioned ion exchange resin the water-soluble salt solution of ion-exchange, absorption, precipitation and/or dipping.More preferably, the presoma of the active ingredient of above-mentioned catalyst and/or auxiliary agent is to carry out simultaneously the water-soluble salt solution of ion-exchange, absorption, precipitation and dipping with above-mentioned ion exchange resin.
Usually, ion exchange resin is made with methodology of organic synthesis.Raw material commonly used is styrene or acrylic acid (ester), by polymerisation, generate the skeleton with three dimensions dimensional network structure, on skeleton, import again the dissimilar chemical active radical that is generally acidity or basic group, thereby make it possess the characteristic of ion-exchange.
Water insoluble and the common solvent of ion exchange resin.Most of granulation shapes, also have some to make fibrous or powdery.The size of resin particle is generally in 0.3-1.2 millimeter scope, and major part is between 0.4～0.6.They have higher mechanical strength, and chemical property is also very stable, and arranged long service life under normal circumstances.
In ion exchange resin, contain one or more chemical active radicals, it is namely exchange functional group, can be from solving some cation, for example H in the aqueous solution
+Or Na
+Or anion, for example OH
-Or Cl
-, simultaneously, other cations or the anion that in adsorbent solution, originally had.Be that ion in resin and the ion in solution are realized intercoursing.
In ion exchange resin, the chemical active radical kind has determined its main character and classification.At first, it is divided into resin cation and the large class of resin anion (R.A.) two, they can be respectively with solution in cation and anion carry out ion-exchange.Resin cation is divided into again highly acid and faintly acid two classes, and resin anion (R.A.) is divided into again strong basicity and alkalescent two classes.
Ion exchange resin is divided into phenylethylene resin series and acrylic resin according to the kind of its matrix, and can be divided into according to the physical arrangement of resin gel-type ion-exchange resin and macroreticular ion exchange resin.
Macroreticular ion exchange resin is when polymerisation, to add pore-foaming agent, forms the skeleton of mandruka columnar structure, and there are a large amount of permanent micropores and/or duct in inside, then imports cation exchange groups and make.It also has minute aperture and large mesh, and when it was wetting, aperture reached 100～500 nanometers, and its size and number can be controlled in the preparation.The surface area in duct can increase to over 1000m
2/ g.This not only provides good contact conditions for ion-exchange, shorten the distance of ion diffusion, also increased many chain links activated centre, by intermolecular Van der Waals force, can produce the Molecular Adsorption effect, can as active carbon, adsorb various nonionic materials, enlarge its function.
The hole of macroreticular ion exchange resin inside is many, and surface area is large, and activated centre is many, and the ion diffusion velocity is fast, and ion-exchange speed is also fast, usually, and its approximately than gel-type ion-exchange resin fast approximately ten times.During use, effect is fast, efficiency is high, and the required processing time shortens.Macroreticular ion exchange resin also has multiple advantage: swelling resistance, and not easily broken, resistance to oxidation, wear-resistant, heat-resisting and heatproof degree changes.
Therefore, in the present invention, most preferably, the presoma that is used as the carbon ball of catalyst carrier is various types of macroreticular ion exchange resins.such resin properties and structure make its not only can with the active ingredient of catalyst, auxiliary agent and/or their precursor solution are realized sufficient ion exchange process, also can adsorb easily, precipitation and/or dipping process, thereby, the active ingredient of catalyst and/or the load capacity of auxiliary agent are significantly increased, and, can just can realize in the short period of time the active ingredient of catalyst, auxiliary agent and/or their presoma high degree of dispersion and be evenly distributed in the surface and duct of ion exchange resin, and then guarantee in the active ingredient of ion exchange resin carbonization rear catalyst and/or auxiliary agent can high degree of dispersion and be evenly distributed on the carbon ball surface and duct as catalyst carrier.
It should be noted that: catalyst of the present invention comprises any loaded catalyst take the carbon ball as carrier, especially, and the supported oxide catalyst take the carbon ball as carrier, particularly, the loading type iron oxide take the carbon ball as carrier and/or ferrous-carbide catalyst.
Equally, it should be noted that: catalyst of the present invention is not restricted to oxide catalyst or ferrum-based catalyst, and catalyst of the present invention comprises any loaded catalyst take the carbon ball as carrier, and wherein, carbon ball carrier is the ion exchange resin microballoon of carbonization; The active principle of described catalyst and/or auxiliary agent or their precursor can be loaded in the surface and/or duct of ion exchange resin equably through ion-exchange, absorption, precipitation and/or dipping before the carbonization of described ion exchange resin microballoon becomes the carbon ball.
Theoretically, in the present invention, the relative scale between catalyst active principle and auxiliary agent is not done to special restriction, the relative scale between carbon ball carrier and catalyst active principle and/or auxiliary agent is not done to special restriction yet, but preferably, part by weight between catalyst promoter and active principle is 0-1, for example 0-0.5; Part by weight between catalyst active principle and/or auxiliary agent and carbon ball carrier is 0.05-5,0.1-1 for example, particularly, 0.15-0.7.
Particularly, in the present invention, by composition and the preparation parameter of regulating catalyst, can change the selective of catalyst, wherein, ferrum-based catalyst is modal catalyst, when its catalysts as synthesizing low-carbon alkene, with material with carbon element, for example carbon ball, as catalyst carrier, be considered to be conducive to improve selectivity of light olefin, but the catalyst strength by material with carbon element, the load of for example carbon ball is usually not high, so, in use easily loss.Therefore, the catalyst strength of raising carbon ball load is one of free-revving engine of the present invention.
Usually, the selection of the precursor kind of the selection by the amberlite lipid species and/or catalyst active principle and/or auxiliary agent can make the load of carbon ball different catalyst activity component and/or auxiliary agent.For example, when the catalyst active principle on loading on the carbon ball is iron oxide and/or cementite, the selectivity of light olefin of catalyst is just higher, at this moment, catalyst is suitable as the technique by synthesis gas one step producing light olefins, and the catalyst active principle when loading on the carbon ball on is while being mainly iron sulfide, and the methane selectively of catalyst is just higher, at this moment, catalyst is suitable as the technique by preparing methane by synthetic gas.
In the present invention, load on carbon ball surface and duct in catalyst active principle and/or auxiliary agent can exist with the form of nano particle, also can exist with the form of sub-micron and/or micro particles.
Such catalyst is for example catalyst of efficient burning catalyst, the agent of light degradation catalytic organism, petroleum cracking catalyst, synthesis gas one step producing light olefins catalyst, fischer-tropsch synthetic catalyst, methanation catalyst prepared by synthetic gas or while co-producing light olefins, light oil and methane etc.
Below; by exemplary and nonrestrictive specific embodiment, explain in further detail the present invention; so that those of ordinary skills are expressly understood essence of the present invention and marrow more, but following examples do not form any restriction to protection domain of the present invention.
Embodiment
Embodiment 1
The 1.5 gram potassium ferricyanides are dissolved in 300 ml deionized water, be configured to ion exchanged soln, described ion exchanged soln is the precursor solution that the catalyst active principle contains the Fe phase, 30 grams (are purchased by the macroporous type strong-base anion-exchange resin D201 microballoon that styrene polymerization forms, average grain diameter is 0.6 millimeter, density is 0.85 grams per milliliter, and specific area is 550m
2/ g) put into above-mentioned ion exchanged soln, after ultrasonic wave is processed, continuous stirring 24 hours, then with deionized water, wash the unnecessary salting liquid of resin microsphere Adsorption on Surface off, and afterwards, resin microsphere is put into to 90 ℃ of drying boxes oven dry 8 hours, obtain yellow bead.Dried resin microsphere sample (yellow bead) is put into to quartz boat (roaster), at N
2Atmosphere and 500 ℃ of lower roastings 4 hours, obtain black microspheric form catalyst.The mean intensity that records this catalyst granules is 440N/mm.The physical characteristic of this catalyst and chemical composition are respectively as shown in Table 1 and Table 2.
Fig. 1 is the scanning electron photo of the loaded catalyst of the present invention of preparation in embodiment 1, from Fig. 1, can obviously finding out: the sphericity of loaded catalyst particle of the present invention is very good, its surface uniform ground catalyst active principle that distributing contains the Fe phase, and containing Fe does not have agglomeration on carbon ball carrier surface.
The comparative example 1
(be purchased, average grain diameter is 0.6 millimeter to the macroporous type strong-base anion-exchange resin D201 microballoon that 30 grams are formed by styrene polymerization, and density is 0.85 grams per milliliter, and specific area is 550m
2/ g) put into 90 ℃ of drying boxes to dry 12 hours.Dried resin microsphere sample is put into to quartz boat (roaster), at N
2Atmosphere and 500 ℃ of lower roastings 4 hours, obtain hollow carbon balls, and this carbon ball intensity is extremely low, and hand touches namely broken, can't carry out the load of catalyst active principle and/or auxiliary agent.
Embodiment 2
3.8 gram ammonium ferric oxalates are dissolved in 300 ml deionized water, be configured to ion exchanged soln, described ion exchanged soln is the precursor solution that the catalyst active principle contains the Fe phase, 10 grams (are purchased by the macroporous type strong-base anion-exchange resin D201 microballoon that styrene polymerization forms, average grain diameter is 0.5 millimeter, density is 0.75 grams per milliliter, and specific area is 450m
2/ g) put into above-mentioned ion exchanged soln, after ultrasonic wave is processed, continuous stirring 12 hours, then with deionized water, wash the unnecessary salting liquid of resin microsphere Adsorption on Surface off, and afterwards, resin microsphere was put into to 120 ℃ of drying bakers dry 10 hours, obtain combining the look bead.Dried resin microsphere sample (brown bead) is put into to quartz boat (roaster), at N
2Atmosphere and 700 ℃ of lower roastings 4 hours, obtain black microspheric form catalyst.The mean intensity that records this catalyst granules is 285N/mm.The physical characteristic of this catalyst and chemical composition are respectively as shown in Table 1 and Table 2.
Embodiment 3
1.1 gram ferric citrates are dissolved in 800 ml deionized water, be configured to ion exchanged soln, described ion exchanged soln is the precursor solution that the catalyst active principle contains the Fe phase, 20 grams (are purchased by the macroporous type strong-base anion-exchange resin D201 microballoon that styrene polymerization forms, average grain diameter is 0.6 millimeter, density is 0.85 grams per milliliter, and specific area is 550m
2/ g) put into above-mentioned ion exchanged soln, after ultrasonic wave is processed, continuous stirring 24 hours, with deionized water, wash again the unnecessary salting liquid of resin microsphere Adsorption on Surface off, afterwards, resin microsphere is put into to 120 ℃ of drying box oven dry 12 hours, obtain pale red comprehensive look bead.Dried resin microsphere sample (pale red comprehensive look bead) is put into to quartz boat (roaster), at N
2Atmosphere and 500 ℃ of lower roastings 4 hours, obtain black microspheric form catalyst.The mean intensity that records this catalyst granules is 363N/mm.The physical characteristic of this catalyst and chemical composition are as shown in Table 1 and Table 2.
Embodiment 4
3.0 gram iron chloride are dissolved in 300 ml deionized water, be configured to ion exchanged soln, described ion exchanged soln is the precursor solution that the catalyst active principle contains the Fe phase, 20 grams (are purchased by macroporous type storng-acid cation exchange resin 732 microballoons that styrene polymerization forms, average grain diameter is 0.8 millimeter, density is 0.8 grams per milliliter, and specific area is 450m
2/ g) put into above-mentioned ion exchanged soln, after ultrasonic wave is processed, continuous stirring 12 hours, with deionized water, wash again the unnecessary salting liquid of resin microsphere Adsorption on Surface off, afterwards, resin microsphere is put into to 60 ℃ of drying box oven dry 12 hours, obtain the light red transparent beads.Dried resin microsphere sample (light red transparent beads) is put into to quartz boat (roaster), at N
2Atmosphere and 700 ℃ of lower roastings 4 hours, obtain black microspheric form catalyst.The mean intensity that records this catalyst granules is 212N/mm.The physical characteristic of this catalyst and chemical composition are as shown in Table 1 and Table 2.
The comparative example 2
6.54 gram ferric citrates are dissolved in 10 ml deionized water, be configured to dipping solution, described dipping solution is the precursor solution that the catalyst active principle contains the Fe phase, 5 grams (are purchased with porous carbon ball carrier prepared by the phenolic resins polymerization, average grain diameter is 0.4 millimeter, density is 1.35 grams per milliliters, and specific area is 500m
2/ g) put into above-mentioned dipping solution, after ultrasonic wave is processed, standing 12 hours, then the carbon ball carrier after flooding was put into 120 ℃ of drying bakers dry 16 hours.To flood and dried carbon ball carrier in still air and 500 ℃ of lower roastings 4 hours, obtain black microspheric form catalyst.The mean intensity that records this catalyst granules is 187N/mm.The physical characteristic of this catalyst and chemical composition are as shown in Table 1 and Table 2.
The comparative example 3
6.5 gram ferric citrates are dissolved in 10 ml deionized water, are configured to dipping solution, described dipping solution is the precursor solution that the catalyst active principle contains the Fe phase, by 5 gram spheric active carbon carriers (be purchased,, average grain diameter is 0.5 millimeter, density 0.55 grams per milliliter, specific area are 1500m
2/ g) put into above-mentioned dipping solution, after ultrasonic wave is processed, standing 12 hours, then the absorbent charcoal carrier after flooding is put into 120 ℃ of drying box oven dry 14 hours.To flood with dried absorbent charcoal carrier at N
2Atmosphere and 350 ℃ of lower roastings 4 hours, obtain black microspheric form catalyst.The mean intensity that records this catalyst granules is 195N/mm.The physical characteristic of this catalyst and chemical composition are as shown in Table 1 and Table 2.
Table 1
Table 2
Test case
Test case 1
The catalyst for preparing in embodiment 1-3 and comparative example 2-3 is carried out to catalytic performance test in laboratory scale fixed bed reactors, experiment condition is: air speed 6000ml/g/h, 340 ℃ of reaction temperatures, reaction pressure 2Mpa.
The raw material of synthetic gas H that uses
2/ CO volume ratio is 2.0, when reactor brings into operation, and H
2Be preheated to 250 ℃ before CO is in entering reactor, catalyst carries out reduction activation with hydrogen before use, acquired results represents in the following Table 3.
Table 3
From the data of table 3, can find out: with respect to existing catalyst (comparative example 1 and 2), use hydrocarbon content, C in the gas-phase product that catalyst of the present invention (embodiment 1 and 3) forms
2-C
4Olefin(e) centent, C
5+ hydrocarbon content obviously increases, simultaneously, the mean intensity of catalyst granules and the ethylenic alkoxy rate in gas-phase product also obviously improve, this explanation: the physics of catalyst of the present invention (embodiment 1 and 3) and catalytic performance, especially catalyst granules ball-type degree and mechanical strength are obviously improved, it shows higher catalytic activity and excellent selectivity of light olefin in the synthesis gas conversion reaction, this catalyst that is prepared by existing method is unattainable.The data of table 2 also illustrate: Fe-series catalyst prepared by the inventive method (embodiment 1 and 3) is particularly suitable for being used in the technique of synthesis gas one step producing light olefins.
Test case 2
The catalyst of preparation in embodiment 4 is carried out to catalytic performance test in laboratory scale fixed bed reactors, experiment condition is: air speed 6000ml/g/h, 340 ℃ of reaction temperatures, reaction pressure 1Mpa.
The raw material of synthetic gas H that uses
2/ CO volume ratio is 2.0, when reactor brings into operation, and H
2Be preheated to 250 ℃ before CO is in entering reactor, catalyst carries out reduction activation with hydrogen before use, acquired results represents in the following Table 4.
Table 4
From the data of table 4, can find out: use the gas-phase product of catalyst of the present invention (embodiment 4) formation, the content of methane is the highest, this explanation: this catalyst has catalytic activity preferably to methanation reaction and methane production is had higher selective, and it is suitable for use in the technique of preparing methane by synthetic gas.
The term that this specification is used and form of presentation only are used as descriptive and nonrestrictive term and form of presentation, when using these terms and form of presentation, are not intended to the feature that will represent and describe or any equivalent exclusion of its part.
Although represented and described several embodiment of the present invention, the present invention is not restricted to described embodiment.On the contrary, those of ordinary skills should recognize that in the situation that do not break away from principle of the present invention and spirit can be carried out any accommodation and improvement to these embodiments, protection scope of the present invention is determined by appended claim and equivalent thereof.
Claims (10)
1. catalyst that loads on the carbon ball is characterized in that:
This carbon ball carrier is the ion exchange resin of carbonization, and the active principle of described catalyst and/or auxiliary agent or their precursor are loaded in the surface and/or duct of ion exchange resin equably through ion-exchange, absorption, precipitation and/or dipping before described ion exchange resin carbonization.
2. catalyst according to claim 1, wherein, described ion exchange resin is highly basic or weak basic anion exchange resin microballoon or strong acid or Weak-acid cation exchange resin microballoon.
3. catalyst according to claim 2, wherein said ion exchange resin is further macroporous type highly basic or weak basic anion exchange resin microballoon or macroporous type strong acid or Weak-acid cation exchange resin microballoon.
4. catalyst according to claim 1, wherein, the active principle of described catalyst is oxide and/or the carbide of iron content; The precursor of the active principle of described catalyst is thermal decomposition to be the water-soluble salt solution of the oxide of iron; The auxiliary agent of described catalyst is the oxide of copper, potassium, cobalt, nickel and/or manganese, and the precursor of the auxiliary agent of described catalyst is thermal decomposition to be the water-soluble salt solution of the oxide of copper, potassium, cobalt, nickel and/or manganese.
5. catalyst according to claim 1, wherein, the precursor of the active principle of described catalyst is further anion state metal complex or the cationic slaine of iron that contains iron ion.
6. according to claim 1-5 one of any described catalyst, wherein, described catalyst is used as the catalyst of synthesis gas one step producing light olefins catalyst, fischer-tropsch synthetic catalyst, methanation catalyst prepared by synthetic gas or while co-producing light olefins, light oil and methane.
7. the preparation method of one of any described catalyst comprises the following steps:
(1) described ion exchange resin microballoon is put into to the active principle of described catalyst and/or the aqueous solution of auxiliary agent or their precursor, carry out sufficient Agitation and mixing, so that the active principle of catalyst and/or auxiliary agent or their precursor and described ion exchange resin carry out sufficient ion-exchange, absorption, precipitation and/or dipping.Thereby loaded on equably in the surface and/or duct of described ion exchange resin;
(2) the described ion exchange resin microballoon after cleaning above-mentioned steps (1), to remove unnecessary catalyst active principle and/or auxiliary agent or their precursor, then, carry out drying, to remove moisture;
(3) under inert atmosphere, described ion exchange resin microballoon after roasting above-mentioned steps (2), in order to make the carbonization of described ion exchange resin microballoon become the carbon ball, simultaneously, the active principle of described catalyst and/or the precursor of auxiliary agent are thermal decomposited active principle and/or the auxiliary agent into described catalyst, thereby, obtain active principle and/or auxiliary agent and loaded on equably the catalyst in carbon ball surface and/or duct.
8. method according to claim 7, wherein, in step (1), the Agitation and mixing time is 8-24 hour; In step (2), baking temperature is 80-150 ℃, and be 2-24 hour drying time; In step (3), sintering temperature is 300-650 ℃,, roasting time 2-8 hour.
9. method according to claim 7, wherein, the particle diameter of described ion exchange resin microballoon is the 0.2-1.0 millimeter.
10. method according to claim 7, wherein, the precursor of the active principle of described catalyst is the potassium ferricyanide, ammonium ferric oxalate, ferric ammonium sulfate and/or ferric citrate; Or ironic citrate, iron chloride, ferric nitrate, ferric sulfate, ferrous sulfate, ferric oxalate, ferric acetate, iron pentacarbonyl.
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