CN105478140A - Noble-metal-modified iron-zinc composite oxide catalyst, and preparation method and application thereof - Google Patents
Noble-metal-modified iron-zinc composite oxide catalyst, and preparation method and application thereof Download PDFInfo
- Publication number
- CN105478140A CN105478140A CN201410538577.8A CN201410538577A CN105478140A CN 105478140 A CN105478140 A CN 105478140A CN 201410538577 A CN201410538577 A CN 201410538577A CN 105478140 A CN105478140 A CN 105478140A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- iron
- solution
- zinc
- composite oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a noble-metal-modified iron-zinc composite oxide catalyst. The catalyst comprises an iron-zinc oxide composite phase and a noble metal oxide. The iron-zinc oxide composite phase is composed of iron oxide and zinc oxide. The noble metal is one or more selected from ruthenium, rhodium, palladium, osmium, iridium, and platinum. Calculated according to that the total weight of the iron-zinc oxide composite phase is 100 parts, the content of the noble metal oxide is 0.5-5 parts by weight. The invention also provides a preparation method of the catalyst, and an application of the catalyst in a reaction for preparing butadiene through butane oxidative dehydrogenation.
Description
Technical field
The present invention relates to catalytic field, more particularly, the present invention relates to iron-zinc composite oxide catalyst and the Synthesis and applications thereof of the modified with noble metals for preparing butadiene with butylene oxo-dehydrogenation.
Background technology
As the basic petrochemical materials of one, the status of butadiene in petrochemical industry olefin feedstock is only second to ethene and propylene, is one of important source material of producing the rubber resin industry products such as butadiene-styrene rubber, butadiene rubber, acrylonitrile-butadiene rubber, ABS resin, SBS thermoplastic elastomer and butadiene styrene resin.The output of butadiene becomes an important symbol of whole petrochemical industry development level.
The method of industrial production butadiene mainly contains extraction fractional distillation and dehydriding.Extraction fractional distillation refers to extract from ethylene cracker by-product mixing C-4-fraction and obtains, and the 1,3-butadiene in the whole world 90% adopts the method at present.The flourish surge having driven rubber product demand of auto industry in recent years, simple extraction process can not be met the need of market, and remain C 4 fraction and be often mainly used as fuel after extraction, butane wherein, butylene are not reasonably utilized, and dehydriding adopts the method for dehydrogenation to produce butadiene with butane and butylene for raw material, butane and butylene is made to obtain the lifting be worth.
Utilize butylene and oxygen reaction to generate 1,3-butadiene and water, this water generation reaction is favourable to reaction.Can see from following formula, butylene oxidation-dehydrogenation reaction itself is the reaction of strong heat release, water is as a kind of stable product on the one hand, product can be removed in time, reaction is carried out to forward, reaction liberated heat can be removed while on the other hand removing water, reduce reaction temperature, slagging prevention and making charcoal.
C
4H
8+1/2O
2→C
4H
6+H
2O-ΔH
298K,1MPa＝127.9kJ.mol
-1
Researcher in this field starts to go in for the study work to butadiene catalyst made by butylene oxidation dehydrogen from the sixties in last century, successively have developed the phosphorus molybdenum bismuth-based catalysts of the first generation, the catalyst with base of molybdenum of the second generation and the ferrum-based catalyst of the third generation, wherein ferrum-based catalyst takes into account the advantage that catalytic activity is high and object selectivity of product is high.Coprecipitation is mostly adopted to produce ferrum-based catalyst in prior art.And it is as known in people, coprecipitation is produced in catalyst process many influence factors, as the concentration of mixing speed, precipitating reagent, the change of the rear aspect such as butt concentration, washings consumption of precipitation all may have an impact to the activity of catalyst, physical strength.In addition, adopt existing coprecipitation for ferrum-based catalyst amplification produce time, often success rate is all very low, and the possibility of Catalyst Production failure is very big.Existing coprecipitation also exists the problem that can not perform well in actual production in enormous quantities catalyst.Therefore, people need to improve it on existing coprecipitation basis, develop a kind ofly to produce the new method with the catalyst of desired properties in enormous quantities with more high efficiency.
On the other hand, the catalyst developed at present still haves much room for improvement in butene conversion, butadiene selective and yield, catalyst stability and mechanical strength etc., people also need to develop a kind of above-mentioned one or more in all obtain the catalyst significantly improved, to meet this area demand growing to butadiene.
Summary of the invention
For this area Problems existing, this invention exploits a kind of catalyst of novelty, this catalyst is with multiple noble metal to iron-zinc composite oxide, and particularly iron system spinel carries out modification.Compared with the existing catalyst in this area, catalyst of the present invention shows splendid catalytic activity, there is higher conversion ratio, selective and yield, catalyst life is long, physical characteristic is stablized, there is lower race loss rate and wear rate, and in reaction, the mol ratio of steam and butylene reduces, and carbon deposition rate reduces.In addition, the method for the large-scale production that present invention also offers to amplify catalyst of the present invention.Specifically, inventor is by preparing solution, basified, aging washing, the series of steps such as shaping and roasting prepare described catalyst, and the optimization process condition successfully determined for this extensive Catalyst Production technique, substantially increase described catalyst and amplifying the success rate in producing, eliminate conventional coprecipitation low, unmanageable problem of product property of success rate in the amplification of catalyst is produced.
First aspect of the present invention provides a kind of iron-zinc composite oxide catalyst of modified with noble metals, this catalyst comprises iron-zinc composite oxide phase and metal oxide containing precious metals, wherein iron-zinc composite oxide is made up of iron oxide and zinc oxide, described noble metal be selected from ruthenium, rhodium, palladium, osmium, iridium, platinum one or more, be 100 parts by weight with the gross weight of described iron-zinc composite oxide phase, the content of described metal oxide containing precious metals is 0.5-5 weight portion.Of the present invention one preferred embodiment in, described catalyst is made up of iron zinc composite oxide phase and metal oxide containing precious metals.
In an embodiment of the invention, described iron-zinc composite oxide belongs to spinelle crystal formation mutually, and its molecular formula is Zn
xfe
2o
y, wherein x is that 0.5 ~ 1.18, y depends on the numerical value of x and the valence state of iron and zinc, makes iron-zinc composite oxide meet charge balance mutually.
Second aspect of the present invention provides a kind of method being used for preparing the iron-zinc composite oxide catalyst of modified with noble metals of the present invention, and the method comprises the following steps:
(1) formed and comprise the solution of molysite, zinc salt, precious metal salt and surfactant, wherein said noble metal be selected from ruthenium, rhodium, palladium, osmium, iridium, platinum one or more;
(2) make the pH value of the solution of step (1) gained raise, obtain slurries;
(3) heat ageing and washing operation are carried out to the slurries of step (2) gained;
(4) forming operation is carried out to the material of step (3) gained, obtained catalyst precarsor;
(5) roasting is carried out to described catalyst precarsor, the iron zinc composite oxide catalyst of obtained described modified with noble metals.
In an embodiment of the invention, described step (1) and (2) are carried out in the reaction vessel that volume is 1-20 cubic meter, and in other words, method of the present invention is for the technique of the scale of amplification.
In yet another embodiment of the present invention, for step (1), described molysite, zinc salt and precious metal salt are selected from the water-soluble metal salt of these elements, and described water-soluble metal salt comprises nitrate, sulfate, sulphite, phosphate and oxalates; Described surfactant is selected from sesbania powder, methylcellulose, polyvinyl alcohol; In the described aqueous solution, the molar concentration of iron ion is 0.5-2mol/l, and the molar concentration of zinc ion is 0.1-1.5mol/l, and the molar concentration of precious metal ion is 0.01-0.5mol/l.
In yet another embodiment of the present invention, for step (2), by alkaline solution being added the solution of step (1) gained, the pH value of this solution is made to be elevated to 6.5-10.5, thus obtained slurries; Preferably, described alkaline solution to be weight concentration be 5% ~ 25% ammoniacal liquor.
In yet another embodiment of the present invention, for step (3), first obtained to step (2) at the temperature of 30-100 DEG C slurries heat ageing 0.5-1.5 hour, then filter, then wash filtering the solid material obtained with water, until the pH value of washings is 7.0-8.0, and the inorganic anion concentration in washings is 0.001-0.1 mol/L.
In yet another embodiment of the present invention, for step (4), described forming operation is selected from extruded moulding and mist projection granulating is shaping; In described extruded moulding, the solid material input extruded moulding equipment that step (3) is obtained, the diameter of obtained bar is 2-5mm, and length is 3-5cm; In described mist projection granulating is shaping, solid material step (3) obtained suspends and forms the suspension that solid-weight content is 25-40 % by weight in a solvent, then with 100-200ml/min, the speed of preferred 100-150ml/min is by this suspension input spraying drying granulating equipment, the inlet temperature of described spraying drying granulating equipment is 150-350 DEG C, discharging opening temperature is 50-250 DEG C, and the particle diameter of obtained microspheres with solid is 20-200 micron.
In yet another embodiment of the present invention, for step (5), by product obtained for step (4) at 80-150 DEG C, dry 5-50 hour at the temperature of preferred 80-120 DEG C, preferred 5-30 hour, more preferably 12-25 hour, then at 300-1000 DEG C, preferred 300-700 DEG C, more preferably the roasting temperature 3-25 hour of 500-700 DEG C, preferred 8-15 hour, the iron zinc composite oxide catalyst of obtained described modified with noble metals.
3rd aspect of the present invention provides one by Oxidative Dehydrogenation of Butene for 1, the method of 3-butadiene, the method comprises: at reaction conditions, makes to comprise the raw mixture of butylene, oxygen and steam and catalyst exposure of the present invention, generate 1,3-butadiene product;
In described raw mixture, the gas hourly space velocity of butylene is 200-600 hour
-1, preferred 400-600 hour
-1; The mol ratio of oxygen and butylene is 0.5-1.0, preferred 0.6-0.8; The mol ratio of steam and butylene is 5-16, preferred 9-12; Reaction temperature is 300-400 DEG C, preferred 330-400 DEG C; Reaction pressure is 0.001 ~ 1MPa, is preferably 0.05-0.2MPa, most preferably is 0.08-0.14MPa.
Detailed description of the invention
" scope " disclosed herein limits with the form of lower limit and the upper limit.One or more lower limit can be respectively, and one or more upper limit.Given range is limited by a selected lower limit and a upper limit.Selected lower limit and the upper limit define the border of special scope.All scopes that can carry out by this way limiting comprise end value and can combine mutually, and namely any lower limit can be combined to form a scope with any upper limit.Such as, list the scope of 60-120 and 80-110 for special parameter, be interpreted as that the scope of 60-110 and 80-120 also expects.In addition, if the minimum zone value listed 1 and 2, and if list maximum magnitude value 3,4 and 5, then the scope below can all expect: 1-3,1-4,1-5,2-3,2-4 and 2-5.
In the present invention, unless otherwise indicated, the breviary of any real combinings that number range " a-b " represents between a to b represents, wherein a and b is real number.Such as number range " 0-5 " represents the whole real numbers all listed between " 0-5 " herein, and the breviary of " 0-5 " just these combinations of values represents.
If do not particularly not pointed out, this description term " two kinds " used refers to " at least two kinds ".
In the present invention, if do not illustrated especially, all embodiments mentioned in this article and preferred embodiment can be combined to form new technical scheme mutually.
In the present invention, if do not illustrated especially, all technical characteristics mentioned in this article and preferred feature can be combined to form new technical scheme mutually.
In the present invention, if do not illustrated especially, mentioned in this article sequentially can to carry out in steps, also can carry out at random, but preferably order is carried out.Such as, described method comprises step (a) and (b), represents that described method can comprise the step (a) and (b) of sequentially carrying out, also can comprise the step (b) and (a) of sequentially carrying out.Such as, describedly mention described method and also can comprise step (c), represent that step (c) random order can join described method, such as, described method can comprise step (a), (b) and (c), also step (a), (c) and (b) be can comprise, step (c), (a) and (b) etc. also can be comprised.
In the present invention, if do not illustrated especially, " comprising " mentioned in this article represents open, also can be closed.Such as, described " comprising " can represent other components that can also comprise and not list, and also can only comprise the component listed.
Catalyst of the present invention passes through with one or more the noble metal be selected from ruthenium, rhodium, palladium, osmium, iridium, platinum to iron zinc composite oxide, and particularly iron system spinel adulterates, and provides a kind of catalyst with superregulated property and intensity.This catalyst can show excellent catalytic performance in the reaction of preparing butadiene with butylene oxo-dehydrogenation.Spinelle is the general name of class mineral, has general formula X Y
2o
4, be isometric system, oxygen atom is that cubic close is piled up, and X and Y accounts for the part octahedral and tetrahedral space in lattice.X, Y can be the cations of divalence, trivalent or tetravalence, the oxygen in spinelle also can be other oxygen group elements substitute.Spinelle in catalyst of the present invention is made up of the oxide of iron and zinc, the i.e. situation of X to be Zn, Y be Fe, substantially wherein the mol ratio of Zn and Fe is 1:2, but due to error inevitable in reactant ratio and course of reaction, in product, the actual mol ratio of Zn and Fe can be floated in the scope of 0.5:2 to 1.18:2, there is vacancy in some positions that the situation of these non-stoichiometrics is equivalent in spinel crystal lattice, but the overall lattice of spinelle and catalytic activity are still kept.In some cases, the gathering of local may be there is in a small amount of zinc and the oxide of iron, may occur that the feature of the zinc oxide that intensity is more weak or iron oxide derives peak thus in the XRD spectrum of catalyst of the present invention, but in the present invention, still these zinc oxide or iron oxide are regarded as a part for Spinel.In other words, as long as the mol ratio of zinc and iron limits within the scope that mol ratio is 0.5:2 to 1.18:2 in the present invention, even if there is a small amount of iron oxide or the localized clusters of zinc oxide in Spinel, still think to define iron system spinel phase, such situation is included within limited range of the present invention.Of the present invention one preferred embodiment in, the chemical formula of the Spinel in catalyst of the present invention is ZnFe
2o
4.Of the present invention one preferred embodiment in, the noble metal of doping exists with the form of metal oxide, be 100 parts by weight with the gross weight of described iron zinc composite oxide phase, the content of metal oxide containing precious metals described in catalyst of the present invention is 0.5-5 weight portion.Of the present invention another preferred embodiment in, the particle diameter of described catalyst is 20-200 micron, preferred 50-150 micron.
Catalyst of the present invention is prepared by coprecipitation-spray drying process integration.The method comprises the following steps:
(1) formed and comprise the solution of molysite, zinc salt, precious metal salt and surfactant, wherein said noble metal be selected from ruthenium, rhodium, palladium, osmium, iridium, platinum one or more;
(2) make the pH value of the solution of step (1) gained be increased to 6.5-10.5, obtain slurries;
(3) heat ageing and washing operation are carried out to the slurries of step (2) gained;
(4) forming operation is carried out to the material of step (3) gained, obtained catalyst precarsor;
(5) roasting is carried out to described catalyst precarsor, iron the zinc composite oxide catalyst, particularly iron spinel catalyst of obtained described modified with noble metals.
Technique of the present invention is specially adapted to the Catalyst Production technique of amplification scale.In the present invention, so-called " amplification scale " is relative with the catalyst synthesis processes of " lab scale " scale, comprises pilot scale and plant-scale production.The catalyst synthesis of bench scale is usually carried out being no more than at most in the reaction vessel of 5 liters, and process for synthetic catalyst of the present invention can be greater than in the reaction vessel of 1 cubic metre at volume and carries out.In a preferred embodiment of the present invention, the volume of described reaction vessel is 1-200 cubic meter, preferred 1-20 cubic meter.The ratio of height to diameter of reactor is 1:0.5 to 1:2, preferred 1:1 to 1:1.5, more preferably 1:1.38.
In a preferred embodiment of the present invention, in step (1), water-soluble or the water-soluble solvent by the salt and surfactant that comprise iron, zinc and noble metal, obtain required solution, wherein precious metal element is selected from one or more in ruthenium, rhodium, palladium, osmium, iridium, platinum.The salt of described iron, zinc and noble metal is the water-soluble metal salt being selected from these elements, comprises nitrate, sulfate, sulphite, phosphate and oxalates.Described water-soluble solvent is any solvent that can be miscible with water, as alcohols, ethers, or the mixture of these solvents and water.
In one preferred embodiment, by soluble in water for the salt of iron, zinc and noble metal, solution A is obtained.Then, surfactant is added in water as above or water-soluble solvent, obtains solution B.In one preferred embodiment, surfactant is dissolved in alcohol, form solution B, described alcohol can be selected from methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, sec-butyl alcohol, isobutanol, the tert-butyl alcohol, hexylene glycol, glycerine, propane diols etc.Then, solution B is added in solution A, and stir 10-90 minute, preferred 30-60 minute, obtain clarifying homogeneous solution.Described surfactant can improve uniformity and the fluid property of this slurry system in slurry stage, be also conducive to the overall mechanical strength improving final obtained catalyst simultaneously, significantly improve its wearability.Described surfactant is selected from sesbania powder, methylcellulose, polyvinyl alcohol.
Of the present invention one preferred embodiment in, in the solution that the described clarification obtained is homogeneous, the content of surfactant is 1-10 mol/L, preferred 1-3 mol/L.
In step (2), by dripping alkaline solution in the obtained solution of step (1), the pH value of reaction system being adjusted to 6.5-10.5, preferred 7.0-8.0, the metal ion in solution being precipitated, obtains slurries.Described alkaline solution can be concentration be 5 % by weight ~ 25 % by weight ammoniacal liquor, be preferably the ammoniacal liquor of 5-15 % by weight.
In step (3), the slurries of above-mentioned steps gained are heated to 30-100 DEG C, preferred 50-90 DEG C, and keep 0.5-1.5 hour, preferred 0.5-1 hour at this temperature, thus carry out aging.Described ageing process is carried out under the condition stirred.After aging, slurries being filtered, then washing filtering the solid product obtained with water.Continue to carry out this washing operation, until the pH of washings is 7.0 ~ 8.0, and in washings, the concentration of inorganic anion is 0.001 ~ 0.1mol/L.
In step (4), the solid product obtained to step (3) carries out forming operation, obtained catalyst precarsor.Described forming operation can comprise extruded moulding or spray drying forming.
If obtained catalyst will be used for fixed bed applications, extruded moulding equipment will be used directly to carry out extrusion molding to the filter cake obtained after filtration, obtained catalyst precarsor.Described extruded moulding equipment can be arbitrary equipment known in the art, such as Hydron L-DJ-40, Hydron DJ-40 type extrusion equipment.In an embodiment of the invention, the present invention preferably uses Hydron DJ-40 type extrusion equipment.In an embodiment of the invention, the feed rate that filter cake inputs described extrusion equipment is 15-30kg/h, and the diameter of obtained catalyst precarsor bar is 2-5mm, and length is 3-5cm.
If obtained catalyst will be used for fluidized bed applications, use solvent that filter cake is made suspension again, and make the solid content in suspension be 25-40 % by weight, this content in the gross weight of this suspension for benchmark.Spraying drying granulating equipment is used to carry out spraying dry to described suspension, obtained catalyst precursor microspheres.Described spraying drying granulating equipment can be arbitrary equipment known in the art, such as press spray drying-granulating equipment, pneumatic spray drying Granulation Equipments or atomizer Granulation Equipments.In an embodiment of the invention, the present invention preferably uses QPG-5 type pneumatic spray drying comminutor.In an embodiment of the invention; the feed rate that described suspension inputs described spray drying granulation machine is 100-200ml/min; the inlet temperature of described spray drying granulation machine is 150-350 DEG C; discharging opening temperature is 20-250 DEG C; the particle diameter of obtained catalyst precursor microspheres is 20-200 micron, preferred 50-150 micron.
In step (5), the catalyst precarsor that step (4) is obtained puts into infrared baking box or forced ventilation convection oven, dry 5-50 hour at the temperature of preferred 80-150 DEG C, preferred 5-30 hour, more preferably 12-25 hour, then transfer in Muffle furnace, in air atmosphere, at the roasting temperature 3-25 hour of 30-1000 DEG C, preferably 500-700 DEG C, preferred 5-20, preferred 8-15 hour, thus obtained catalyst of the present invention.
Catalyst of the present invention is suitable for the reaction of preparing butadiene with butylene oxo-dehydrogenation.This reaction can use the raw material be made up of same butylene isomer (as cis-2-butene) to prepare butadiene, also raw material that the mixture of different butylene isomer (as 1-butylene, cis-2-butene and Trans-2-butene) forms can be used to prepare butadiene, these components even can also comprise other components except butylene in this raw material, as long as can not cause adverse effect to the separation of the carrying out of this reaction or product.In an embodiment of the invention, the C comprising butane and various butylene isomer is used
4mixture (i.e. C4 after ether) prepares butadiene for raw material.After described ether, C4 can be the C that petroleum cracking product obtains
4cut also can be the material mainly comprising butane and various butylene isomer that other chemical technologies obtain.
In the present invention, in time using the mixture of other components and butylene as raw material, the gas hourly space velocity of described butylene represents total gas hourly space velocity of all butylene isomers, and the mol ratio of butylene and steam and oxygen is also calculate with the integral molar quantity of all butylene isomers.
In an embodiment of the invention, after use ether, C4 prepares in the reaction of butadiene, and the gas hourly space velocity of butylene is 200-600 hour
-1, preferred 400-600 hour
-1; The mol ratio of oxygen and butylene is 0.5-1.0, preferred 0.6-0.8; The mol ratio of steam and butylene is 5-16, preferred 9-12; Reaction temperature is 300-400 DEG C, preferred 330-400 DEG C; Reaction pressure is 0.001 ~ 1MPa, is preferably 0.05-0.2MPa, most preferably is 0.08-0.14MPa.
In the present invention, by preparing in the reaction of butadiene to the catalyst that iron-zinc oxide spinel catalyst carries out doping obtained by butylene with metal oxide containing precious metals, achieve relative to conventional ferrum-based catalyst in catalytic activity and reaction efficiency and significantly improve, if butene conversion is up to 80-90%, butadiene selective is up to 93%-98%, and therefore catalyst of the present invention improves 4.8-12.3%, 1.6-6.0%, 5.2-16.4% respectively compared to the conventional ferrum-based catalyst of use in butene conversion, butadiene selective and yield.In addition, the carbon deposition rate of this catalyst reduces, and the property retention of catalyst is stablized in course of reaction.In addition, the optimization process condition developed by the present invention, can produce catalyst of the present invention with the scale of amplifying by co-precipitation-spray shaping method.
Embodiment
The present invention will describe technical scheme of the present invention in detail by embodiment, but protection scope of the present invention is not limited thereto, and these embodiments are only presented for purposes of illustration.
Below in an example, the extruded moulding equipment used is the DJ-40 type extruded moulding equipment that Hydron Mechanology Inc. produces.The spray drying granulation machine used is the QPG-5 type pneumatic spray drying comminutor that Changzhou Hu Bang drying equipment Co., Ltd produces.Unless otherwise indicated, other all reagent used are commercially available AR.
Embodiment 1 uses nitrate raw material to prepare the catalyst of platiniferous in the mode of extruded moulding
550 liters of deionized waters, 420 kilograms of ferric nitrates, 95 kilograms of zinc nitrates, 10 kilograms of platinum nitrates are added in 2 cubic metres of reactors, stirs 30 minutes to obtain solution A with 100r/min rotating speed.1.5 kilograms of sesbania powder are dissolved in the ethanol of 3 liters and obtain solution B.At room temperature, solution B to be added in solution A and to stir 30 minutes, obtaining settled solution.Under intense agitation the ammoniacal liquor of 20 % by weight is instilled in above-mentioned solution, until its PH=9.0, produce precipitation in the process, form slurries.Then maintenance stir while the temperature of slurries is elevated to 80 DEG C, at this temperature keep 0.5 hour aging to carry out.Filter slurries with Buchner funnel, wash filtering the solid obtained with water, until the pH value making final washings is 8.0, in washings, the concentration of nitrate anion is 0.01mol/l.Filter cake is inputted extruded moulding equipment, obtain length 5cm, the strip catalyst precarsor of diameter 3mm.Then this catalyst precarsor is transferred in infrared heater, 120 DEG C of dryings 12 hours, then transfer in Muffle furnace, 600 DEG C of calcinings 10 hours, obtain catalyst 1#.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Pt=1:0.283:0.026.
Automolite ZnFe can be seen in the XRD spectrum of synthetic catalyst 1#
2o
4characteristic peak (with " S " mark 2 θ=30 °, 35.5 °, 36.5 °, 43 °, 53 °, 56.5 °, 62.5 °) and the more weak α-Fe of intensity
2o
3characteristic peak (with " α " mark 2 θ=33.5 °, 41 °, 49 °, 54 °, 64 °), confirm the Fe-series catalyst that can obtain having spinel structure by synthetic method of the present invention.
Embodiment 2 uses nitrate raw material to prepare the catalyst of rhodium-containing in the mode of extruded moulding
550 liters of deionized waters, 420 kilograms of ferric nitrates, 95 kilograms of zinc nitrates, 10 kilograms of rhodium nitrates are added in 2 cubic metres of reactors, stirs 30 minutes to obtain solution A with 100r/min rotating speed.1.5 kilograms of sesbania powder are dissolved in the ethanol of 3 liters and obtain solution B.At room temperature, solution B to be added in solution A and to stir 30 minutes, obtaining settled solution.Under intense agitation the ammoniacal liquor of 20 % by weight is instilled in above-mentioned solution, until its PH=9.0, produce precipitation in the process, form slurries.Then maintenance stir while the temperature of slurries is elevated to 85 DEG C, at this temperature keep 1.0 hours aging to carry out.Filter slurries with Buchner funnel, wash filtering the solid obtained with water, until the pH value making final washings is 8.0, in washings, the concentration of nitrate anion is 0.01mol/l.Filter cake is inputted extruded moulding equipment, obtain length 5cm, the strip catalyst precarsor of diameter 3mm.Then this catalyst precarsor is transferred in infrared heater, 120 DEG C of dryings 12 hours, then transfer in Muffle furnace, 600 DEG C of calcinings 10 hours, obtain catalyst 2#.The mol ratio being recorded various element in catalyst by icp analysis is Fe:Zn:Rh=1:0.275:0.00081.Automolite ZnFe can be observed in the XRD spectrum of synthetic catalyst 2#
2o
4characteristic peak 2 θ=30 °, 35.5 °, 36.5 °, 43 °, 53 °, 56.5 °, 62.5 °, α-Fe
2o
3characteristic peak 2 θ=33.5 °, 41 °, 49 °, 54 °, 64 °, confirm the Fe-series catalyst that can obtain having spinel structure by synthetic method of the present invention.
Embodiment 3 uses sulfate starting material to prepare the catalyst of platiniferous in the mode of extruded moulding
550 liters of deionized waters, 420 kilo sulfuric acid iron, 95 kilo sulfuric acid zinc, 10 kilo sulfuric acid platinum are added in 2 cubic metres of reactors, stirs 30 minutes to obtain solution A with 100r/min rotating speed.1.5 kilograms of sesbania powder are dissolved in the ethanol of 3 liters and obtain solution B.At room temperature, solution B to be added in solution A and to stir 30 minutes, obtaining settled solution.Under intense agitation the ammoniacal liquor of 20 % by weight is instilled in above-mentioned solution, until its PH=7.0, produce precipitation in the process, form slurries.Then maintenance stir while the temperature of slurries is elevated to 70 DEG C, at this temperature keep 1.5 hours aging to carry out.Filter slurries with Buchner funnel, wash filtering the solid obtained with water, until the pH value making final washings is 8.0, in washings, the concentration of nitrate anion is 0.01mol/l.Filter cake is inputted extruded moulding equipment, obtain length 5cm, the strip catalyst precarsor of diameter 3mm.Then this catalyst precarsor is transferred in infrared heater, 120 DEG C of dryings 12 hours, then transfer in Muffle furnace, 600 DEG C of calcinings 10 hours, obtain catalyst 3#.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Pt=1:0.253:0.018.In the XRD spectrum of synthetic catalyst 3#, automolite ZnFe
2o
4characteristic peak 2 θ=30 °, 35.5 °, 36.5 °, 43 °, 53 °, 56.5 °, 62.5 °, α-Fe
2o
3characteristic peak 2 θ=33.5 °, 41 °, 49 °, 54 °, 64 °, confirm the Fe-series catalyst that can obtain having spinel structure by synthetic method of the present invention.
Embodiment 4 uses nitrate raw material to prepare the catalyst of platiniferous in the mode of extruded moulding
550 liters of deionized waters, 420 kilograms of ferric nitrates, 95 kilograms of zinc nitrates, 10 kilograms of platinum nitrates are added in 2 cubic metres of reactors, stirs 30 minutes to obtain solution A with 100r/min rotating speed.2 kilograms of sesbania powder are dissolved in the ethanol of 3 liters and obtain solution B.At room temperature, solution B to be added in solution A and to stir 30 minutes, obtaining settled solution.Under intense agitation the ammoniacal liquor of 20 % by weight is instilled in above-mentioned settled solution, until its PH=8.0, produce precipitation in the process, form slurries.Then maintenance stir while the temperature of slurries is elevated to 90 DEG C, at this temperature keep 0.5 hour aging to carry out.Filter slurries with Buchner funnel, wash filtering the solid obtained with water, until the pH value making final washings is 8.0, in washings, the concentration of nitrate anion is 0.01mol/l.Filter cake is inputted extruded moulding equipment, obtain length 5cm, the strip catalyst precarsor of diameter 3mm.Then this catalyst precarsor is transferred in infrared heater, 120 DEG C of dryings 12 hours, then transfer in Muffle furnace, 600 DEG C of calcinings 10 hours, obtain catalyst 4#.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Pt=1:0.261:0.023.ZnFe is demonstrated in the XRD spectrum of synthetic catalyst 4#
2o
4with α-Fe
2o
3characteristic peak, confirm the Fe-series catalyst that can obtain having spinel structure by synthetic method of the present invention.
Embodiment 5 uses nitrate raw material to prepare the catalyst of platiniferous in the mode of extruded moulding
550 liters of deionized waters, 420 kilograms of ferric nitrates, 95 kilograms of zinc nitrates, 10 kilograms of platinum nitrates are added in 2 cubic metres of reactors, stirs 30 minutes to obtain solution A with 100r/min rotating speed.2 kilograms of sesbania powder are dissolved in the ethanol of 3 liters and obtain solution B.At room temperature, solution B to be added in solution A and to stir 30 minutes, obtaining settled solution.Under intense agitation the ammoniacal liquor of 20 % by weight is instilled in above-mentioned solution, until its PH=10.0, produce precipitation in the process, form slurries.Then maintenance stir while the temperature of slurries is elevated to 60 DEG C, at this temperature keep 1.5 hours aging to carry out.Filter slurries with Buchner funnel, wash filtering the solid obtained with water, until the pH value making final washings is 8.0, in washings, the concentration of nitrate anion is 0.01mol/l.Filter cake is inputted extruded moulding equipment, obtain length 5cm, the strip catalyst precarsor of diameter 3mm.Then this catalyst precarsor is transferred in infrared heater, 120 DEG C of dryings 12 hours, then transfer in Muffle furnace, 600 DEG C of calcinings 10 hours, obtain catalyst 5#.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Pt=1:0.258:0.025.ZnFe is demonstrated in the XRD spectrum of synthetic catalyst 5#
2o
4with α-Fe
2o
3characteristic peak, confirm the Fe-series catalyst that can obtain having spinel structure by synthetic method of the present invention.
Embodiment 6 uses sulfate starting material to prepare the catalyst containing palladium in the mode of extruded moulding
550 liters of deionized waters, 420 kilo sulfuric acid iron, 95 kilo sulfuric acid zinc, 10 kilo sulfuric acid palladiums are added in 2 cubic metres of reactors, stirs 30 minutes to obtain solution A with 100r/min rotating speed.2 kilograms of sesbania powder are dissolved in the ethanol of 3 liters and obtain solution B.At room temperature, solution B to be added in solution A and to stir 30 minutes, obtaining settled solution.Under intense agitation the ammoniacal liquor of 15 % by weight is instilled in above-mentioned solution, until its PH=11.0, produce precipitation in the process, form slurries.Then maintenance stir while the temperature of slurries is elevated to 75 DEG C, at this temperature keep 1.0 hours aging to carry out.Filter slurries with Buchner funnel, wash filtering the solid obtained with water, until the pH value making final washings is 8.0, in washings, the concentration of nitrate anion is 0.01mol/l.Filter cake is inputted extruded moulding equipment, obtain length 5cm, the strip catalyst precarsor of diameter 3mm.Then this catalyst precarsor is transferred in infrared heater, 120 DEG C of dryings 12 hours, then transfer in Muffle furnace, 600 DEG C of calcinings 10 hours, obtain catalyst 6#.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Pd=1:0.29:0.026.ZnFe is demonstrated in the XRD spectrum of synthetic catalyst 6#
2o
4with α-Fe
2o
3characteristic peak, confirm the Fe-series catalyst that can obtain having spinel structure by synthetic method of the present invention.
Embodiment 7 uses nitrate raw material to prepare the catalyst of platiniferous in the mode of extruded moulding
550 liters of deionized waters, 420 kilograms of ferric nitrates, 95 kilograms of zinc nitrates, 10 kilograms of platinum nitrates are added in 2 cubic metres of reactors, stirs 30 minutes to obtain solution A with 100r/min rotating speed.2 kilograms of sesbania powder are dissolved in the ethanol of 3 liters and obtain solution B.At room temperature, solution B to be added in solution A and to stir 30 minutes, obtaining settled solution.Under intense agitation the ammoniacal liquor of 5 % by weight is instilled in above-mentioned solution, until its PH=9.0, produce precipitation in the process, form slurries.Then maintenance stir while the temperature of slurries is elevated to 90 DEG C, at this temperature keep 0.5 hour aging to carry out.Filter slurries with Buchner funnel, wash filtering the solid obtained with water, until the pH value making final washings is 8.0, in washings, the concentration of nitrate anion is 0.01mol/l.Filter cake is inputted extruded moulding equipment, obtain length 5cm, the strip catalyst precarsor of diameter 3mm.Then this catalyst precarsor is transferred in infrared heater, 120 DEG C of dryings 12 hours, then transfer in Muffle furnace, 600 DEG C of calcinings 10 hours, obtain catalyst 7#.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Pt=1:0.287:0.026.ZnFe is demonstrated in the XRD spectrum of synthetic catalyst 7#
2o
4with α-Fe
2o
3characteristic peak, confirm the Fe-series catalyst that can obtain having spinel structure by synthetic method of the present invention.
Embodiment 8 uses nitrate raw material to prepare the catalyst of platiniferous in the mode of extruded moulding
550 liters of deionized waters, 420 kilograms of ferric nitrates, 95 kilograms of zinc nitrates, 10 kilograms of platinum nitrates are added in 2 cubic metres of reactors, stirs 30 minutes to obtain solution A with 100r/min rotating speed.2 kilograms of sesbania powder are dissolved in the ethanol of 3 liters and obtain solution B.At room temperature, solution B to be added in solution A and to stir 30 minutes, obtaining settled solution.Under intense agitation the ammoniacal liquor of 15 % by weight is instilled in above-mentioned solution, until its PH=10.5, produce precipitation in the process, form slurries.Then maintenance stir while the temperature of slurries is elevated to 55 DEG C, at this temperature keep 1.5 hours aging to carry out.Filter slurries with Buchner funnel, wash filtering the solid obtained with water, until the pH value making final washings is 8.0, in washings, the concentration of nitrate anion is 0.1mol/l.Filter cake is inputted extruded moulding equipment, obtain length 5cm, the strip catalyst precarsor of diameter 3mm.Then this catalyst precarsor is transferred in infrared heater, 120 DEG C of dryings 12 hours, then transfer in Muffle furnace, 600 DEG C of calcinings 10 hours, obtain catalyst 8#.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Pt=1:0.288:0.026.ZnFe is demonstrated in the XRD spectrum of synthetic catalyst 8#
2o
4with α-Fe
2o
3characteristic peak, confirm the Fe-series catalyst that can obtain having spinel structure by synthetic method of the present invention.
Embodiment 9 uses nitrate raw material to prepare the catalyst of platiniferous in the mode of extruded moulding
550 liters of deionized waters, 420 kilograms of ferric nitrates, 95 kilograms of zinc nitrates, 10 kilograms of platinum nitrates are added in 2 cubic metres of reactors, stirs 30 minutes to obtain solution A with 100r/min rotating speed.2 kilograms of sesbania powder are dissolved in the ethanol of 3 liters and obtain solution B.At room temperature, solution B to be added in solution A and to stir 30 minutes, obtaining settled solution.Under intense agitation the ammoniacal liquor of 15 % by weight is instilled in above-mentioned solution, until its PH=12.5, produce precipitation in the process, form slurries.Then maintenance stir while the temperature of slurries is elevated to 65 DEG C, at this temperature keep 1.0 hours aging to carry out.Filter slurries with Buchner funnel, wash filtering the solid obtained with water, until the pH value making final washings is 8.0, in washings, the concentration of nitrate anion is 0.1mol/l.Filter cake is inputted extruded moulding equipment, obtain length 5cm, the strip catalyst precarsor of diameter 3mm.Then this catalyst precarsor is transferred in infrared heater, 120 DEG C of dryings 12 hours, then transfer in Muffle furnace, 600 DEG C of calcinings 10 hours, obtain catalyst 9#.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Pt=1:0.283:0.026.ZnFe is demonstrated in the XRD spectrum of synthetic catalyst 9#
2o
4with α-Fe
2o
3characteristic peak, confirm the Fe-series catalyst that can obtain having spinel structure by synthetic method of the present invention.
Embodiment 10 uses sulfate starting material to prepare the catalyst of platiniferous in the mode of spray shaping
550 liters of deionized waters, 420 kilo sulfuric acid iron, 95 kilo sulfuric acid zinc, 10 kilo sulfuric acid platinum are added in 2 cubic metres of reactors, stirs 30 minutes to obtain solution A with 100r/min rotating speed.2 kilograms of sesbania powder are dissolved in the ethanol of 3 liters and obtain solution B.At room temperature, solution B to be added in solution A and to stir 30 minutes, obtaining settled solution.Under intense agitation the ammoniacal liquor of 15 % by weight is instilled in above-mentioned solution, until its PH=6.5, produce precipitation in the process, form slurries.Then maintenance stir while the temperature of slurries is elevated to 50 DEG C, at this temperature keep 1.5 hours aging to carry out.Filter slurries with Buchner funnel, wash filtering the solid obtained with water, until the pH value making final washings is 8.0, in washings, the concentration of sulfate radical is 0.1mol/l.
Filter cake is mixed to obtain mixed slurry with deionized water; the two mixing quality than being 1:1.2, after by gained mixed slurry with the flow velocity of 180 ls/h input pneumatic spray drying comminutor, inlet temperature is 300 DEG C; outlet temperature is 200 DEG C, obtains catalyst precursor microspheres.
Then this catalyst precarsor is transferred in infrared heater, 120 DEG C of dryings 12 hours, then transfer in Muffle furnace, 600 DEG C of calcinings 10 hours, obtain catalyst 10#.Recorded by the analysis of S3500 type laser fineness gage, the granularity of this catalyst granules is 20-200 micron.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Pt=1:0.271:0.025.
ZnFe is demonstrated in the XRD spectrum of synthetic catalyst 10#
2o
4with α-Fe
2o
3characteristic peak, confirm the Fe-series catalyst that can obtain having spinel structure by synthetic method of the present invention.
Embodiment 11 uses phosphatic raw materials to prepare the catalyst of rhodium-containing in the mode of spray shaping
By 550 liters of deionized waters, 420 kilograms of ferric phosphates, 95 kilograms of trbasic zinc phosphates, (phosphoric acid rhodium is commercially available to 10 kilograms of phosphoric acid rhodiums, purchased from Chengdu Ai Keda chemical reagent Co., Ltd) add in 2 cubic metres of reactors, stir 30 minutes to obtain solution A with 100r/min rotating speed.2 kilograms of sesbania powder are dissolved in the ethanol of 3 liters and obtain solution B.At room temperature, solution B to be added in solution A and to stir 30 minutes, obtaining settled solution.Under intense agitation the ammoniacal liquor of 5 % by weight is instilled in above-mentioned solution, until its PH=7.0, produce precipitation in the process, form slurries.Then maintenance stir while the temperature of slurries is elevated to 80 DEG C, at this temperature keep 0.5 hour aging to carry out.Filter slurries with Buchner funnel, wash filtering the solid obtained with water, until the pH value making final washings is 8.0, in washings, the concentration of sulfate radical is 0.1mol/l.
Filter cake is mixed to obtain mixed slurry with deionized water; the two mixing quality than being 1:1.2, after by gained mixed slurry with the flow velocity of 150 ls/h input pneumatic spray drying comminutor, inlet temperature is 320 DEG C; outlet temperature is 230 DEG C, obtains catalyst precursor microspheres.
Then this catalyst precarsor is transferred in infrared heater, 80 DEG C of dryings 50 hours, then transfer in Muffle furnace, 800 DEG C of calcinings 5 hours, obtain catalyst 11#.Recorded by the analysis of S3500 type laser fineness gage, the granularity of this catalyst granules is 20-200 micron.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Rh=1:0.251:0.079.
ZnFe is demonstrated in the XRD spectrum of synthetic catalyst 11#
2o
4with α-Fe
2o
3characteristic peak, confirm the Fe-series catalyst that can obtain having spinel structure by synthetic method of the present invention.
Embodiment 12 uses nitrate raw material to prepare the catalyst containing ruthenium in the mode of spray shaping
550 liters of deionized waters, 420 kilograms of ferric nitrates, 95 kilograms of zinc nitrates, 10 kilograms of nitric acid rutheniums are added in 2 cubic metres of reactors, stirs 30 minutes to obtain solution A with 100r/min rotating speed.2 kilograms of methylcellulose are dissolved in the ethanol of 3 liters and obtain solution B.At room temperature, solution B to be added in solution A and to stir 30 minutes, obtaining settled solution.Under intense agitation the ammoniacal liquor of 10 % by weight is instilled in above-mentioned solution, until its PH=7.0, produce precipitation in the process, form slurries.Then maintenance stir while the temperature of slurries is elevated to 80 DEG C, at this temperature keep 0.5 hour aging to carry out.Filter slurries with Buchner funnel, wash filtering the solid obtained with water, until the pH value making final washings is 8.0, in washings, the concentration of phosphate radical is 0.1mol/l.
Filter cake is mixed to obtain mixed slurry with deionized water; the two mixing quality than being 1:1.2, after by gained mixed slurry with the flow velocity of 100 ls/h input pneumatic spray drying comminutor, inlet temperature is 250 DEG C; outlet temperature is 180 DEG C, obtains catalyst precursor microspheres.
Then this catalyst precarsor is transferred in infrared heater, 150 DEG C of dryings 5 hours, then transfer in Muffle furnace, 700 DEG C of calcinings 10 hours, obtain catalyst 12#.Recorded by the analysis of S3500 type laser fineness gage, the granularity of this catalyst granules is 20-200 micron.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Ru=1:0.252:0.028.
ZnFe is demonstrated in the XRD spectrum of synthetic catalyst 12#
2o
4with α-Fe
2o
3characteristic peak, confirm the Fe-series catalyst that can obtain having spinel structure by synthetic method of the present invention.
Embodiment 13 uses nitrate raw material to prepare the catalyst containing palladium in the mode of spray shaping
550 liters of deionized waters, 420 kilograms of ferric nitrates, 95 kilograms of zinc nitrates, 10 kilograms of palladium nitrates are added in 2 cubic metres of reactors, stirs 30 minutes to obtain solution A with 100r/min rotating speed.2 kilograms of methylcellulose are dissolved in the ethanol of 3 liters and obtain solution B.At room temperature, solution B to be added in solution A and to stir 30 minutes, obtaining settled solution.Under intense agitation the ammoniacal liquor of 15 % by weight is instilled in above-mentioned solution, until its PH=9.0, produce precipitation in the process, form slurries.Then maintenance stir while the temperature of slurries is elevated to 80 DEG C, at this temperature keep 0.5 hour aging to carry out.Filter slurries with Buchner funnel, wash filtering the solid obtained with water, until the pH value making final washings is 8.0, in washings, the concentration of sulfate radical is 0.1mol/l.
Filter cake is mixed to obtain mixed slurry with deionized water; the two mixing quality than being 1:1.2, after by gained mixed slurry with the flow velocity of 200 ls/h input pneumatic spray drying comminutor, inlet temperature is 150 DEG C; outlet temperature is 100 DEG C, obtains catalyst precursor microspheres.
Then this catalyst precarsor is transferred in infrared heater, 120 DEG C of dryings 20 hours, then transfer in Muffle furnace, 500 DEG C of calcinings 20 hours, obtain catalyst 13#.Recorded by the analysis of S3500 type laser fineness gage, the granularity of this catalyst granules is 20-200 micron.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Pd=1:0.285:0.04.
ZnFe is demonstrated in the XRD spectrum of synthetic catalyst 13#
2o
4with α-Fe
2o
3characteristic peak, confirm the Fe-series catalyst that can obtain having spinel structure by synthetic method of the present invention.
Embodiment 14 uses nitrate raw material to prepare the catalyst containing osmium in the mode of spray shaping
550 liters of deionized waters, 420 kilograms of ferric nitrates, 95 kilograms of zinc nitrates, 10 kilograms of nitric acid osmiums are added in 2 cubic metres of reactors, stirs 30 minutes to obtain solution A with 100r/min rotating speed.2 kilograms of methylcellulose are dissolved in the ethylene glycol of 3 liters and obtain solution B.At room temperature, solution B to be added in solution A and to stir 30 minutes, obtaining settled solution.Under intense agitation the ammoniacal liquor of 10 % by weight is instilled in above-mentioned solution, until its PH=9.0, produce precipitation in the process, form slurries.Then maintenance stir while the temperature of slurries is elevated to 80 DEG C, at this temperature keep 0.5 hour aging to carry out.Filter slurries with Buchner funnel, wash filtering the solid obtained with water, until the pH value making final washings is 8.0, in washings, the concentration of sulfate radical is 0.1mol/l.
Filter cake is mixed to obtain mixed slurry with deionized water; the two mixing quality than being 1:1.2, after by gained mixed slurry with the flow velocity of 120 ls/h input pneumatic spray drying comminutor, inlet temperature is 150 DEG C; outlet temperature is 80 DEG C, obtains catalyst precursor microspheres.
Then this catalyst precarsor is transferred in infrared heater, 140 DEG C of dryings 12 hours, then transfer in Muffle furnace, 900 DEG C of calcinings 5 hours, obtain catalyst 14#.Recorded by the analysis of S3500 type laser fineness gage, the granularity of this catalyst granules is 20-200 micron.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Os=1:0.273:0.035.
ZnFe is demonstrated in the XRD spectrum of synthetic catalyst 14#
2o
4with α-Fe
2o
3characteristic peak, confirm the Fe-series catalyst that can obtain having spinel structure by synthetic method of the present invention.
Embodiment 15 uses nitrate raw material to prepare the catalyst containing iridium in the mode of spray shaping
550 liters of deionized waters, 420 kilograms of ferric acetates, 95 kilograms of zinc acetates, 10 kilograms of acetic acid iridium are added in 2 cubic metres of reactors, stirs 30 minutes to obtain solution A with 100r/min rotating speed.2 kilograms of polyvinyl alcohol are dissolved in the ethylene glycol of 3 liters and obtain solution B.At room temperature, solution B to be added in solution A and to stir 30 minutes, obtaining settled solution.Under intense agitation the ammoniacal liquor of 25 % by weight is instilled in above-mentioned solution, until its PH=9.0, produce precipitation in the process, form slurries.Then maintenance stir while the temperature of slurries is elevated to 80 DEG C, at this temperature keep 0.5 hour aging to carry out.Filter slurries with Buchner funnel, wash filtering the solid obtained with water, until the pH value making final washings is 8.0, in washings, the concentration of nitrate anion is 0.1mol/l.
Filter cake is mixed to obtain mixed slurry with deionized water; the two mixing quality than being 1:1.2, after by gained mixed slurry with the flow velocity of 150 ls/h input pneumatic spray drying comminutor, inlet temperature is 350 DEG C; outlet temperature is 250 DEG C, obtains catalyst precursor microspheres.
Then this catalyst precarsor is transferred in infrared heater, 120 DEG C of dryings 30 hours, then transfer in Muffle furnace, 600 DEG C of calcinings 10 hours, obtain catalyst 15#.Recorded by the analysis of S3500 type laser fineness gage, the granularity of this catalyst granules is 20-200 micron.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Ir=1:0.27:0.015.
ZnFe is shown in the XRD spectrum of synthetic catalyst 15#
2o
4with α-Fe
2o
3characteristic peak, confirm the Fe-series catalyst that can obtain having spinel structure by synthetic method of the present invention.
Comparative example
Comparative example 1: with the method preparation described in embodiment 1 not containing the catalyst of the Fe-Zn spinelle of precious metal element
550 liters of deionized waters, 420 kilograms of ferric nitrates, 95 kilograms of zinc nitrates are added in 2 cubic metres of reactors, stirs 30 minutes to obtain solution A with 100r/min rotating speed.1.5 kilograms of sesbania powder are dissolved in the ethanol of 3 liters and obtain solution B.At room temperature, solution B to be added in solution A and to stir 30 minutes, obtaining settled solution.Under intense agitation the ammoniacal liquor of 20 % by weight is instilled in above-mentioned solution, until its PH=9.0, produce precipitation in the process, form slurries.Then maintenance stir while the temperature of slurries is elevated to 80 DEG C, at this temperature keep 0.5 hour aging to carry out.Filter slurries with Buchner funnel, wash filtering the solid obtained with water, until the pH value making final washings is 8.0, in washings, the concentration of nitrate anion is 0.01mol/l.Filter cake is inputted extruded moulding equipment, obtain length 5cm, the strip catalyst precarsor of diameter 3mm.Then this catalyst precarsor is transferred in infrared heater, 120 DEG C of dryings 12 hours, then transfer in Muffle furnace, 600 DEG C of calcinings 10 hours, obtain catalyst D1#.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn=1:0.256.
Comparative example 2 investigates the impact of the pH value of precipitation terminal: less pH value
According to the step of embodiment 1,550 liters of deionized waters, 420 kilograms of ferric nitrates, 95 kilograms of zinc nitrates, 10 kilograms of platinum nitrates are added in 2 cubic metres of reactors, stir 30 minutes to obtain solution A with 100r/min rotating speed.1.5 kilograms of sesbania powder are dissolved in the ethanol of 3 liters and obtain solution B.At room temperature, solution B to be added in solution A and to stir 30 minutes, obtaining settled solution.Difference is, is instilled in above-mentioned solution by the ammoniacal liquor of 20 % by weight under intense agitation, until its PH=5.0, produces precipitation in the process, forms slurries.
Then maintenance stir while the temperature of slurries is elevated to 80 DEG C, at this temperature keep 0.5 hour aging to carry out.Filter slurries with Buchner funnel, wash filtering the solid obtained with water, until the pH value making final washings is 8, in washings, the concentration of nitrate anion is 0.01mol/l.Filter cake is inputted extruded moulding equipment, obtain length 5cm, the strip catalyst precarsor of diameter 3mm.Then this catalyst precarsor is transferred in infrared heater, 120 DEG C of dryings 12 hours, then transfer in Muffle furnace, 600 DEG C of calcinings 10 hours, obtain catalyst D2#.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Pt=1:0.22:0.025.
Comparative example 3 investigates the impact of the pH value of precipitation terminal: larger pH value
According to the step of embodiment 1,550 liters of deionized waters, 420 kilograms of ferric nitrates, 95 kilograms of zinc nitrates, 10 kilograms of platinum nitrates are added in 2 cubic metres of reactors, stir 30 minutes to obtain solution A with 100r/min rotating speed.1.5 kilograms of sesbania powder are dissolved in the ethanol of 3 liters and obtain solution B.At room temperature, solution B to be added in solution A and to stir 30 minutes, obtaining settled solution.Difference is, is instilled in above-mentioned solution by the ammoniacal liquor of 20 % by weight under intense agitation, until its PH=12.0, produces precipitation in the process, forms slurries.
Then maintenance stir while the temperature of slurries is elevated to 80 DEG C, at this temperature keep 0.5 hour aging to carry out.Filter slurries with Buchner funnel, wash filtering the solid obtained with water, until the pH value making final washings is 8, in washings, the concentration of nitrate anion is 0.01mol/l.Filter cake is inputted extruded moulding equipment, obtain length 5cm, the strip catalyst precarsor of diameter 3mm.Then this catalyst precarsor is transferred in infrared heater, 120 DEG C of dryings 12 hours, then transfer in Muffle furnace, 600 DEG C of calcinings 10 hours, obtain catalyst D3#.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Pt=1:0.18:0.025.
Comparative example 4 investigates the impact of ammonia concn used in co-precipitation step: less ammonia concn
According to the step of embodiment 1, according to the step of embodiment 1,550 liters of deionized waters, 420 kilograms of ferric nitrates, 95 kilograms of zinc nitrates, 10 kilograms of platinum nitrates are added in 2 cubic metres of reactors, stir 30 minutes to obtain solution A with 100r/min rotating speed.1.5 kilograms of sesbania powder are dissolved in the ethanol of 3 liters and obtain solution B.At room temperature, solution B to be added in solution A and to stir 30 minutes, obtaining settled solution.Difference is, is instilled in above-mentioned solution by the ammoniacal liquor of 2 % by weight under intense agitation, until its PH=9.0, produces precipitation in the process, forms slurries.
Then maintenance stir while the temperature of slurries is elevated to 80 DEG C, at this temperature keep 0.5 hour aging to carry out.Filter slurries with Buchner funnel, wash filtering the solid obtained with water, until the pH value making final washings is 8, in washings, the concentration of nitrate anion is 0.01mol/l.Filter cake is inputted extruded moulding equipment, obtain length 5cm, the strip catalyst precarsor of diameter 3mm.Then this catalyst precarsor is transferred in infrared heater, 120 DEG C of dryings 12 hours, then transfer in Muffle furnace, 600 DEG C of calcinings 10 hours, obtain catalyst D4#.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Pt=1:0.279:0.025.
Comparative example 5 investigates the impact of ammonia concn used in co-precipitation step: larger ammonia concn
According to the step of embodiment 1,550 liters of deionized waters, 420 kilograms of ferric nitrates, 95 kilograms of zinc nitrates, 10 kilograms of platinum nitrates are added in 2 cubic metres of reactors, stir 30 minutes to obtain solution A with 100r/min rotating speed.1.5 kilograms of sesbania powder are dissolved in the ethanol of 3 liters and obtain solution B.At room temperature, solution B to be added in solution A and to stir 30 minutes, obtaining settled solution.Difference is, is instilled in above-mentioned solution by the ammoniacal liquor of 30 % by weight under intense agitation, until its PH=9.0, produces precipitation in the process, forms slurries.
Then maintenance stir while the temperature of slurries is elevated to 80 DEG C, at this temperature keep 0.5 hour aging to carry out.Filter slurries with Buchner funnel, wash filtering the solid obtained with water, until the pH value making final washings is 8, in washings, the concentration of nitrate anion is 0.01mol/l.Filter cake is inputted extruded moulding equipment, obtain length 5cm, the strip catalyst precarsor of diameter 3mm.Then this catalyst precarsor is transferred in infrared heater, 120 DEG C of dryings 12 hours, then transfer in Muffle furnace, 600 DEG C of calcinings 10 hours, obtain catalyst D5#.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Pt=1:0.267:0.025.
Reaction embodiment
In this embodiment, the catalyst of above embodiment 1-15 and comparative example 1-5 is used to carry out the reaction of preparing butadiene with butylene oxo-dehydrogenation.Specifically, by various catalyst compressing tablet, being crushed to granularity with ball mill is 20-40 order, and getting 10 grams of Catalyst packings, to enter volume be in the stainless steel fixed bed reactors of 10 milliliters.Use the mist containing butylene of industrial source as butene reaction raw material, shown in this reaction raw materials table composed as follows:
The composition of butene reaction unstripped gas
| Raw material forms | Butane | Trans-2-butene | 1-butylene | Cis-2-butene |
| Molar content % | 32.1 | 37.2 | 11.6 | 19.1 |
Pass in described fixed bed reactors after this reaction raw materials, air and steam being mixed, reaction condition is as follows: butylene air speed: 400 hours
-1, steam/butene molar ratio=12, oxygen/butene molar ratio=0.67, reaction temperature 340 DEG C, reaction pressure is normal pressure.Characterize the composition of product gas flow by gas-chromatography in exit, reaction result is as shown in table 2 below:
The expression activitiy of the catalyst of table 1 embodiment 1-15 and comparative example 1-5.
| Contained element | Butene conversion % | Butadiene selective % | Butadiene yield % | |
| Embodiment 1 | Fe:Zn:Pt | 85.60％ | 94.90％ | 81.20％ |
| Embodiment 2 | Fe:Zn:Ph | 84.70％ | 93.20％ | 78.90％ |
| Embodiment 3 | Fe:Zn:Pt | 83.20％ | 94.70％ | 78.80％ |
| Embodiment 4 | Fe:Zn:Pt | 84.70％ | 95.20％ | 80.60％ |
| Embodiment 5 | Fe:Zn:Pt | 83.90％ | 93.80％ | 78.60％ |
| Embodiment 6 | Fe:Zn:Pd | 88.00％ | 96.80％ | 85.10％ |
| Embodiment 7 | Fe:Zn:Pt | 86.30％ | 96.50％ | 83.30％ |
| Embodiment 8 | Fe:Zn:Pt | 86.80％ | 95.10％ | 82.50％ |
| Embodiment 9 | Fe:Zn:Pt | 85.30％ | 96.90％ | 82.60％ |
| Embodiment 10 | Fe:Zn:Pt | 85.70％ | 96.20％ | 82.40％ |
| Embodiment 11 | Fe:Zn:Rh | 82.20％ | 93.70％ | 77.00％ |
| Embodiment 12 | Fe:Zn:Ru | 83.00％ | 94.30％ | 78.30％ |
| Embodiment 13 | Fe:Zn:Pd | 86.00％ | 96.20％ | 82.70％ |
| Embodiment 14 | Fe:Zn:Os | 81.70％ | 93.90％ | 76.70％ |
| Embodiment 15 | Fe:Zn:Ir | 80.50％ | 91.80％ | 73.90％ |
| Comparative example 1 | Fe:Zn | 75.70％ | 90.80％ | 68.70％ |
| Comparative example 2 | Fe:Zn:Pt | 65.20％ | 89.20％ | 58.20％ |
| Comparative example 3 | Fe:Zn:Pt | 55.80％ | 87.60％ | 48.90％ |
| Comparative example 4 | Fe:Zn:Pt | 75.30％ | 85.30％ | 73.60％ |
| Comparative example 5 | Fe:Zn:Pt | 72.90％ | 83.30％ | 71.70％ |
As can be seen from Table 1, catalyst of the present invention is being prepared in the reaction of butadiene by butylene, achieve relative to conventional ferrum-based catalyst in catalytic activity and reaction efficiency and significantly improve, in butene conversion, butadiene selective and yield, improve 4.8-12.3%, 1.6-6.0%, 5.2-16.4% respectively compared to the conventional ferrum-based catalyst not containing noble metal.
co-precipitation terminal pH is on the impact of catalyst
Table 2
| PH | Butene conversion % | Butadiene selective % | Butadiene yield % | |
| Embodiment 3 | 7.0 | 83.2％ | 94.7％ | 78.8％ |
| Embodiment 4 | 8.0 | 84.7％ | 95.2％ | 80.6％ |
| Embodiment 1 | 9.0 | 85.6％ | 94.9％ | 81.2％ |
| Embodiment 5 | 10.0 | 83.9％ | 93.8％ | 78.6％ |
| Comparative example 2 | 5.0 | 65.2％ | 89.2％ | 58.2％ |
| Comparative example 3 | 12.0 | 55.8％ | 87.6％ | 48.9％ |
As can be seen from Table 2, when the pH value of co-precipitation terminal is outside 6.5-10.5, obtained catalyst activity obviously reduces.
ammonia concn is on the impact of catalyst
Table 3
| Ammonia concn % | Butene conversion % | Butadiene selective % | Butadiene yield % | |
| Embodiment 1 | 20％ | 85.6％ | 94.9％ | 81.2％ |
| Embodiment 6 | 15％ | 88.0％ | 96.8％ | 85.1％ |
| Embodiment 7 | 5％ | 86.3％ | 96.5％ | 83.3％ |
| Comparative example 4 | 2％ | 75.30％ | 85.30％ | 73.60％ |
| Comparative example 5 | 30％ | 72.90％ | 83.30％ | 71.70％ |
As can be seen from Table 3, in co-precipitation step, when the ammonia concn used is outside 5-25% scope, obtained catalyst activity obviously reduces.
moulding process is on the impact of catalyst:
Table 4
| Moulding process | Butene conversion % | Butadiene selective % | Butadiene yield % | |
| Embodiment 1 | Extruded moulding | 85.6％ | 94.9％ | 81.2％ |
| Embodiment 12 | Mist projection granulating is shaping | 83.0％ | 94.3％ | 78.3％ |
As can be seen from the data of table 4, no matter be that the catalyst of the present invention prepared by extruded moulding or the mist projection granulating method of forming can obtain excellent catalytic effect.
Claims (10)
1. iron-zinc composite oxide the catalyst of a modified with noble metals, this catalyst comprises iron-zinc composite oxide phase and metal oxide containing precious metals, wherein iron-zinc composite oxide is made up of iron oxide and zinc oxide, described noble metal be selected from ruthenium, rhodium, palladium, osmium, iridium, platinum one or more, be 100 parts by weight with the gross weight of described iron-zinc composite oxide phase, the content of described metal oxide containing precious metals is 0.5-5 weight portion.
2. iron-zinc composite oxide the catalyst of modified with noble metals as claimed in claim 1, it is characterized in that, described iron-zinc composite oxide belongs to spinelle crystal formation mutually, and its molecular formula is Zn
xfe
2o
y, wherein x is that 0.5 ~ 1.18, y depends on the numerical value of x and the valence state of iron and zinc, makes described iron-zinc composite oxide meet charge balance mutually.
3. be used for the method for the iron-zinc composite oxide catalyst preparing modified with noble metals according to any one of claim 1-2, the method comprises the following steps:
(1) formed and comprise the solution of molysite, zinc salt, precious metal salt and surfactant, wherein said noble metal be selected from ruthenium, rhodium, palladium, osmium, iridium, platinum one or more;
(2) make the pH value of the solution of step (1) gained raise, obtain slurries;
(3) heat ageing and washing operation are carried out to the slurries of step (2) gained;
(4) forming operation is carried out to the material of step (3) gained, obtained catalyst precarsor;
(5) roasting is carried out to described catalyst precarsor, the iron-zinc composite oxide catalyst of obtained described modified with noble metals.
4. method as claimed in claim 3, it is characterized in that, described step (1) and (2) are carried out in the reaction vessel that volume is 1-20 cubic meter.
5. method as claimed in claim 3, it is characterized in that, for step (1), described molysite, zinc salt and precious metal salt are selected from the water-soluble metal salt of these elements, and described water-soluble metal salt comprises nitrate, sulfate, sulphite, phosphate and oxalates; Described surfactant is selected from sesbania powder, methylcellulose, polyvinyl alcohol; In described solution, the molar concentration of iron ion is 0.5-2mol/l, and the molar concentration of zinc ion is 0.1-1.5mol/l, and the molar concentration of precious metal ion is 0.01-0.5mol/l.
6. method as claimed in claim 3, is characterized in that, for step (2), by alkaline solution being added the solution of step (1) gained, making the pH value of this solution be elevated to 6.5-10.5, thus obtained slurries; Preferably, described alkaline solution to be weight concentration be 5% ~ 25% ammoniacal liquor.
7. method as claimed in claim 3, it is characterized in that, for step (3), first obtained to step (2) at the temperature of 30-100 DEG C slurries heat ageing 0.5-1.5 hour, then filter, then wash filtering the solid material obtained with water, until the pH value of washings is 7.0-8.0, and the inorganic anion concentration in washings is 0.001-0.1 mol/L.
8. method as claimed in claim 3, it is characterized in that, for step (4), described forming operation is selected from extruded moulding and mist projection granulating is shaping; In described extruded moulding, the solid material input extruded moulding equipment that step (3) is obtained, the diameter of obtained bar is 2-5mm, and length is 3-5cm; In described mist projection granulating is shaping, solid material step (3) obtained suspends and forms the suspension that solid-weight content is 25-40 % by weight in a solvent, then with the speed of 100-200ml/min, this suspension is inputted spraying drying granulating equipment, the inlet temperature of described spraying drying granulating equipment is 150-350 DEG C, discharging opening temperature is 50-250 DEG C, and the particle diameter of obtained microspheres with solid is 20-200 micron.
9. method as claimed in claim 3, it is characterized in that, for step (5), product under the temperature of 80-150 DEG C the dry 5-50 hour obtained by step (4), preferred 12-25 hour, then at 300-1000 DEG C, the roasting temperature 3-25 hour of preferred 500-700 DEG C, preferred 8-15 hour, the iron-zinc composite oxide catalyst of obtained described modified with noble metals.
10. one kind by Oxidative Dehydrogenation of Butene for 1, the method of 3-butadiene, the method comprises: at reaction conditions, makes to comprise the raw mixture of butylene, oxygen and steam and the catalyst exposure according to any one of claim 1-2, generate 1,3-butadiene product;
In described raw mixture, the gas hourly space velocity of butylene is 200-600 hour
-1, preferred 400-600 hour
-1; The mol ratio of oxygen and butylene is 0.5-1.0, preferred 0.6-0.8; The mol ratio of steam and butylene is 5-16, preferred 9-12; Reaction temperature is 300-400 DEG C, preferred 330-400 DEG C; Reaction pressure is 0.001 ~ 1MPa, is preferably 0.05-0.2MPa, most preferably is 0.08-0.14MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410538577.8A CN105478140B (en) | 2014-10-13 | 2014-10-13 | A kind of iron zinc composite oxide catalyst of modified with noble metals and its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410538577.8A CN105478140B (en) | 2014-10-13 | 2014-10-13 | A kind of iron zinc composite oxide catalyst of modified with noble metals and its preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105478140A true CN105478140A (en) | 2016-04-13 |
| CN105478140B CN105478140B (en) | 2018-02-27 |
Family
ID=55665621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410538577.8A Expired - Fee Related CN105478140B (en) | 2014-10-13 | 2014-10-13 | A kind of iron zinc composite oxide catalyst of modified with noble metals and its preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105478140B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101674883A (en) * | 2007-05-10 | 2010-03-17 | Sk能源株式会社 | Zinc ferrite catalysts, method of preparing thereof and method of preparing 1,3-butadiene using thereof |
| US20120059208A1 (en) * | 2010-09-02 | 2012-03-08 | Aghaddin Mamedov | Modified zinc ferrite catalyst and method of preparation and use |
| CN103102238A (en) * | 2011-11-14 | 2013-05-15 | 中国石油化工股份有限公司 | Method for producing butadiene by oxidatively dehydrogenating butene and used catalyst |
| CN103965000A (en) * | 2013-01-30 | 2014-08-06 | 中国石油化工股份有限公司 | Method for producing butadiene through oxidation dehydrogenation of butene |
-
2014
- 2014-10-13 CN CN201410538577.8A patent/CN105478140B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101674883A (en) * | 2007-05-10 | 2010-03-17 | Sk能源株式会社 | Zinc ferrite catalysts, method of preparing thereof and method of preparing 1,3-butadiene using thereof |
| US20120059208A1 (en) * | 2010-09-02 | 2012-03-08 | Aghaddin Mamedov | Modified zinc ferrite catalyst and method of preparation and use |
| CN103102238A (en) * | 2011-11-14 | 2013-05-15 | 中国石油化工股份有限公司 | Method for producing butadiene by oxidatively dehydrogenating butene and used catalyst |
| CN103965000A (en) * | 2013-01-30 | 2014-08-06 | 中国石油化工股份有限公司 | Method for producing butadiene through oxidation dehydrogenation of butene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105478140B (en) | 2018-02-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105381796B (en) | The catalyst of organic oxygen-containing compound hydrogenation deoxidation and preparation method and application in a kind of oil product | |
| CN105315130B (en) | A kind of method that 1,3 dihydric alcohols are prepared by Prins condensation reactions | |
| CN103657704A (en) | Catalyst for preparing tetrahydronaphthalene by naphthalene via selective hydrogenation as well as preparation method and application thereof | |
| CN104383928A (en) | Preparing method of high-performance catalyst for hydrogenation of carbon dioxide for synthesizing methyl alcohol | |
| CN102989490A (en) | Copper-hydroxyapatite catalyst for synthesizing methyl glycolate and ethylene glycol and preparation method thereof | |
| CN113492021B (en) | Preparation method of rhodium catalyst | |
| CN105561997A (en) | Preparation method of nickel liquid phase hydrogenation catalyst | |
| CN103100410B (en) | Preparation method of hydrogenation catalyst containing molecular sieve | |
| CN113042060A (en) | Aldehyde hydrogenation catalyst and preparation method thereof | |
| CN102649742B (en) | Method for increasing selectivity of glycollic acid ester | |
| CN104549318A (en) | Catalyst for preparing furfuryl alcohol through hydrogenating furfural liquid phase and preparation method of catalyst | |
| CN105478140A (en) | Noble-metal-modified iron-zinc composite oxide catalyst, and preparation method and application thereof | |
| CN101168124A (en) | Catalyst used for alcohol dehydration producing ethylene and preparation method | |
| CN104437577A (en) | Iron spinel composite oxide catalyst and application thereof | |
| CN111170829A (en) | Preparation method of hexamethyl indanol | |
| CN105562007A (en) | Fe-based metal oxide catalyst, and preparation method and application thereof | |
| CN104117373B (en) | Mixed metal oxide catalyst of P Modification and its preparation method and application | |
| CN104525219A (en) | Method for preparing catalyst for preparing methyl glycolate by adding hydrogen into dimethyl oxalate | |
| CN108164383A (en) | A kind of method for preparing cis-pinane | |
| CN109420510A (en) | A kind of preparing cyclohexane by hydrogenating benzene catalyst and preparation method thereof | |
| CN103241746B (en) | In-situ synthetic method of modified molecular sieve for preparing ethylene by transforming ethanol | |
| CN104117364B (en) | A kind of mixed metal oxide catalyst and its preparation method and application | |
| CN102649744A (en) | Production method for glycolic acid ester | |
| CN100584813C (en) | Method for preparing terephthalyl alcohol by hydrogenation of terephthalic acid | |
| CN112439434A (en) | Ethylene glycol hydrofining agent and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180227 Termination date: 20191013 |