CN105562007A - Fe-based metal oxide catalyst, and preparation method and application thereof - Google Patents
Fe-based metal oxide catalyst, and preparation method and application thereof Download PDFInfo
- Publication number
- CN105562007A CN105562007A CN201410537815.3A CN201410537815A CN105562007A CN 105562007 A CN105562007 A CN 105562007A CN 201410537815 A CN201410537815 A CN 201410537815A CN 105562007 A CN105562007 A CN 105562007A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- mixed slurry
- content
- molar part
- butylene
- 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
Abstract
The invention provides a solid oxide catalyst used for preparation of butadiene from butylene through oxidative dehydrogenation. The catalyst comprises oxides of the following elements: Fe, X, Y and Z, wherein X is one selected from a group consisting of Zn, Mg and Mo, Y is one selected from a group consisting of Ca, Mn, Ni and Co, Z is one selected from a group consisting of Pt and Cu, and on the basis of 100 parts of Fe in the catalyst by mol, the contents of X, Y and Z are 10 to 80 parts by mol, 0.1 to 5 parts by mol and 0.05 to 5 parts by mol. The invention also provides a preparation method for the catalyst and application of the catalyst in preparation of butadiene from butylene through oxidative dehydrogenation.
Description
Technical field
The present invention relates to catalytic field, more particularly, the present invention relates to the ferrum-based catalyst for preparing butadiene with butylene oxo-dehydrogenation and Synthesis and applications thereof.
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, course of reaction 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 series catalysts of the first generation, the molybdenum series catalyst of the second generation and the Fe-series catalyst of the third generation, wherein Fe-series catalyst takes into account the advantage that catalytic activity is high and object selectivity of product is high.Fe-series catalyst of the prior art is substantially all adopt coprecipitation Kaolinite Preparation of Catalyst presoma, so-called coprecipitation refers in the solution containing two or more cations, they exist in solution with homogeneous phase, add precipitating reagent, after precipitation reaction, can obtain the homogeneous precipitation of various composition, it is the important method of the Ultrafines for complex oxide body of preparation containing two or more metallic element.The control of Coprecipitation is the key determining catalyst performance, then through washing, oven dry, roasting.
But said method takes time and effort, coprecipitation process and washing process are difficult to control, and the possibility of Catalyst Production failure is very big, and therefore people need to develop a kind of new method can with the catalyst of desired properties.
On the other hand, the catalyst developed at present still haves much room for improvement in butene conversion, butadiene selective and yield, catalyst life, 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 various metals carries out modification to iron-based oxide, and is prepared by the mode of spray-drying process.Compared with the existing catalyst in this area, catalyst of the present invention shows splendid catalytic activity, and have higher conversion ratio, selective and yield, catalyst life is long, and physical characteristic is stablized, and has lower race loss rate and wear rate.In addition, catalyst of the present invention is synthesized by spray drying granulation method, can be very easy and prepare required catalyst at low cost by this kind of mode, and eliminates that conventional coprecipitation success rate is low, the unmanageable problem of product property.
First aspect of the present invention provides a kind of solid oxide catalyst for Oxidative Dehydrogenation of Butene into Butadiene reaction, and this catalyst comprises the oxide of following element: Fe, X, Y and Z; Wherein X is selected from the one in Zn, Mg and Mo; Y is selected from the one in Ca, Mn, Ni and Co; Z is selected from the one in Pt and Cu; Be 100 molar part in the mole of Fe in this catalyst, the content of X is 10-80 molar part, and the content of Y is 0.1-5 molar part, and the content of Z is 0.05-5 molar part.Preferably, be 100 molar part in the mole of Fe in described solid oxide catalyst, the content of X is 40-60 molar part, and the content of Y is 0.2-0.8 molar part, and the content of Z is 0.5-1 molar part.
Second aspect of the present invention provides a kind of method being used for preparing solid oxide catalyst of the present invention, and the method comprises the following steps: the presoma of Fe, X, Y and Z element mixes with binding agent and water by (1), obtains mixed slurry; (2) spraying dry is carried out to described mixed slurry, obtained catalyst precursor microspheres; (3) roasting is carried out to described catalyst precursor microspheres.
In an embodiment of the invention, the presoma of described Fe, X, Y and Z element is selected from one or more in the nitrate of these elements, sulfate, hydroxide, oxide, metal acid ammonium.
Preferably, said method comprising the steps of: first described presoma is pulverized by (1), then dry under the condition of 80-200 DEG C, preferably 80-160 DEG C, form dry solid oxide compound mixture, then the solid oxide compound mixture of this drying is mixed with binding agent and water, obtain mixed slurry, in the gross mass of this mixed slurry for benchmark, the solids content of this mixed slurry is 10-50 quality %, preferred 20-40 quality %; (2) spraying dry is carried out to described mixed slurry, obtained catalyst precursor microspheres; (3) described catalyst precursor microspheres dry 12-24 hour at the temperature of 80-160 DEG C, at the roasting temperature 10-24 hour of 300-700, forms described solid oxide catalyst.
Of the present invention another preferred embodiment in, described binding agent is selected from one in sesbania powder, methylcellulose, polyvinyl alcohol or two or more, in the gross mass of described mixed slurry for benchmark, the content of described binding agent is 0.1-8 quality %, preferred 3-6 quality %.
Of the present invention another preferred embodiment in, spraying drying granulating equipment is used to carry out spray drying granulation to described raw slurry, the feed rate that raw slurry inputs described spray dryer is 100-150ml/min, the inlet temperature of described spraying drying granulating equipment is 150-350 DEG C, discharging opening temperature is 80 DEG C-180 DEG C, and the particle diameter of obtained microspheres with solid is 20 microns ~ 600 microns.
It is that raw material prepares 1 by oxidative dehydrogenation with butylene that 3rd aspect of the present invention provides a kind of, 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.Preferably, in described raw mixture, the gas hourly space velocity of butylene is 200-600 hour-1; The mol ratio of oxygen and butylene is 0.4-1.0; The mol ratio of steam and butylene is 8-16; Reaction temperature is 300-400 DEG C, and reaction pressure is 0 ~ 1MPa.
Detailed description of the invention
" scope " disclosed herein is 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 and may be combined with, 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.
The invention provides a kind of solid oxide catalyst for Oxidative Dehydrogenation of Butene into Butadiene reaction, this catalyst comprises the oxide of following element: Fe, X, Y and Z; Wherein X is selected from the one in Zn, Mg and Mo; Y is selected from the one in Ca, Mn, Ni and Co; Z is selected from the one in Pt and Cu; Be 100 molar part in the mole of Fe in this catalyst, the content of X is 10-80 molar part, and the content of Y is 0.1-5 molar part, and the content of Z is 0.05-5 molar part.Except the oxide component that these have catalytic activity, catalyst of the present invention also may comprise the impurity of various auxiliary agent and minute quantity as required, described auxiliary agent can comprise co-catalyst, structure reinforcing agent, filler etc., and described impurity inevitably may be introduced in preparation process by various raw material and process equipment.Of the present invention one preferred embodiment in, solid oxide catalyst of the present invention by described Fe, X, Y and Z oxide and inevitably impurity composition form.
In an embodiment of the invention, be 100 molar part in the mole of Fe in this catalyst, the content of X is 20-80 molar part, or 30-70 molar part, or 35-65 molar part, or 40-60 molar part.In yet another embodiment of the present invention, be 100 molar part in the mole of Fe in this catalyst, the content of Y is 0.2-0.8 molar part, or 0.3-0.7 molar part, or 0.4-0.5 molar part.In yet another embodiment of the present invention, the content of Z is 0.1-1.8 molar part, or 0.2-1.6 molar part, or 0.4-1.1 molar part, or 0.5-1 molar part, or 0.6-0.8 molar part.
The present invention also provides a kind of method preparing above-mentioned solid oxide catalyst, and the method comprises the following steps:
(1) presoma of Fe, X, Y and Z element is mixed with binding agent and water, obtain mixed slurry; Wherein X is selected from the one in Zn, Mg and Mo; Y is selected from the one in Ca, Mn, Ni and Co; Z is selected from the one in Pt and Cu;
(2) spraying dry is carried out to described mixed slurry, obtained catalyst precursor microspheres;
(3) roasting is carried out to described catalyst precursor microspheres.
For the situation comprising other auxiliary agents in described solid oxide catalyst in addition, described auxiliary agent can be added in the obtained mixed slurry of step (1).
Specifically, first described presoma is pulverized, then dry under the condition of 80-200 DEG C, preferably 80-160 DEG C, form dry solid oxide compound mixture, then the solid oxide compound mixture of this drying is mixed with binding agent and water, obtain mixed slurry, in the gross mass of this mixed slurry for benchmark, the solids content of this mixed slurry is 20-40 quality %; Then, spraying dry is carried out to described mixed slurry, obtained catalyst precursor microspheres; Finally, described catalyst precursor microspheres is dry 12-24 hour at 80-160 DEG C, at the roasting temperature 10-24 hour of 300-700 DEG C, forms described solid oxide catalyst.
In catalyst of the present invention, the metal oxide of activating oxide component is derived from corresponding metal precursor, and described presoma comprises the nitrate of corresponding metallic element, sulfate, hydroxide, oxide and metal acid ammonium.Such as, when X element is Mo time, ammonium molybdate can be used as the presoma of molybdenum.
The present invention by spray drying granulation method Kaolinite Preparation of Catalyst, thus eliminates the catalyst composition by existing during coprecipitation Kaolinite Preparation of Catalyst, the active and unmanageable problem of performance, and effectively simplifies technique, reduces cost.Because the granularity of various metal precursor raw material does not often meet the demands, usually need first with disintegrating apparatus, these precursors to be broken to required granularity.Described disintegrating apparatus can be arbitrary equipment known in the art, such as tooth-like pulverizer, beater grinder, airslide disintegrating mill, micronizer, ball mill, roller pulverizer, blade pulverizer, turbine type crushing machine etc., as long as can by these metal precursor Raw material processings to required granularity.In an embodiment of the invention, DFT-250 type high speed disintegrator is used.In yet another embodiment of the present invention, by described presoma according to after target proportion mixing, in disintegrating apparatus, 0.1-150 micron is crushed to.
After precursor mixture is crushed to required granularity, at 80-200 DEG C, at the temperature of preferred 80-160 DEG C, drying is carried out to this mixture, thus remove the moisture that may comprise in described mixture.The duration of described drying depends on the moisture specifically comprised in presoma, such as, can be 1-10 hour, preferred 1-5 hour, more preferably 2-4 hour, most preferably 0.5-3 hour.
After drying, described precursor mixture is mixed with water and binding agent, form mixed slurry.Described binding agent 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 binding agent is selected from one in sesbania powder, methylcellulose, polyvinyl alcohol or two or more, and in the gross mass of described mixed slurry for benchmark, the content of described binding agent is 0.1-8 quality %, preferred 3-6 quality %.In the gross mass of described mixed slurry for benchmark, in this mixed slurry, the total content (i.e. solids content) of all components is in addition to water 10 ~ 50 quality %, preferably 20 ~ 40 quality %.
In step (2), spraying drying granulating equipment is used to carry out spraying dry to described mixed slurry, obtained catalyst precursor microspheres.Described spraying drying granulating equipment can be the arbitrary equipment that this neighborhood is known, 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 spray drying granulation machine; the feed rate that described mixed slurry inputs described spray drying granulation machine is 100-150ml/min; the inlet temperature of described spray drying granulation machine is 150-350 DEG C; discharging opening temperature is 80-130 DEG C; the particle diameter of obtained catalyst precursor microspheres is 20-600 micron, preferably 80 microns ~ 300 microns.
In step (3), described catalyst precursor microspheres puts into infrared baking box or forced ventilation convection oven, drying 1 ~ 24 hour at the temperature of 80-200 DEG C, preferably 80-160 DEG C, preferred 10-20 hour, then transfer in Muffle furnace, in air atmosphere, at the roasting temperature 10-24h of 300-900 DEG C, preferably 300-700 DEG C, thus obtained catalyst of the present invention.
It is pointed out that the binding agent of use is selected from methylcellulose, polyvinyl alcohol, sesbania powder at this, and combination, these binding agents can be burnouted completely in roasting process, and obtained catalyst is not containing any adhesion component.
In catalyst of the present invention except activating oxide component, also inevitably comprise the impurity of minute quantity, these impurity are introduced by one or more in the sources such as metal precursor, binding agent, water, process equipment.In an embodiment of the invention, in the gross mass of catalyst of the present invention for benchmark, the content of described impurity composition is less than 1 quality %, is preferably less than 0.5 quality %, is preferably less than 0.1 quality %, is more preferably less than 0.02 quality %.
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 is that butadiene prepared by raw material.Described C
4mixture 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.
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 sesbania powder used is the M375480 type that westernization instrument (Beijing) Science and Technology Ltd. produces.The methylcellulose used is that Xi'an Yue Lai Pharmaceutical Technology Co., Ltd produces.The high speed disintegrator used is the DFT-250 type high speed disintegrator that Shanghai Ding Guang plant equipment Co., Ltd produces, and 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
Take 1mol ferric nitrate, 0.5mol zinc nitrate, 0.005mol calcium nitrate, 0.002mol copper nitrate respectively, it is added in high speed disintegrator together, under the rotating speed of 25000r/min, fully mixing blends 5 minutes, poured out by mixture after pulverizing, 150 DEG C of oven dry dewater 3 hours in an oven, obtain hybrid solid oxide, add 100 grams of sesbania powder more wherein, appropriate amount of deionized water, fully stirs, and obtains the mixed slurry that solid content is 35 quality %.By gained mixed slurry with the flow velocity of 150 ml/min input pneumatic spray drying comminutor; inlet temperature is 250 DEG C; outlet temperature is 150 DEG C; obtain catalyst precursor microspheres; then this catalyst precursor microspheres 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 prod.Recorded by the analysis of S3500 type laser fineness gage, the granularity of this catalyst granules is 50-150 micron.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Ca:Cu=1:0.49:0.005:0.0018.
Embodiment 2
Take 1mol ferric nitrate, 0.6mol magnesium nitrate, 0.005mol manganese nitrate, 0.006mol copper nitrate respectively, it is added in high speed disintegrator together, under the rotating speed of 25000r/min, fully mixing blends 5 minutes, mixture after pulverizing is poured out, dry at the temperature of 180 DEG C and dewater 2 hours, obtain dry hybrid solid oxide, add 100 grams of sesbania powder and appropriate amount of deionized water wherein, abundant stirring, obtains the mixed slurry that solid content is 40 quality %.By gained mixed slurry with the flow velocity of 150 ml/min input pneumatic spray drying comminutor; inlet temperature is 250 DEG C; outlet temperature is 150 DEG C; obtain catalyst precursor microspheres; then this catalyst precursor microspheres 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 prod.Recorded by the analysis of S3500 type laser fineness gage, the granularity of this catalyst granules is 30-180 micron.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Mg:Mn:Cu=1:0.6:0.043:0.0058.
Embodiment 3
Take 1mol ferric nitrate, 0.5mol zinc nitrate, 0.005mol calcium nitrate, 0.006mol platinum nitrate respectively, it is added in high speed disintegrator together, under the rotating speed of 25000r/min, mixing blends 10 minutes, mixture after pulverizing is poured out, dry at the temperature of 150 DEG C and dewater 3 hours, obtain dry hybrid solid oxide, add 100 grams of sesbania powder and deionized water wherein, abundant stirring, obtains the mixed slurry that solid content is 40 quality %.By gained mixed slurry with the flow velocity of 150 ml/min input pneumatic spray drying comminutor; inlet temperature is 250 DEG C; outlet temperature is 150 DEG C; obtain catalyst precursor microspheres; then this catalyst precursor microspheres 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 prod.Recorded by the analysis of S3500 type laser fineness gage, the granularity of this catalyst granules is 30-180 micron.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Ca:Pt=1:0.5:0.0053:0.006.
Embodiment 4
Take 1mol ferric nitrate, 0.5mol zinc nitrate, 0.005mol manganese nitrate, 0.004mol platinum nitrate respectively, it is added in high speed disintegrator together, under the rotating speed of 25000r/min, mixing blends 30 minutes, mixture after pulverizing is poured out, heat at the temperature of 160 DEG C and dewater 3 hours, obtain dry hybrid solid oxide, add 120 grams of methylcellulose and deionized water wherein, abundant stirring, obtains the mixed slurry that solid content is 30 quality %.By gained mixed slurry with the flow velocity of 150 ml/min input pneumatic spray drying comminutor; inlet temperature is 250 DEG C; outlet temperature is 150 DEG C; obtain catalyst precursor microspheres; then this catalyst precursor microspheres 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 prod.Recorded by the analysis of S3500 type laser fineness gage, the granularity of this catalyst granules is 35-175 micron.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Mn:Pt=1:0.5:0.052:0.0041.
Embodiment 5
Take 1mol ferric nitrate, 0.5mol magnesium nitrate, 0.003mol nickel nitrate, 0.001mol copper nitrate respectively, it is added in high speed disintegrator together, under the rotating speed of 25000r/min, mixing blends 8 minutes, mixture after pulverizing is poured out, dewater at the temperature of 160 DEG C dry 3 hours, obtain dry hybrid solid oxide, add 120 grams of methylcellulose and appropriate amount of deionized water wherein, abundant stirring, obtains the mixed slurry that solid content is 45 quality %.By gained mixed slurry with the flow velocity of 150 ml/min input pneumatic spray drying comminutor; inlet temperature is 250 DEG C; outlet temperature is 150 DEG C; obtain catalyst precursor microspheres; then this catalyst precursor microspheres 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 prod.Recorded by the analysis of S3500 type laser fineness gage, the granularity of this catalyst granules is 30-185 micron.
Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Mg:Ni:Cu=1:0.5:0.0035:0.0012.
Embodiment 6:
Take 1mol ferric nitrate, 0.6mol nitric acid molybdenum, 0.008mol nickel nitrate, 0.01mol platinum nitrate respectively, it is added in high speed disintegrator together, under the rotating speed of 25000r/min, mixing blends 6 minutes, mixture after pulverizing is poured out, dewater at the temperature of 160 DEG C dry 3 hours, obtain dry hybrid solid oxide, add 120 grams of methylcellulose and deionized water wherein, abundant stirring, obtains the mixed slurry that solid content is 45 quality %.By gained mixed slurry with the flow velocity of 150 ml/min input pneumatic spray drying comminutor; inlet temperature is 250 DEG C; outlet temperature is 150 DEG C; obtain catalyst precursor microspheres; then this catalyst precursor microspheres 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 prod.Recorded by the analysis of S3500 type laser fineness gage, the granularity of this catalyst granules is 35-185 micron.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Mo:Ni:Pt=1:0.6:0.008:0.011.
Embodiment 7:
Take 1mol ferric nitrate, 0.1mol nitric acid molybdenum, 0.002mol cobalt nitrate, 0.002mol platinum nitrate respectively, it is added in high speed disintegrator together, under the rotating speed of 25000r/min, mixing blends 5 minutes, mixture after pulverizing is poured out, dewater at the temperature of 160 DEG C dry 3 hours, obtain dry hybrid solid oxide, add 100 grams of sesbania powder and deionized water wherein, abundant stirring, obtains the mixed slurry that solid content is 45 quality %.By gained mixed slurry with the flow velocity of 150 ml/min input pneumatic spray drying comminutor; inlet temperature is 150 DEG C; outlet temperature is 150 DEG C; obtain catalyst precursor microspheres; then this catalyst precursor microspheres 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 prod.Recorded by the analysis of S3500 type laser fineness gage, the granularity of this catalyst granules is 30-180 micron.
Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Mg:Co:Pt=1:0.1:0.002:0.0022.
Embodiment 8
Take 1mol ferric nitrate, 0.8mol nitric acid molybdenum, 0.05mol cobalt nitrate, 0.01mol platinum nitrate respectively, it is added in high speed disintegrator together, under the rotating speed of 25000, mixing blends 5 minutes, mixture after pulverizing is poured out, dewater at the temperature of 160 DEG C dry 3 hours, obtain dry hybrid solid oxide, add 100 grams of sesbania powder and deionized water wherein, abundant stirring, obtains the mixed slurry that solid content is 45 quality %.By gained mixed slurry with the flow velocity of 150 ml/min input pneumatic spray drying comminutor; inlet temperature is 250 DEG C; outlet temperature is 150 DEG C; obtain catalyst precursor microspheres; then this catalyst precursor microspheres 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 prod.Recorded by the analysis of S3500 type laser fineness gage, the granularity of this catalyst granules is 30-200 micron.
Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Mo:Co:Pt=1:0.8:0.05:0.0087.
Embodiment 9
Take 1mol ferric nitrate, 0.4mol zinc nitrate, 0.001mol cobalt nitrate, 0.01mol platinum nitrate respectively, it is added in high speed disintegrator together, under the rotating speed of 25000r/min, mixing blends 5 minutes, mixture after pulverizing is poured out, dewater at the temperature of 160 DEG C dry 3 hours, obtain dry hybrid solid oxide, add 100 grams of sesbania powder and deionized water wherein, abundant stirring, obtains the mixed slurry that solid content is 45 quality %.By gained mixed slurry with the flow velocity of 150 ml/min input pneumatic spray drying comminutor; inlet temperature is 250 DEG C; outlet temperature is 150 DEG C; obtain catalyst precursor microspheres; then this catalyst precursor microspheres 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 prod.Recorded by the analysis of S3500 type laser fineness gage, the granularity of this catalyst granules is 40-180 micron.
Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Co:Pt=1:0.4:0.001:0.012.
Embodiment 10
Take 1mol ferric nitrate, 0.3mol magnesium nitrate, 0.04mol cobalt nitrate, 0.01mol copper nitrate respectively, it is added in high speed disintegrator together, under the rotating speed of 25000r/min, mixing blends 5 minutes, mixture after pulverizing is poured out, dewater heating 3 hours at the temperature of 160 DEG C, obtains dry hybrid solid oxide, add 120 grams of methylcellulose and deionized water wherein, abundant stirring, obtains the mixed slurry that solid content is 45 quality %.By gained mixed slurry with the flow velocity of 150 ml/min input pneumatic spray drying comminutor; inlet temperature is 250 DEG C; outlet temperature is 150 DEG C; obtain catalyst precursor microspheres; then this catalyst precursor microspheres 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 prod.Recorded by the analysis of S3500 type laser fineness gage, the granularity of this catalyst granules is 20-190 micron.
Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Mg:Co:Cu=1:0.3:0.043:0.016.
Embodiment 11
Take 1mol ferric nitrate, 0.8mol magnesium nitrate, 0.001mol nickel nitrate, 0.01mol copper nitrate respectively, it is added in high speed disintegrator together, under the rotating speed of 25000r/min, mixing blends 5 minutes, mixture after pulverizing is poured out, dewater at the temperature of 160 DEG C dry 3 hours, obtain dry hybrid solid oxide, add 120 grams of methylcellulose and deionized water wherein, abundant stirring, obtains the mixed slurry that solid content is 45 quality %.By gained mixed slurry with the flow velocity of 150 ml/min input pneumatic spray drying comminutor; inlet temperature is 250 DEG C; outlet temperature is 150 DEG C; obtain catalyst precursor microspheres; then this catalyst precursor microspheres 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 prod.Recorded by the analysis of S3500 type laser fineness gage, the granularity of this catalyst granules is 35-185 micron.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Mg:Ni:Cu=1:0.8:0.0012:0.013.
In following comparative example 1-3, prepare iron-based mixed metal oxide catalyst by the coprecipitation that prior art is known, be used for contrasting with preparation technology of the present invention.
Comparative example 1
Take 1mol ferric nitrate, 1mol zinc nitrate, 0.0001mol calcium nitrate, 0.0002mol copper nitrate respectively, be dissolved in obtained settled solution in 800 ml deionized water, then under the condition stirred, in this solution, the ammoniacal liquor that concentration is 1M is dripped, until the pH value of solution reaches 11.5.Collected by filtration, by deionized water to Washing of Filter Cake 4 times, each washing use 300 ml deionized water, the temperature of washings is 45 DEG C.Precipitated product after washing is added in deionized water together with 100 grams of sesbania powder, stirs and form the mixed slurry that solids content is 43 quality %.By gained mixed slurry with the flow velocity of 150 ml/min input pneumatic spray drying comminutor; inlet temperature is 250 DEG C; outlet temperature is 150 DEG C; obtain catalyst precursor microspheres; then this catalyst precursor microspheres 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 prod.Recorded by the analysis of S3500 type laser fineness gage, the granularity of this catalyst granules is 50-300 micron.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Ca:Cu=1:0.53:0.0007:0.0002.
Comparative example 2
Adopt the step identical with comparative example 1, use different metal nitrates as raw material, by coprecipitation Kaolinite Preparation of Catalyst product.Recorded by the analysis of S3500 type laser fineness gage, the granularity of this catalyst granules is 50-300 micron.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Mg:Mn:Cu=1:0.55:0.0006:0.0001
Comparative example 3
Adopt the step identical with comparative example 1, use different metal nitrates as raw material, by coprecipitation Kaolinite Preparation of Catalyst product.Recorded by the analysis of S3500 type laser fineness gage, the granularity of this catalyst granules is 50-300 micron.Recorded by icp analysis, in catalyst, the mol ratio of various element is Fe:Zn:Ca:Pt=1:0.56:0.0007:0.0004.
Reaction embodiment
In this embodiment, use above embodiment 1-11, reaction that the catalyst of comparative example 1-3 carries out preparing butadiene with butylene oxo-dehydrogenation.Specifically, get 15 grams of catalyst in the cold mould of DN25, purge 1.5 hours with air 400 hours-1 air speeds, after take 10g Catalyst packing and enter in the fluidized-bed reactor of DN25.Use the mist containing butylene of industrial source as butene reaction raw material, shown in this reaction raw materials table 1 composed as follows:
Table 1: 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=0.68, reaction temperature 380 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:
Table 2: catalyst activity characterization result
Can see from the result of table 2, the catalyst prepared by method of the present invention is at feed stock conversion, and the aspect such as selectivity of product and the yield catalyst obtained relative to the precipitation method all obtains significant improvement.
Claims (9)
1., for a solid oxide catalyst for Oxidative Dehydrogenation of Butene into Butadiene reaction, this catalyst comprises the oxide of following element: Fe, X, Y and Z; Wherein X is selected from the one in Zn, Mg and Mo; Y is selected from the one in Ca, Mn, Ni and Co; Z is selected from the one in Pt and Cu; Be 100 molar part in the mole of Fe in this catalyst, the content of X is 10-80 molar part, and the content of Y is 0.1-5 molar part, and the content of Z is 0.05-5 molar part.
2. solid oxide catalyst as claimed in claim 1, it is characterized in that, be 100 molar part in the mole of Fe in described solid oxide catalyst, and the content of X is 40-60 molar part, the content of Y is 0.2-0.8 molar part, and the content of Z is 0.5-1 molar part.
3. be used for preparing a method for solid oxide catalyst as claimed in claim 1 or 2, the method comprises the following steps:
(1) presoma of Fe, X, Y and Z element is mixed with binding agent and water, obtain mixed slurry;
(2) spraying dry is carried out to described mixed slurry, obtained catalyst precursor microspheres;
(3) roasting is carried out to described catalyst precursor microspheres.
4. method as claimed in claim 3, is characterized in that, the presoma of described Fe, X, Y and Z element be selected from the nitrate of these elements, sulfate, hydroxide, oxide, metal acid ammonium one or more.
5. method as claimed in claim 3, is characterized in that, said method comprising the steps of:
(1) first described presoma is pulverized, then dry under the condition of 80-200 DEG C, preferably 80-160 DEG C, form dry solid oxide compound mixture, then the solid oxide compound mixture of this drying is mixed with binding agent and water, obtain mixed slurry, in the gross mass of this mixed slurry for benchmark, the solids content of this mixed slurry is 10-50 quality %, preferred 20-40 quality %;
(2) spraying dry is carried out to described mixed slurry, obtained catalyst precursor microspheres;
(3) described catalyst precursor microspheres dry 12-24 hour at the temperature of 80-160 DEG C, at the roasting temperature 10-24 hour of 300-700, forms described solid oxide catalyst.
6. method as claimed in claim 3, it is characterized in that, described binding agent is selected from one in sesbania powder, methylcellulose, polyvinyl alcohol or two or more, in the gross mass of described mixed slurry for benchmark, the content of described binding agent is 0.1-8 quality %, preferred 3-6 quality %.
7. method as claimed in claim 3, it is characterized in that, spraying drying granulating equipment is used to carry out spray drying granulation to described raw slurry, the feed rate that raw slurry inputs described spray dryer is 100-150ml/min, the inlet temperature of described spraying drying granulating equipment is 150-350 DEG C, discharging opening temperature is 80 DEG C-180 DEG C, and the particle diameter of obtained microspheres with solid is 20 microns ~ 600 microns.
8. one kind is that raw material prepares 1 by oxidative dehydrogenation with butylene, 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 described in claim 1 or 2, generate 1,3-butadiene product.
9. method as claimed in claim 8, it is characterized in that, in described raw mixture, the gas hourly space velocity of butylene is 200-600 hour
-1; The mol ratio of oxygen and butylene is 0.4-1.0; The mol ratio of steam and butylene is 8-16; Reaction temperature is 300-400 DEG C, and reaction pressure is 0 ~ 1MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410537815.3A CN105562007B (en) | 2014-10-13 | 2014-10-13 | A kind of ferrous metals oxide catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410537815.3A CN105562007B (en) | 2014-10-13 | 2014-10-13 | A kind of ferrous metals oxide catalyst and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105562007A true CN105562007A (en) | 2016-05-11 |
| CN105562007B CN105562007B (en) | 2019-04-26 |
Family
ID=55872961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410537815.3A Expired - Fee Related CN105562007B (en) | 2014-10-13 | 2014-10-13 | A kind of ferrous metals oxide catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105562007B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106807453A (en) * | 2017-01-23 | 2017-06-09 | 山东三维石化工程股份有限公司 | The method of preparing butadiene with butylene oxo-dehydrogenation catalyst |
| CN107308942A (en) * | 2016-06-12 | 2017-11-03 | 中国石油化工股份有限公司 | The catalyst and its method of preparing butadiene with butylene oxo-dehydrogenation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4658074A (en) * | 1965-05-28 | 1987-04-14 | Petro-Tex Chemical Corporation | Catalytic oxidative dehydrogenation process |
| CN102716754A (en) * | 2012-07-12 | 2012-10-10 | 上海碧科清洁能源技术有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butene in fluidized bed reactor and preparation method and application thereof |
| CN103752316A (en) * | 2014-01-26 | 2014-04-30 | 惠生工程（中国）有限公司 | Iron catalyst for preparing butadiene through n-butene oxydehydrogenation and preparation method and application of iron catalyst |
-
2014
- 2014-10-13 CN CN201410537815.3A patent/CN105562007B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4658074A (en) * | 1965-05-28 | 1987-04-14 | Petro-Tex Chemical Corporation | Catalytic oxidative dehydrogenation process |
| CN102716754A (en) * | 2012-07-12 | 2012-10-10 | 上海碧科清洁能源技术有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butene in fluidized bed reactor and preparation method and application thereof |
| CN103752316A (en) * | 2014-01-26 | 2014-04-30 | 惠生工程（中国）有限公司 | Iron catalyst for preparing butadiene through n-butene oxydehydrogenation and preparation method and application of iron catalyst |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107308942A (en) * | 2016-06-12 | 2017-11-03 | 中国石油化工股份有限公司 | The catalyst and its method of preparing butadiene with butylene oxo-dehydrogenation |
| CN106807453A (en) * | 2017-01-23 | 2017-06-09 | 山东三维石化工程股份有限公司 | The method of preparing butadiene with butylene oxo-dehydrogenation catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105562007B (en) | 2019-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105582954B (en) | A kind of solid oxide catalyst and its preparation method and application | |
| CN105498787A (en) | Catalyst for producing 2-methylfuran through gas phase hydrogenation of furfural and preparation method of the catalyst | |
| CN103657704A (en) | Catalyst for preparing tetrahydronaphthalene by naphthalene via selective hydrogenation as well as preparation method and application thereof | |
| CN114829004A (en) | Method for preparing Ni-X-based oxide catalyst and application thereof in transfer hydrogenation | |
| CN103100410B (en) | Preparation method of hydrogenation catalyst containing molecular sieve | |
| CN107774303A (en) | Porous metals/molecular sieve composite catalyst, its preparation method and the purposes in preparing low-carbon olefin | |
| CN105562007A (en) | Fe-based metal oxide catalyst, and preparation method and application thereof | |
| CN104549318A (en) | Catalyst for preparing furfuryl alcohol through hydrogenating furfural liquid phase and preparation method of catalyst | |
| CN107866280A (en) | A kind of hydrocracking heavy oil Mo-Ni catalyst and preparation method thereof | |
| CN102041047A (en) | Heavy oil hydrogenation modifying method | |
| CN108383677A (en) | A method of catalysis australene Hydrogenation is for cis-pinane | |
| CN106316763B (en) | The method of lactone compound aromatisation production aromatic hydrocarbons | |
| CN105749930B (en) | Catalyst and preparation method thereof for Oxidative Dehydrogenation of Butene into Butadiene | |
| CN107866279A (en) | One kind is hydrocracked Mo-Ni catalyst and preparation method thereof | |
| CN108164383A (en) | A kind of method for preparing cis-pinane | |
| CN102580774A (en) | Unsaturated polymer hydrogenation catalyst and preparation method thereof | |
| CN110694657B (en) | Simple high-carbon aldehyde synthesis catalyst | |
| CN103769134B (en) | The preparation method of isobutene partial oxidation MAL catalyst | |
| CN106944079B (en) | A kind of preparation method of iso-butane preparing isobutene catalyst | |
| CN103319294B (en) | Method for synthesizing 1,3-butadiene by utilizing Bi/Mo/V (Bismuth/Molybdenum/Vanadium) three-component composite oxide catalyst | |
| CN105478140B (en) | A kind of iron zinc composite oxide catalyst of modified with noble metals and its preparation and application | |
| CN106867579B (en) | A kind of method that lower carbon number hydrocarbons produces alkadienes and gasoline component | |
| CN104117364B (en) | A kind of mixed metal oxide catalyst and its preparation method and application | |
| CN105772017B (en) | The catalyst of butylene oxidation-dehydrogenation and preparation method thereof for fluidized bed | |
| CN103769135A (en) | Preparation method of catalyst for partial oxidization of isobutene to prepare methylacrolein |
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 |
Granted publication date: 20190426 Termination date: 20191013 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |