CN108325534A - A kind of catalyst of PROPENE IN GAS PHASE OXIDATION acrolein and its application - Google Patents

A kind of catalyst of PROPENE IN GAS PHASE OXIDATION acrolein and its application Download PDF

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Publication number
CN108325534A
CN108325534A CN201810106223.4A CN201810106223A CN108325534A CN 108325534 A CN108325534 A CN 108325534A CN 201810106223 A CN201810106223 A CN 201810106223A CN 108325534 A CN108325534 A CN 108325534A
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Prior art keywords
catalyst
metal oxide
crystal structure
added
oxide
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郭薇
李鹏
潘彪
王宇
赵小平
郭耀星
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GANSU DONGHUA CATALYST Co Ltd
DONGHUA ENVIRONMENT ENGINEERING Co Ltd SHANGHAI
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GANSU DONGHUA CATALYST Co Ltd
DONGHUA ENVIRONMENT ENGINEERING Co Ltd SHANGHAI
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Publication of CN108325534A publication Critical patent/CN108325534A/en
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract

The invention belongs to catalyst preparation technical field, catalyst and its application that a kind of PROPENE IN GAS PHASE OXIDATION prepares methacrylaldehyde are disclosed, which includes molybdenum bismuth-system compound oxide and metal oxide, and the metal oxide is selected from TiO2、NiO、ZnO、La2O3、CeO2、CuO、Ga2O3、MgO、SnO2At least one of, the metal oxide has crystal structure.The corresponding metallic element of the quasi-metal oxides is mostly variable valency metal element, and the outermost electron of atom can form plurality of stable form, be conducive to the progress of oxidation-reduction process.Meanwhile the addition of the quasi-metal oxides, the transmission capacity of Lattice Oxygen and electronics in catalyst is changed, the activity of catalyst is increased, improves the selectivity of catalyst.In addition, the metal oxide with crystal structure, which is added, can also adjust the acid-base property of catalyst, and then the activity and selectivity of catalyst is improved, reduces side reaction and the generation of carbon distribution.

Description

A kind of catalyst of PROPENE IN GAS PHASE OXIDATION acrolein and its application
Technical field
The invention belongs to catalyst preparation technical field, the catalyst that a kind of PROPENE IN GAS PHASE OXIDATION prepares methacrylaldehyde is disclosed And its application.
Background technology
By using the multitubular reactor of fixed bed of shell and tube heat exchange type, under Mo-Bi (containing molybdenum-bismuth) oxidation catalyst, Using oxygen molecule or the gas of oxygen-containing molecules, prepares methacrylaldehyde by gas phase haptoreaction propylene oxide and be widely used in In industry.
It is adjoint other than main reaction has heat release since the gas phase oxidation of propylene is violent exothermic reaction Side reaction can also release a large amount of heat.Therefore, it is easy to form hot spot in the catalyst layer in each reaction tube.Hot spot goes out Peroxidating, the selectivity of reaction is now caused to decline, the amount of target product methacrylaldehyde is reduced, and the by-products such as oxycarbide significantly increase Add, the performance of catalyst can also be damaged by being enriched in the carbon distribution by-product of catalyst surface, or even occur leading to catalyst inactivation Phenomenon has seriously affected the service life of catalyst.Therefore, the activity and selectivity for improving catalyst, to improving target product Yield, reduce by-product formation and extend catalyst service life, have vital effect.
In the prior art, Chinese patent literature CN101850260A disclose one kind be used to prepare (methyl) methacrylaldehyde and The catalyst of (methyl) acrylic acid, the catalyst are a kind of composite oxide catalysts containing molybdenum bismuth iron, are mainly used for propylene Or isobutene (tert-butyl alcohol) selective oxidation produces (methyl) methacrylaldehyde and (methyl) acrylic acid process, the catalyst is in preparation process In be added to oxide nanocrystal, the oxide nanocrystal is aluminium oxide, silica, molybdenum oxide, tungsten oxide, oxidation The mixture that one or more of cobalt, iron oxide, antimony-nickel oxide oxide is mixed with any proportion, above-mentioned oxidation Object nanocrystal has not only acted as the effect for adjusting catalyst acid alkalinity, improves (methyl) methacrylaldehyde and (methyl) acrylic acid Selectivity, reduces the yield of by-product carbonoxide, and enhance the mechanical strength of catalyst.However, above-mentioned document discloses Catalyst it is not high to the selectivity of target product (methyl) methacrylaldehyde, material total air speed be 1500h-1When, the catalyst Selectivity to aldehyde is up to 84.4%, and under higher air speed, selectivity and conversion ratio are greatly lowered.
Invention content
Therefore, the technical problem to be solved in the present invention is the catalysis for overcoming existing PROPENE IN GAS PHASE OXIDATION to prepare methacrylaldehyde Agent not high problem of selectivity under high-speed, to provide a kind of good stability, high mechanical strength and still have under high-speed There is the catalyst of good selectivity.
In order to solve the above technical problems, the present invention provides a kind of catalyst preparing methacrylaldehyde, including molybdenum-bismuth system is compound There is crystal structure, the metal oxide to be selected from TiO for oxide and metal oxide, the metal oxide2、NiO、ZnO、 La2O3、CeO2、CuO、Ga2O3、MgO、SnO2At least one of.
Further, the crystal structure of the metal oxide is needle-shaped or sheet.
Further, the crystal structure of the metal oxide be needle-shaped, a diameter of 2~200nm, length be 0.05~ 100μm。
Further, the crystal structure of the metal oxide be sheet, length be 10~300nm, width be 10~ 100nm。
Further, the crystal specific surface area of the metal oxide is 20~200m2/g。
Further, the addition quality of the metal oxide account for the molybdenum-bismuth-system compound oxide quality 0.5~ 40%.
In the present invention, the feed postition of metal oxide is not particularly limited, as long as metal oxide can be made equably It is dispersed in catalyst activity component.The starting material liquid that metal oxide can both be added to catalyst activity component is mixed It closes in object, can also be added in the catalyst activity component after drying and crushing, add together with binder and shaping assistant Enter.In addition, metal oxide can be added at one time, can also be added several times.
Further, the molybdenum-bismuth-system compound oxide has the general formula as shown in formula (I)：
Mo12BiaFebCocNidAeBfCgOn(Ⅰ)；
Wherein：
Mo, Bi, Fe, Co, Ni indicate molybdenum, bismuth, iron, cobalt and nickel respectively, A in alkali metal, alkaline-earth metal, thallium at least A kind of element, B are selected from chromium, tin, zinc, antimony, phosphorus, tungsten, manganese, at least one of cerium element, C in silicon, zirconium, aluminium, titanium extremely A kind of few element, O is oxygen；A, b, c, d, e, f, g and n indicate the atomic ratio of Bi, Fe, Co, Ni, A, B, C and O respectively；1 ＜ a≤ 5,1 ＜ b≤6,0.5 ＜ c≤7,0.01 ＜ d≤8, the 0.02 ＜ ＜ of e≤3,0.01≤f≤5,0.2 g≤20, n is according to each element Oxidation state determine numerical value.
In the present invention, the well-known precipitation method may be used in the preparation of catalyst active component, and the molding of catalyst can It is realized in a manner of using single screw extrusion machine, double screw extruder, tablet press machine etc..
The present invention also provides the preparation method of above-mentioned catalyst, the metal oxide be applied directly to catalyst activity at In the material liquid divided；Or be added during shaping of catalyst, then roasting obtains the catalyst.
The application of the catalyst prepared the present invention also provides above-mentioned catalyst or according to the above method, the catalyst are used Methacrylaldehyde is produced in Selective Oxidation of Propylene.
Further, the oxidation reaction existing for molecular oxygen or molecule-containing keto under the conditions of carry out.
Further, oxidation reaction is using reaction condition identical with industrial production (tube inner diameter 25.4mm, reaction Tubulation length 4000mm, 3000~3500mm of catalyst packing height), reaction raw materials propylene, water, oxygen and nitrogen are through 150 DEG C It is entered back into reactor after the above preheater preheating, reaction condition is 315~350 DEG C of salt temperature, 600~2500h of air speed-1, Oxygen：Nitrogen：Vapor：Propylene=(1~5)：(0.5~10)：(0.5~5)：1.
Technical scheme of the present invention has the following advantages that：
1. a kind of PROPENE IN GAS PHASE OXIDATION provided by the invention prepares the catalyst of methacrylaldehyde, including molybdenum-bismuth system combined oxidation Object and metal oxide, the metal oxide are selected from TiO2、NiO、ZnO、La2O3、CeO2、CuO、Ga2O3、MgO、SnO2In At least one, the metal oxide have crystal structure, and the corresponding metallic element of the quasi-metal oxides is mostly the gold that appraises at the current rate Belong to element, the outermost electron of atom can form plurality of stable form, be conducive to the progress of oxidation-reduction process.Meanwhile it should The addition of quasi-metal oxides changes the transmission capacity of Lattice Oxygen and electronics in catalyst, increases the activity of catalyst, carries The high selectivity of catalyst.In addition, the metal oxide with crystal structure, which is added, can also adjust the acid-base property of catalyst, into And the activity and selectivity of catalyst is improved, reduce side reaction and the generation of carbon distribution.
2. a kind of PROPENE IN GAS PHASE OXIDATION provided by the invention prepares the catalyst of methacrylaldehyde, the crystal of the metal oxide Structure is needle or sheet, and the metal oxide of the specific structure can connect catalyst granules, that is, enhance catalyst particles well Connection between grain, improves the stability and mechanicalness of catalyst, extends the service life of catalyst, is catalytic oxidation It is smoothed out to provide and effectively ensure.
3. a kind of PROPENE IN GAS PHASE OXIDATION provided by the invention prepares the catalyst of methacrylaldehyde, the metal is further defined The quality of oxide and the size of crystal and specific surface area, further increase the selectivity, stability and mechanicalness of catalyst.
4. a kind of PROPENE IN GAS PHASE OXIDATION provided by the invention prepares the catalyst of methacrylaldehyde, active constituent is in addition to molybdenum bismuth group Exceptionally, all multicomponents being additionally added including alkali metal, alkaline-earth metal etc., by adjusting the type and relative quantity of institute's addition element, It is further improved the performance of catalyst, improves the activity and selectivity of catalyst.
It, can will be described 5. a kind of PROPENE IN GAS PHASE OXIDATION provided by the invention prepares the preparation method of methacrylaldehyde catalyst Metal oxide is applied directly in the material liquid of catalyst active component, or in catalyst together with binder, shaping assistant It is added in forming process, then roasting obtains the finished product of the catalyst, easy to operate, it is easy to accomplish, it is suitble to industrial catalyst Preparation and macrocyclic commercial Application.
6. a kind of PROPENE IN GAS PHASE OXIDATION provided by the invention prepares the application of methacrylaldehyde catalyst, in molecular oxygen or contain molecule Under the conditions of oxygen is existing, methacrylaldehyde is prepared using the catalyst propylene oxide.It is reacted using identical with industrial production Condition (tube inner diameter 25.4mm, reaction tube length 4000mm, 3000~3500mm of catalyst packing height), it is total in material Air speed is 600~2500h-1Under conditions of, for the high selectivity of acrylic acid up to 87.5%, yield is up to 86.6%, achieves preferably Technique effect, can large-scale promotion application in the industrial production.
Specific implementation mode
Technical scheme of the present invention will be clearly and completely described below, it is clear that described embodiment is this hair Bright a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having There is the every other embodiment obtained under the premise of making creative work, shall fall within the protection scope of the present invention.In addition, below Involved technical characteristic as long as they do not conflict with each other can be mutual in described different embodiments of the present invention In conjunction with.
In embodiments given below, acrolein conversion rate, acrylic acid yield and selectivity and dropping impact strength, Dusting degree is defined as follows：
Acrolein conversion rate (%)=(methacrylaldehyde molal quantity in methacrylaldehyde molal quantity/raw material of reaction) × 100%
Acrylic acid yield (%)=(methacrylaldehyde molal quantity in acrylic acid molal quantity/raw material of generation) × 100%
Acrylic acid selectivity (%)=(the methacrylaldehyde molal quantity of acrylic acid molal quantity/reaction of generation) × 100%
Mechanical strength (%)=(remain in the catalyst quality on sieve/catalyst quality fallen) × 100
Dusting degree (%)=(catalyst quality-remains in the catalyst quality on sieve)/catalyst quality × 100
Present disclosure is further elaborated below by embodiment.
Embodiment 1
The catalyst that a kind of PROPENE IN GAS PHASE OXIDATION prepares methacrylaldehyde is present embodiments provided, preparation method is as follows：
800.0g ammonium molybdates and 1.7g potassium hydroxide are dissolved under heating stirring in 2000g distilled water and form solution A；It will 305.1g ferric nitrates, 637.4g cobalt nitrates and 329.4g nickel nitrates, which are dissolved in 500g distilled water, forms B solution；In 300g distilled water Middle addition 50g concentrated nitric acids (mass concentration 65%) form acidic aqueous solution, and it is molten that 329.7g bismuth nitrates formation C is added thereto Liquid；B solution and C solution are mixed to form solution D；Solution A is heated and be vigorously stirred, shape is slowly added dropwise into solution A in solution D At suspension, suspension is placed in oven and dried to decorating film.Obtained decorating film is crushed to 200 μm hereinafter, being urged The reactive powder of agent.Be added into above-mentioned reactive powder account for the length of its quality 5% be 10~50nm, width be 80~ 100nm, the ZnO that crystal structure is sheet add the Ludox that 100mL mass concentrations are 15~40% and are used as kneading agent, squeeze Go out molding, obtains the hollow cylindrical particle of outer diameter 5mm, internal diameter 2mm, length 5mm, activated at 460 DEG C in air atmosphere 5h obtains finished catalyst.
In the present embodiment, other than oxygen, the composition of the reactive powder is：
Mo12Bi1.8Fe2.0Co5.8Ni3.0K0.08。
In the present embodiment, the crystal structure is that the preparation process of sheet ZnO is specially：It is mixed with 500g water-ethanols molten (the two volume ratio is 1 to liquid:1) it is used as solvent, 50g zinc chloride and 125g urea are added in water-ethanol mixed solution, heating rises Temperature is stirred 5h to 55 DEG C, is filtered, washed, and filter cake dry 1.5h at 88 DEG C is subsequently placed in Muffle furnace at 218 DEG C 3h is roasted, the ZnO powder that crystal structure is sheet is obtained.
Embodiment 2
Present embodiments provide the catalyst that a kind of PROPENE IN GAS PHASE OXIDATION prepares methacrylaldehyde, preparation method with embodiment 1, The difference is that in the present embodiment, length that its quality 40% is added into reactive powder is 4~6 μm, a diameter of 30~ 80nm, crystal structure are acicular NiO, add the Ludox that 100mL mass concentrations are 15~40% and are used as kneading agent, squeeze out Molding, obtains the hollow cylindrical particle of outer diameter 5mm, internal diameter 2mm, length 5mm, 5h is activated at 520 DEG C in air atmosphere Obtain finished catalyst.
In the present embodiment, the crystal structure is that the preparation process of needle-shaped NiO is specially：It, will using 500mL water as solvent 430g nickel nitrates are added to the water with 518g oxalic acid, are heated to 80 DEG C, are stirred 5h, are filtered, washed, and filter cake is at 88 DEG C Lower dry 15h, is subsequently placed in Muffle furnace and roasts 3h at 360 DEG C, and it is acicular NiO sprills to obtain crystal structure.
Embodiment 3
Present embodiments provide the catalyst that a kind of PROPENE IN GAS PHASE OXIDATION prepares methacrylaldehyde, preparation method with embodiment 1, The difference is that in the present embodiment, be added into reactive powder 8~12 μm of the length of its quality 20%, diameter 160~ 200nm, crystal structure are acicular TiO2, then add 100mL to enter the Ludox that mass concentration is 15~40% and be used as kneading agent, it squeezes Go out molding, obtains the hollow cylindrical particle of outer diameter 5mm, internal diameter 2mm, length 5mm, activated at 490 DEG C in air atmosphere 5h obtains finished catalyst.
In the present embodiment, the crystal structure is needle-shaped TiO2Preparation process be specially：By 800mL butyl titanates, delay Slowly it is added in 2000mL absolute ethyl alcohols, magnetic agitation 10min to system is uniformly mixed, and forms solution A；By 300mL glacial acetic acid It is added in 3000mL absolute ethyl alcohols with 800mL water, stirs to get solution B, salt acid for adjusting pH value is added to 1.5；Solution A is added Into solution B, after stirring 30min, 40 DEG C of heating water baths obtain leucosol after 60min, are dried at 108 DEG C, through 500 DEG C It is acicular TiO that roasting 8h, which obtains crystal structure,2Powder.
Embodiment 4
Present embodiments provide the catalyst that a kind of PROPENE IN GAS PHASE OXIDATION prepares methacrylaldehyde, preparation method with embodiment 1, The difference is that 90~100 μm of the length of its quality 3%, 50~80nm of diameter, crystal structure be added into reactive powder being Acicular Ga2O3, add the Ludox that 100mL mass concentrations are 15%~40% and obtained outer as agent, extrusion molding is mediated The hollow cylindrical particle of diameter 5mm, internal diameter 2mm, length 5mm, activation 5h obtains finished product catalysis at 550 DEG C in air atmosphere Agent.
The crystal structure is needle-shaped Ga2O3Preparation process be specially：500g gallium nitrates are dissolved in 1000mL water, it is molten Solution is completely rear to be added the basic sodium sulfonate of 58g dodecanes, 180 DEG C of reactions in the autoclave with polytetrafluoroethyllining lining 15h is cooled to room temperature, and is filtered, washed, and dry 15h, 5h is roasted at 580 DEG C at 80 DEG C, and it is acicular to obtain crystal structure Ga2O3Powder.
Embodiment 5
The catalyst that a kind of PROPENE IN GAS PHASE OXIDATION prepares methacrylaldehyde is present embodiments provided, preparation method is as follows：
800.0g ammonium molybdates, 160.4g ammonium paratungstates and 110.4g cesium nitrates are dissolved in 2000g distillations under heating stirring Solution A is formed in water；686.5g ferric nitrates, 306.6g cobalt nitrates and 570.9g nickel nitrates are dissolved in 500g distilled water and form B Solution；50g concentrated nitric acids (mass concentration 65%) are added in 300g distilled water and form acidic aqueous solution, are added thereto 549.5g bismuth nitrate forms C solution；B solution and C solution are mixed to form solution D；Solution A is heated and is vigorously stirred, by solution D Be slowly added dropwise into solution A and form suspension, be added into suspension 250~300nm of length of its quality 30%, width 50~ 80nm, the CuO that crystal structure is sheet, after stirring evenly, suspension is placed in oven and dried to decorating film.Consolidate what is obtained Shape object is crushed to 200 μm and mediates agent hereinafter, adding the Ludox that 100mL mass concentrations are 15%~40% and being used as, and is extruded into Type obtains outer diameter 5mm, internal diameter 1mm, the hollow cylindrical particle that length is 5mm, 5h is activated at 540 DEG C in air atmosphere Obtain finished catalyst.
In the present embodiment, other than oxygen, the composition of the reactive powder is：
Mo12Bi3.0Fe4.5Co2.8Ni5.2Cs1.5W1.5。
In the present embodiment, the crystal structure is that the preparation process of sheet CuO is specially：400g copper nitrates are dissolved in In 1000mL water, 50g ethylenediamines are slowly added to, stirring is complete to mixing at 30 DEG C, then careless acid for adjusting pH value is added dropwise to 2.0, Filtering, filter cake are washed with 200mL water, 200mL ethyl alcohol respectively after the reaction was complete, and after dry at 80 DEG C, 500 DEG C of roasting 8h are obtained Crystal structure is the CuO powder of sheet.
Embodiment 6
Present embodiments provide the catalyst that a kind of PROPENE IN GAS PHASE OXIDATION prepares methacrylaldehyde, preparation method with embodiment 5, The difference is that 0.05~3 μm of the length of its quality 0.5%, 15~50nm of diameter, crystal structure be added into suspension being Acicular MgO, adds the Ludox that 100mL mass concentrations are 15%~40%, and extrusion molding obtains outer diameter 5mm, internal diameter The hollow cylindrical particle of 2mm, length 5mm, activation 5h obtains finished catalyst at 500 DEG C in air atmosphere.
In the present embodiment, the crystal structure is that the preparation process of needle-shaped MgO is specially：500g magnesium nitrates are dissolved in (the two volume ratio is 1 to 2000mL water-absolute ethyl alcohol:1) in solution, lemon acid for adjusting pH value is added thereto to 1.0, will mix Liquid is put into the autoclave with polytetrafluoroethyllining lining, is reacted 5h at 110 DEG C, is cooled to room temperature, respectively use 200mL water, 200mL ethyl alcohol washing precipitates, the dry 5h at 80 DEG C, 630 DEG C of roasting 5h, it is acicular MgO powder to obtain crystal structure.
Embodiment 7
Present embodiments provide the catalyst that a kind of PROPENE IN GAS PHASE OXIDATION prepares methacrylaldehyde, preparation method with embodiment 5, The difference is that 150~200nm of length of its quality 10%, 10~40nm of width, crystal structure be added into suspension being The SnO of sheet2, add the Ludox that 100mL mass concentrations are 15%~40% and obtained outer as agent, extrusion molding is mediated Diameter 5mm, internal diameter 2mm, the hollow cylindrical particle that length is 5mm, in air atmosphere activating 5h at 480 DEG C obtains finished product and urges Agent.
In the present embodiment, the crystal structure is sheet SnO2Preparation process be specially：500g stannic chlorides are added to In 2000mL water, then by 50g cetyl trimethylammonium bromides be dissolved in 500mL mass fractions be 10% ammonia spirit in, Reaction 5h is mixed in two parts of solution later, obtains white slurry shape precipitation, is aged 36h, washing, filtering, 58 at room temperature Dry 5h at DEG C, 290 DEG C of roasting 1h, obtains the SnO that crystal structure is sheet2Powder.
Embodiment 8
Present embodiments provide the catalyst that a kind of PROPENE IN GAS PHASE OXIDATION prepares methacrylaldehyde, preparation method with embodiment 5, The difference is that it is needle-shaped that 0.5~5 μm of the length of its quality 15%, 2~5nm of diameter, crystal structure are added into suspension CeO2, the Ludox that 100mL mass concentrations are 15~40% is added, extrusion molding obtains outer diameter 5mm, internal diameter 2mm, length The hollow cylindrical particle for spending 5mm, activation 5h obtains finished catalyst at 480 DEG C in air atmosphere.
In the present embodiment, the crystal structure is needle-shaped CeO2Preparation process be specially：500g cerous nitrates are dissolved in In 2000mL water, be added 200g urea, it is to be dissolved completely after, mixed liquor is put into the autoclave with polytetrafluoroethyllining lining It is interior, 5h is reacted at 180 DEG C, is cooled to room temperature, uses 200mL water, 200mL ethyl alcohol washing precipitates respectively, it is dry at 80 DEG C 5h, 360 DEG C of roasting 5h, it is acicular CeO to obtain crystal structure2Powder.
Embodiment 9
Present embodiments provide the catalyst that a kind of PROPENE IN GAS PHASE OXIDATION prepares methacrylaldehyde, preparation method with embodiment 5, The difference is that it is needle that 6~10 μm of the length of its quality 1.8%, 4~10nm of diameter, crystal structure are added into suspension The La of shape2O3, the Ludox that 100ml mass concentrations are 15%~40wt% is added, extrusion molding obtains outer diameter 5mm, internal diameter The hollow cylindrical particle of 1mm, length 5mm, activation 5h obtains finished catalyst at 490 DEG C in air atmosphere.
In the present embodiment, the crystal structure is needle-shaped La2O3Preparation process be specially：It is by 2000mL mass concentrations Sodium hydroxide that 30% lanthanum chloride solution and 800mL mass concentrations are 20% is water-soluble to be mixed, and by the precipitation filtering of generation, is washed It washs, filter cake dries pulverizing at 108 DEG C, it is needle-shaped La that 700 DEG C of roasting 5h, which obtain crystal structure,2O3Powder.
Embodiment 10
The catalyst that a kind of PROPENE IN GAS PHASE OXIDATION prepares methacrylaldehyde is present embodiments provided, preparation method is as follows：
800.0g ammonium molybdates and 6.7g tantalic chlorides are dissolved under heating stirring in 2000g distilled water and form solution A；It will It is molten that 815.5g ferric nitrates, 208.1g cobalt nitrates, 283.3g aluminum nitrates and 178.1g nickel nitrates are dissolved in formation B in 500g distilled water Liquid；50g concentrated nitric acids (mass concentration 65%) are added in 300g distilled water and form acidic aqueous solution, and are added thereto 798.9g bismuth nitrate forms C solution；B solution and C solution are mixed to form solution D；Solution A is heated and is vigorously stirred, by solution D It is slowly added dropwise into solution A and forms suspension, suspension is placed in oven and dried to decorating film.Obtained decorating film is crushed To 200 μm hereinafter, obtaining the reactive powder of catalyst.The length that its quality 20% is added into reactive powder is 4~6 μm, straight Diameter is 30~80nm, crystal structure is acicular NiO, and it is that the conduct of 15~40wt% Ludox is pinched to add 100mL mass concentrations Mixture, extrusion molding obtain the hollow cylindrical particle of outer diameter 5mm, internal diameter 1mm, length 5mm, in 490 DEG C in air atmosphere Lower activation 5h obtains finished catalyst.
In the present embodiment, other than oxygen, the composition of the reactive powder is：
Mo12Bi4.4Fe5.3Co1.9Ni1.6Ta0.05Al2.0。
Embodiment 11
The catalyst that a kind of PROPENE IN GAS PHASE OXIDATION prepares methacrylaldehyde is present embodiments provided, preparation method is as follows：
800.0g ammonium molybdates and 198.7g cesium nitrates are dissolved under heating stirring in 2000g distilled water and form solution A；It will 152.6g ferric nitrates, 758.8g cobalt nitrates, 49g zirconium nitrates and 663.3g nickel nitrates, which are dissolved in 500g distilled water, forms B solution； 50g concentrated nitric acids (mass concentration 65%) are added in 300g distilled water and form acidic aqueous solution, and 250.5g nitre is added thereto Sour bismuth forms C solution；B solution and C solution are mixed to form solution D；Solution A is heated and be vigorously stirred, solution D is slowly added dropwise To suspension is formed in solution A, suspension is placed in oven and dried to decorating film.Obtained decorating film is crushed to 200 μm Hereinafter, obtaining the reactive powder of catalyst.Be added into reactive powder 8~12 μm of the length of its quality 10%, diameter 160~ 200nm, crystal structure are acicular TiO2, it is that 15~40wt% Ludox is used as kneading agent to add 100mL mass concentrations, is squeezed Go out molding, obtains the hollow cylindrical particle of outer diameter 5mm, internal diameter 1mm, length 5mm, activated at 490 DEG C in air atmosphere 5h obtains finished catalyst.
In the present embodiment, other than oxygen, the composition of the active constituent is：
Mo12Bi1.3Fe1.0Co6.9Ni6.0Cs2.7Zr0.3。
Embodiment 12
The catalyst that a kind of PROPENE IN GAS PHASE OXIDATION prepares methacrylaldehyde is present embodiments provided, preparation method is as follows：
800.0g ammonium molybdates and 21.2g potassium hydroxide are dissolved under heating stirring in 2000g distilled water and form solution A； It is molten that 423.6g ferric nitrates, 466.3g cobalt nitrates, 81.5g nitric acid antimony and 431.6g nickel nitrates are dissolved in formation B in 500g distilled water Liquid；50g concentrated nitric acids (mass concentration 65%) are added in 300g distilled water and form acidic aqueous solution, and are added thereto 636.3g bismuth nitrate forms C solution；B solution and C solution are mixed to form solution D；Solution A is heated and is vigorously stirred, by solution D It is slowly added dropwise into solution A and forms suspension, 0.05~3 μm of the length, straight of reactive powder quality 2.5% is added into suspension 15~50nm of diameter, crystal structure are acicular MgO, and suspension is placed in oven and dried to decorating film.The decorating film that will be obtained 200 μm are crushed to hereinafter, obtaining the reactive powder of catalyst.It is 15~40% that 100mL mass concentrations are added into reactive powder Ludox obtains the hollow cylindrical particle of outer diameter 5mm, internal diameter 2mm, length 5mm, in air as agent, extrusion molding is mediated 5h is activated at 500 DEG C obtain finished catalyst in atmosphere.
In the present embodiment, other than oxygen, the composition of the reactive powder is：
Mo12Bi3.5Fe2.8Co4.3Ni4.0Sb0.7K1.0。
Comparative example 1
This comparative example provides the catalyst that a kind of PROPENE IN GAS PHASE OXIDATION prepares methacrylaldehyde, preparation method with embodiment 1, The difference is that being added without the ZnO that crystal structure is sheet in this comparative example, in catalyst preparation process.
Comparative example 2
This comparative example provides the catalyst that a kind of PROPENE IN GAS PHASE OXIDATION prepares methacrylaldehyde, preparation method with embodiment 1, The difference is that a diameter of 3~4nm is added in this comparative example, in catalyst preparation process, the oxidation that length is 7~10 μm Fe nanowire.
Comparative example 3
This comparative example provides the catalyst that a kind of PROPENE IN GAS PHASE OXIDATION prepares methacrylaldehyde, preparation method with embodiment 1, The difference is that a diameter of 30~40nm is added in this comparative example, in catalyst preparation process, the oxygen that length is 50~70 μm SiClx nanometer rods.
1 catalytic mechanical strength test of experimental example
100g catalyst is placed in the stainless steel tube top of 3.5 meters of the length, internal diameter 25.4mm that stand vertically, unclamps, makes it It freely falls on the stainless steel plate of thick 2mm of stainless steel tube bottom, the catalyst fallen is sieved with 20 mesh sample sifters, measurement is stayed The quality of catalyst on sample sifter, calculates the mechanical strength of catalyst, is as a result listed in table 1.
2 catalytic performance of experimental example is tested
In internal diameter 25.4mm, the fixed bed reactors of pipe range 4000mm, 1.4~1.7L catalyst is loaded or with inertia porcelain The dilution type catalyst of ball mixing introduces propylene, oxygen, nitrogen and vapor thereto, and the wherein molar concentration of propylene is 7.5 ~10%, propylene：Air：Nitrogen：Vapor=(7.5~10):(70~80):(16~20):(6.5~15).Material is always empty 600~2500h of speed-1, carry out oxidation reaction under conditions of reaction temperature is 315~350 DEG C, pressure is 1.0MPa, react into The results are shown in Table 1 after 800 hours for row.
The evaluation result of 1 embodiment of table and comparative example
The performance of the embodiment of the present invention 1-12 catalyst is substantially better than comparative example 1-3 catalyst it can be seen from upper table 1 Performance.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or It changes still within the protection scope of the invention.

Claims (10)

1. a kind of catalyst preparing methacrylaldehyde, which is characterized in that including molybdenum-bismuth-system compound oxide and metal oxide, institute It states metal oxide and is selected from TiO2、NiO、ZnO、La2O3、CeO2、CuO、Ga2O3、MgO、SnO2At least one of, the metal Oxide has crystal structure.
2. catalyst according to claim 1, which is characterized in that the crystal structure of the metal oxide is needle-shaped or piece Shape.
3. catalyst according to claim 2, which is characterized in that the crystal structure of the metal oxide be it is needle-shaped, directly Diameter is 2~200nm, and length is 0.05~100 μm.
4. catalyst according to claim 2, which is characterized in that the crystal structure of the metal oxide is sheet, long Degree is 10~300nm, and width is 10~100nm.
5. according to claim 1-4 any one of them catalyst, which is characterized in that the crystal specific surface of the metal oxide Product is 20~200m2/g。
6. according to claim 1-5 any one of them catalyst, which is characterized in that the quality of the metal oxide accounts for described The 0.5~40% of molybdenum-bismuth-system compound oxide quality.
7. according to claim 1-6 any one of them catalyst, which is characterized in that the molybdenum-bismuth-system compound oxide has The general formula as shown in formula (I)：
Mo12BiaFebCocNidAeBfCgOn(Ⅰ)；
Wherein：
Mo, Bi, Fe, Co, Ni indicate that molybdenum, bismuth, iron, cobalt and nickel, A are selected from least one of alkali metal, alkaline-earth metal, thallium respectively Element, B are selected from chromium, tin, zinc, antimony, phosphorus, tungsten, manganese, at least one of cerium element, C in silicon, zirconium, aluminium, titanium at least one Kind element, O is oxygen；A, b, c, d, e, f, g and n indicate the atomic ratio of Bi, Fe, Co, Ni, A, B, C and O respectively；1 ＜ a≤5,1 ＜ B≤6,0.5 ＜ c≤7,0.01 ＜ d≤8, the 0.02 ＜ ＜ of e≤3,0.01≤f≤5,0.2 g≤8, n is the oxidation according to each element The numerical value that state determines.
8. the preparation method of claim 1-7 any one of them catalyst, which is characterized in that the metal oxide directly adds Into the material liquid of catalyst active component；Or be added during shaping of catalyst, then roasting obtains the catalyst.
9. claim 1-7 any one of them catalyst or the according to the method for claim 8 catalyst of preparation are answered With, which is characterized in that the catalyst produces methacrylaldehyde for Selective Oxidation of Propylene.
10. the application of catalyst according to claim 9, which is characterized in that the oxidation reaction molecular oxygen or containing point It is carried out under the conditions of sub- oxygen is existing.
CN201810106223.4A 2018-02-02 2018-02-02 A kind of catalyst of PROPENE IN GAS PHASE OXIDATION acrolein and its application Pending CN108325534A (en)

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