CN105582950A - Catalyst for producing acrylic acid, preparation method and use method thereof - Google Patents
Catalyst for producing acrylic acid, preparation method and use method thereof Download PDFInfo
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Abstract
The invention provides a catalyst for producing acrylic acid, which is composed of a composite active oxide coating and an inert carrier. Through high-temperature passivation treatment, the catalyst is used for oxidatively esterifying acrylic acid into acrylates. The most external layer of the composite active oxide coating is a nano Sb2O3 coating which is formed by spray-coating the inert carrier, on which other active components, besides the antimony, has been coated, with an ethylene glycol antimony anhydrous solution, and then hydrolyzing and drying the catalyst. The catalyst is greatly improved in anti-wear property, can inhibit reduction on heat resistance of the catalyst due to addition of the Sb2O3 while the yield is increased at the same time, and is improved in stability and process safety of the catalyst containing the Sb2O3.
Description
Technical field
The present invention relates to a kind of solid catalyst, particularly relate to a kind of for methacrylaldehyde selective oxidation production thirdThe catalyst of olefin(e) acid, and the preparation and application of this catalyst.
Background technology
Acrylic acid is one of important derivatives of propylene, and within 2013, global acrylic acid output reaches approximately 6,000,000 tons,Wherein domestic production capacity reaches 2,400,000 tons, estimates that domestic production capacity in 2015 will reach 4,000,000 tons/year. At present,The mainstream technology route that acrylic acid is produced is still industrialized propylene two-step method selective oxidation in 70 years last century workSkill, propylene partial oxidation is methacrylaldehyde, afterwards the selected acrylic acid that is oxidized to of methacrylaldehyde. So large production capacityEven if yield increases by 0.2%, also will bring huge economic benefit, therefore lot of domestic and foreign major company is still diligentThe improvement of tireless pursuit selective oxidation catalyst.
Acrylic acid selective oxidation process belongs to strong exothermal reaction, the more difficult control of reactor hot(test)-spot temperature, particularlySecond oxidation process slightly temperature runaway catalyst loses activity, and therefore how to ensure stable operation, the raising of reactionAcrylic acid yield and minimizing accessory substance are the difficult problem in this field all the time.
Researcher in this field mentions (MoVW)5O14Structure, V5+/V4+Ratio, the introducing of W, edgeMaterial direction in reactor tubulation changes active component concentration, changes dense inside and outside catalyst coat of MoThe modes such as degree improve the selective focus that also suppresses as far as possible.
In catalyst, add Sb2O3, utilize its oxygen overflow effect to improve yield, but when improving yield,Catalyst is the inactivation due to overtemperature more easily. Add antimony trioxide with powder type, easily generation mixes inhomogeneousProblem, causes overtemperature and inactivation; Add antimony acetate, although promoted even mixing, improved the machinery of coatingIntensity, but antimony acetate has higher toxicity, and cause the variation of mixed solution pH value, make multicomponentThe preparation of composite oxides precursor solution becomes more difficult; Therefore, need the methacrylaldehyde of development of new to be converted intoAcrylic acid catalyst, to suppress Sb2O3Add and cause the stable on heating decline of catalyst.
Summary of the invention
In order to suppress Sb2O3Add and cause the stable on heating decline of catalyst, the invention provides a kind of methacrylaldehyde and turnTurn to acrylic acid catalyst and preparation and application thereof, improved stability and the process safety of catalystProperty.
It is to realize like this that methacrylaldehyde of the present invention is converted into acrylic acid catalyst:
Described catalyst is made up of activating oxide coating and inert carrier, and described activating oxide is shown with general formula 1Show:
General formula 1
MoaVbNbcCudNieSbfXjOk
In formula,
A=12, b=3～6, c=0.5～2, d=0.1～1, e=0.1～2, f=0.1～1.2, j=0.1～0.5, k is fullThe numerical value of other element states of oxidation of foot;
X is selected from one or more in following metal: Na, K, Rb, Cs, Sr, Ba, Ca, Mg;
Described catalyst is after described inert carrier higher slice applies described activating oxide coating, then warpCross that high temperature Passivation Treatment obtains;
The outermost layer of described activating oxide coating is the antimony trioxide coating applying separately, described antimony trioxideThe coating procedure of coating comprises the following steps successively:
(1) apply, applying also catalyst half one-tenth of other active components except antimony of Roasting DecompositionOn product, spraying antimony glycol anhydrous solution; Application temperature is 60 DEG C～200 DEG C;
(2) hydrolysis, to spraying the catalyst semi-finished product of described antimony glycol anhydrous solution, adopts steam to enterRow surface treatment, antimony glycol is hydrolyzed to antimony oxide; The thickness of described antimony trioxide coating after surface treatmentFor 0.1um～100um;
(3) dry, to through described surface-treated catalyst semi-finished product, be dried processing;
Described dry catalyst semi-finished product after treatment obtain described catalyst through high temperature Passivation Treatment again; InstituteThe passivation atmosphere material of stating Passivation Treatment consists of: methacrylaldehyde 0.1vol%～0.5vol%, the volume of methacrylaldehyde/oxygenThan being 1:1～1:3, steam 5vol%～30vol%, all the other are nitrogen; Passivation temperature is 300 DEG C～400 DEG C,Passivation time is 0.1hr～24hr, and passivation load is 1hr-1～100hr-1。
In the specific implementation, described inert carrier specific area is 0.5～5m2/ g. Described inert carrier canUse the carrier of low specific surface area well known in the art, as carborundum, talcum, aluminium oxide, titanium dioxide, twoZirconia, magnesium silicate and silicon alumina etc. Inert carrier can adopt ring-type, spherical and column, spherical employing directlyFootpath is 2～15mm, preferably 3～10mm.
In the specific implementation, described application temperature is 80～160 DEG C; The thickness of described antimony trioxide coating is0.5～20um, is preferably 1～5um; Described passivation temperature is 320～380 DEG C, and passivation time is 1～5hr.
In prior art, higher for the coated catalysts load factor of acrylic acid selective oxidation, with respect to calciningAfter coating compound and the gross weight of inert carrier, the coating powder weight on carrier is generally up to 10～50wt%,General 0.1～the 3mm of its coating layer thickness. So coating weight and coating layer thickness, need to consider coating on the one handProblems of mechanical strength, to consider on the other hand the heat of the inner or single catalyst granules inside of coatingBe difficult to effectively transmit and cause internal temperature higher, thereby bring the volatilization of Mo to run off, if in coating inside stillSo there are a large amount of Sb, easily cause the sintering deactivation of catalyst; Therefore the present invention has adopted um level three oxygenChange two antimony coats, solve the problem of the inner sintering of catalyst coat; Good etc. owing to thering is the little and caking property of toxicityFeature, the present invention has selected antimony glycol anhydrous solution as spray coating liquor.
The preparation method of catalyst of the present invention realizes like this:
The preparation method of described catalyst is made up of following process: apply described activity at inert carrier higher sliceOxide coating and high temperature Passivation Treatment;
The outermost layer of described activating oxide coating is the antimony trioxide coating applying separately, described antimony trioxideThe coating procedure of coating comprises the following steps successively:
(1) apply; Applying also catalyst half one-tenth of other active components except antimony of Roasting DecompositionOn product, spraying antimony glycol anhydrous solution; Application temperature is 60～200 DEG C;
(2) hydrolysis; To the catalyst semi-finished product of spraying antimony glycol anhydrous solution, adopt steam to showFace processing, antimony glycol is hydrolyzed to antimony oxide; After surface treatment, the thickness of described antimony trioxide coating is0.1～100um；
(3) dry, the catalyst semi-finished product of effects on surface processing, are dried processing;
Dry catalyst semi-finished product after treatment obtain described catalyst through high temperature Passivation Treatment; Described passivationThe passivation atmosphere material of processing consists of: methacrylaldehyde 0.1～0.5vol%, and the volume ratio of methacrylaldehyde/oxygen is 1:1～3,Steam 5～30vol%, all the other are nitrogen; Passivation temperature is 300～400 DEG C, and passivation time is 0.1～24hr,Passivation load is 1～100hr-1。
The using method of catalyst of the present invention is to realize like this:
Methacrylaldehyde and water, after evaporator evaporation gasification, enter gas mixer with nitrogen, oxygen simultaneously and mixClose; Mixed gas enters the reactor for oxidation reactions of loading described catalyst; Described oxidation reactionReaction pressure is 10～90kPa, and reaction temperature is 240～300 DEG C, and air speed is 1～2000hr-1; Hot(test)-spot temperature needsControl, temperature runaway is set as 400 DEG C.
In the specific implementation, described reaction pressure is 20～50kPa; Described reactor is upper entering and lower leaving mode;In view of this reaction is strong exothermal reaction, reactor adopts salt bath heat and remove heat, and overtemperature temperature runaway is reported to the police,Temperature runaway need stop propylene and air simultaneously.
The composite oxide coating catalyst providing of the present invention, is oxidized two antimony coat isoreactivity oxygen by um levelCompound coating and inert carrier composition, after high temperature Passivation Treatment, for being propylene by acrylic acid oxidative esterificationAcid. This catalyst can suppress Sb2O3Add the catalyst heat resistance causing to decline, there is wider reactionTemperature operation window, and the wearability of catalyst significantly improves, thus the loss of active constituent and large reducedWidth reduces the Potential feasibility that causes technique to stop up, and has improved stability and the process safety of catalyst.
Detailed description of the invention
Be described in further detail technical scheme of the present invention below in conjunction with embodiment, protection scope of the present invention is not limited toIn following detailed description of the invention.
Method of testing
XRD (X-raydiffraction, X-ray diffraction): the XpertMPD that adopts Dutch Philips companyType X-ray diffractometer analysis of catalyst phase structure, radiation source is CuK α, sweep limits is 20～80 DEG C,Adopt Scherrer formula to calculate size of microcrystal.
Specific surface test: adopt the physical adsorption appearance of the Nova3000e of Kang Ta company of the U.S., carry out specific surfaceIntegration is analysed. At liquid nitrogen temperature-196 DEG C, use N2Determination of adsorption method surface area and pore-size distribution, sample is at 300 DEG CUnder vacuumize pretreatment to pressure and be less than 10-3Pa, assay method is static method. Adopt according to adsorption isothermBET method is calculated specific surface.
Feed purity
In embodiment and comparative example, copper nitrate Cu (NO3)2.3H2The purity of O is 99.0%, nickel nitrate pureDegree is 99.0%, ammonium metavanadate NH4VO3Purity be 99.0%, the purity of antimony oxide is 99.0%,Ammonium molybdate (NH4)6Mo7O24.4H2O, strontium nitrate Sr (NO3)2Purity be more than or equal to 99.5%, magnesium nitrate,Ammonium niobium oxalate NH4NbO(C2H4)2(H2O)3Be analysis pure.
Reaction result calculates
Acrolein conversion rate (mol) %=100 × (the methacrylaldehyde molal quantity of reaction)/(the methacrylaldehyde molal quantity of charging)
Acrylic acid selective (mol) %=100 × (the acrylic acid molal quantity of generation)/(methacrylaldehyde mole that reaction transformsNumber)
The selective yield of acrylic acid (mol) %=100 × (the acrylic acid molal quantity of generation)/(methacrylaldehyde mole of chargingNumber)
Abrasion test
The catalyst sample of putting into rotary drum is rotated 10 minutes under 25rpm, and use 2.36mm standard screenSieve.
Wearability (wt%)=100 × (sample size of input-be retained in the sample size on 2.36mm sieve)/(inputSample size)
Embodiment 1
1. in five mouthfuls of flasks of 20L, add the distilled water of 10L, add afterwards a certain amount of copper nitrate,Nickel nitrate, ammonium metavanadate, ammonium molybdate, ammonium niobium oxalate and magnesium nitrate, be uniformly mixed into slurry state;Afterwards this mixed solution is pumped in spray dryer and be dried, spray dryer inlet temperature is 200 DEG C, goes outMouth temperature is not less than 80 DEG C; After being milled 2 hours in ball mill, the dry powder obtaining obtains fine powder material; TurningIn drum comminutor, add fine powder material while adding distil water, it is Φ 4 talcums that this fine powder material is wrapped in to diameterOn ball type carrier; Roasting 6 hours at 380 DEG C afterwards, obtains catalyst carrier.
2., after 1 part of antimony glycol being dissolved in absolute ethyl alcohol, adopt spray pattern to be sprayed on above-mentioned catalystOn carrier; In the baking oven of 120 DEG C, dry afterwards, and adopt steam to process at 90 DEG C within 6 hours, to carry out waterSeparate, obtain coated catalysts. The active constituent of this coated catalysts isMo12V3Nb0.5Cu0.4Ni0.8Sb0.2Mg0.1Ox, coating layer thickness is 1.2um, rate of wear is 0.032wt%.
3. above-mentioned coated catalysts being added to internal diameter is in the reactor of 25.2mm, adopts the reaction of underloadAtmosphere is carried out passivation. Material component is: methacrylaldehyde 0.05vol%, oxygen 0.15vol%, steam29.8vol%, nitrogen 70vol%, the volume space velocity of unstrpped gas is 100hr-1, adopt salt bath control reactionTemperature, catalyst structure is complete. Catalyst is numbered 1#。
Embodiment 2
Adopt as preparation method 1. and 2. in embodiment 1, obtain active constituent and beMo12V3Nb0.5Cu0.4Ni0.8Sb0.5Mg0.1Ox, coating layer thickness is 1.5um, rate of wear is 0.027wt%Coated catalysts.
It is in the reactor of 25.2mm that above-mentioned coated catalysts is added to internal diameter, adopts the reaction gas of underloadAtmosphere carries out passivation. Material component is: methacrylaldehyde 0.45vol%, oxygen 0.45vol%, steam 29.1vol%,Nitrogen 70vol%, the volume space velocity of unstrpped gas is 10hr-1, adopts salt bath control reaction temperature, catalysisAgent passivation is complete. Catalyst is numbered 2#。
Embodiment 3
Adopt as preparation method 1. and 2. in embodiment 1, obtain active constituent and beMo12V3Nb0.5Cu0.4Ni0.8Sb1.0Mg0.1Ox, coating layer thickness is 2.8um, the painting that rate of wear is 0.02wt%Layer catalyst.
It is in the reactor of 25.2mm that above-mentioned coated catalysts is added to internal diameter, adopts the reaction gas of underloadAtmosphere carries out passivation. Material component is: methacrylaldehyde 0.25vol%, oxygen 0.50vol%, steam 5.25vol%,Nitrogen 84vol%, the volume space velocity of unstrpped gas is 50hr-1, adopt salt bath control reaction temperature, catalystPassivation is complete. Catalyst is numbered 3#。
Embodiment 4
Adopt as preparation method 1. and 2. in embodiment 1, obtain active constituent and beMo12V3Nb0.5Cu0.4Ni0.8Sb5.0Mg0.1Ox, coating layer thickness is 2.5um, rate of wear is 0.012wt%Coated catalysts.
It is in the reactor of 25.2mm that above-mentioned coated catalysts is added to internal diameter, adopts the reaction gas of underloadAtmosphere carries out passivation. Material component is: methacrylaldehyde 0.25vol%, oxygen 0.50vol%, steam15.25vol%, nitrogen 74vol%, the volume space velocity of unstrpped gas is 80hr-1, adopt salt bath control reaction temperatureDegree, catalyst structure is complete. Catalyst is numbered 4#。
Comparative example 1 (not adding antimony)
Adopt as preparation method 1. in embodiment 1, obtain active constituent and beMo12V3Nb0.5Cu0.4Ni0.8Mg0.1Ox, the catalyst that rate of wear is 0.05wt%. Adopt and embodiment 1 phaseSame condition Passivation Treatment, catalyst is numbered 5#。
Comparative example 2 (conventional preparation method)
Adopt conventional hybrid mode to add antimony (not adopting antimony glycol), and the employing bar identical with embodiment 1Part Passivation Treatment.
In five mouthfuls of flasks of 20L, put into the distilled water of 10L, add afterwards a certain amount of copper nitrate, nitreAcid nickel, ammonium metavanadate, ammonium molybdate, strontium nitrate and magnesium nitrate, be uniformly mixed into slurry state; Now addEnter antimony oxide powder, afterwards this mixed solution is pumped in spray dryer and be dried, spray dryer entranceTemperature is 200 DEG C, and outlet is not less than 80 DEG C. After being milled 2 hours in ball mill, the dry powder obtaining obtainsFine powder, in rotary drum granulator, adds dry powder while distilled water is wrapped in this powder on talcum carrier, itAfter roasting 6 hours at 380 DEG C. Making active constituent is Mo12V3Nb0.5Cu0.4Ni0.8Sb0.2Mg0.1Ox，The rate of wear of catalyst is 0.05wt%. Catalyst is numbered 6#。
Comparative example 3 (conventional preparation method)
As comparative example 2, adopt conventional hybrid mode to add antimony (not adopting antimony glycol), and adopt and implementThe condition Passivation Treatment that example 1 is identical.
Making active constituent is Mo12V3Nb0.5Cu0.4Ni0.8Sb1.0Mg0.1Ox, the rate of wear of catalyst is0.05wt%. Catalyst is numbered 7#。
Comparative example 4 (the compound antimony preparation method that adds)
Mo prepared by comparative example 212V3Nb0.5Cu0.4Ni0.8Sb0.2Mg0.1OxCatalyst.
Again as described in Example 1, carry out antimony glycol coating and hydrolysis, made Mo12V3Nb0.5Cu0.4Ni0.8Sb1.0Mg0.1OxCatalyst, coating layer thickness is 2.2um, the rate of wear of catalyst is 0.012wt%.Adopt identical condition Passivation Treatment, catalyst is numbered 8#。
Reaction evaluating and analysis
Adopt the mist of nitrogen, oxygen, methacrylaldehyde and water vapour as raw material, consist of 5% propyleneAldehyde, 7% oxygen, 5% steam, all the other are nitrogen. After adding, methacrylaldehyde and water need to adopt electrical heating to steamHair device evaporation, various materials enters gas mixer mixing simultaneously afterwards, and the flow velocity of mist is 540 marksL/h, volume space velocity is 1800hr-1. For micro anti-evaluation, Catalyst packing volume is 300mL, anti-Answering device is that stainless steel material is made, internal diameter is 25.2mm, has thermocouple to measure reactor in reactorBed temperature. The granular size of catalyst is Φ 4.
Reactor adopts upper entering and lower leaving, and reacting system pressure maintains 20～50KPa; In view of this reaction is strongExothermic reaction, this simulation single tube adopts salt bath to heat and removes heat. Reaction temperature is 240～300 DEG C, heatPoint temperature needs to control, and temperature runaway is set as 400 DEG C, and temperature runaway is reported to the police, and temperature runaway need stop methacrylaldehyde and sky simultaneouslyGas. Reactor product is after gas-liquid separator water-cooled separates, and liquid phase is collected, and gas phase is anti-through useless combustionAnswer device burning rear emptying.
Raw material and product, adopt gas chromatographic analysis. Proximate analysis comprises gas phase and liquid product analysis. Chromatogram1 is Varian3800 chromatogram, and carrier gas is He gas, the porapakQ packed column that chromatographic column adopting is 3 meters long andThe TDX-01 packed column of 5 meters long, adopts two flowing valves to switch, and the order at spectrum peak is followed successively by O2、N2、CO、CO2、C3H6、C3H8. Be worth indicating, it is N that the first root chromatogram column goes out peak2、O2, CO, warpCrossing valve switches the second root chromatogram column to go out peak is CO2、C3H6、C3H8. Outside the content of raw material and product need to pass throughMark method is determined, in view of O before and after reaction2、N2And C3H6Content difference too large, need different gases carry outDemarcate and analyze. Chromatogram 2 is similarly Varian3800 chromatogram, and carrier gas is N2Gas, 30 meters of chromatographic column adopting are longFFAP capillary column and adopt respectively two methods analyst methacrylaldehyde and acrylic acid, two methods adopt respectivelyInternal standard method and external standard method analysis. Be worth indicating, it is N that the first root chromatogram column goes out peak2、O2, CO, processValve switches the second root chromatogram column, and the total acid content of liquid product need to adopt NaOH alkali lye to demarcate.
The contrast of catalyst heat endurance
Salt temperature is 240 DEG C～350 DEG C, investigates conversion ratio, yield, hot(test)-spot temperature and running status. CatalysisAgent heat stabilization test (240 DEG C) the results are shown in Table 1, and catalyst heat stabilization test (280 DEG C) the results are shown in Table2, catalyst heat stabilization test (300 DEG C) the results are shown in Table 3, catalyst heat stabilization test (320 DEG C)The results are shown in Table 4, catalyst heat stabilization test (350 DEG C) the results are shown in Table 5.
Table 1
As can be seen from Table 1, in the time of 240 DEG C of reaction temperatures, no matter adopt antimony glycol (catalyst 1～4#),Antimony oxide (catalyst 6～7#) and compound 8 of the mode that adds#Add mode, yield is substantially suitable; But all far awayFar above than not adding 5 of antimony#Catalyst.
Table 2
As can be seen from Table 2, in the time of 280 DEG C of reaction temperatures, no matter adopt antimony glycol (catalyst 1～4#),Antimony oxide (catalyst 6～7#) and compound 8 of the mode that adds#Add mode, yield is substantially suitable; But allFar away higher than than not adding 5 of antimony#Catalyst.
Table 3
As can be seen from Table 3, in the time of 300 DEG C of reaction temperatures, do not add 5 of antimony#Catalyst yield is lower, and fortuneRow after 6 hours in temperature runaway state. Adopt antimony glycol (catalyst 1～4#) add the yield of mode the highest,Compound 8 of the mode that adds#Catalyst takes second place, and antimony oxide adds mode, and yield is minimum.
Table 4
As can be seen from Table 4, in the time of 320 DEG C of reaction temperatures, do not add 5 of antimony#Catalyst and employing routine add antimony6～7#Yield is lower, and operation 6 hours after in temperature runaway state. Adopt antimony glycol (catalyst 1～4#)Add the yield of mode the highest, far above compound 8 of the mode that adds#Catalyst takes second place.
Table 5
As can be seen from Table 5, in the time of 350 DEG C of reaction temperatures, do not add 5 of antimony#Catalyst, employing routine add antimony6～7#Catalyst and the compound 8# catalyst that adds antimony, all temperature runaway. Adopt antimony glycol (catalyst 1～4#) to addThe yield that enters mode is the highest, still can keep stable operation.
The data of contrast table 1～table 5 can be found out:
1) heat endurance, 240～350 DEG C of reaction temperatures, thermally-stabilised order: antimony glycol preparation method > multipleClose and add antimony preparation method conventional preparation method > do not add antimony preparation method; Antimony glycol preparation method has the widestTemperature operation interval, 240～350 DEG C, and conventional preparation method is only 240～300 DEG C.
2), from product yield, 240～300 DEG C of reaction temperatures, three kinds of acrylic acid yields that add antimony are basicQuite, all far away higher than the catalyst that does not add antimony.
3) wearability, wearability order is the compound antimony preparation method that adds of antimony glycol preparation method ≈ > conventional preparationMethod > do not add antimony preparation method, can think that ethylene glycol coating has improved the wearability of catalyst greatly.
Claims (10)
1. for the production of an acrylic acid catalyst, described catalyst is by activating oxide coating and inert carrier groupBecome,
Described activating oxide represents with general formula 1:
[general formula 1]
MoaVbNbcCudNieSbfXjOk
In formula,
A=12, b=3～6, c=0.5～2, d=0.1～1, e=0.1～2, f=0.1～1.2, j=0.1～0.5, k is fullThe numerical value of other element states of oxidation of foot;
X is selected from one or more in following metal: Na, K, Rb, Cs, Sr, Ba, Ca, Mg;
Described catalyst is after described inert carrier higher slice applies described activating oxide coating, then warpCross that high temperature Passivation Treatment obtains;
The outermost layer of described activating oxide coating is the antimony trioxide coating applying separately, described antimony trioxideThe coating procedure of coating comprises the following steps successively:
(1) apply, applying also catalyst half one-tenth of other active components except antimony of Roasting DecompositionOn product, spraying antimony glycol anhydrous solution; Application temperature is 60 DEG C～200 DEG C;
(2) hydrolysis, to spraying the catalyst semi-finished product of described antimony glycol anhydrous solution, adopts steam to enterRow surface treatment, antimony glycol is hydrolyzed to antimony oxide; The thickness of described antimony trioxide coating after surface treatmentFor 0.1um～100um;
(3) dry, to through described surface-treated catalyst semi-finished product, be dried processing;
Described dry catalyst semi-finished product after treatment obtain described catalyst through high temperature Passivation Treatment again; InstituteThe passivation atmosphere material of stating Passivation Treatment consists of: methacrylaldehyde 0.1vol%～0.5vol%, the volume of methacrylaldehyde/oxygenThan being 1:1～1:3, steam 5vol%～30vol%, all the other are nitrogen; Passivation temperature is 300 DEG C～400 DEG C,Passivation time is 0.1hr～24hr, and passivation load is 1hr-1～100hr-1。
2. catalyst according to claim 1, is characterized in that:
Described inert carrier be shaped as ring-type, spherical or column, specific area is 0.5m2/g～5m2/g。
3. catalyst according to claim 2, is characterized in that:
Being shaped as of described inert carrier is spherical, and its diameter is 3mm～10mm.
4. preparation method according to claim 1, is characterized in that:
Described application temperature is 80 DEG C～160 DEG C.
5. preparation method according to claim 1, is characterized in that:
The thickness of described antimony trioxide coating is 0.5um～20um.
6. preparation method according to claim 5, is characterized in that:
The thickness of described antimony trioxide coating is 1um～5um.
7. preparation method according to claim 1, is characterized in that:
Described passivation temperature is 320 DEG C～380 DEG C, and passivation time is 1hr～5hr.
8. a preparation method for the described catalyst of one of claim 1～7,
Described catalyst is to obtain in inert carrier higher slice coating activating oxide coating and high temperature Passivation Treatment;
The outermost layer of described activating oxide coating is the antimony trioxide coating applying separately, described antimony trioxideThe coating procedure of coating comprises the following steps successively:
(1) apply, applying also catalyst half one-tenth of other active components except antimony of Roasting DecompositionOn product, spraying antimony glycol anhydrous solution; Application temperature is 60 DEG C～200 DEG C;
(2) hydrolysis, to the catalyst semi-finished product of spraying antimony glycol anhydrous solution, adopts steam to showFace processing, antimony glycol is hydrolyzed to antimony oxide; After surface treatment, the thickness of described antimony trioxide coating is0.1um～100um；
(3) dry, to through described surface-treated catalyst semi-finished product, be dried processing;
Described dry catalyst semi-finished product after treatment obtain described catalyst through high temperature Passivation Treatment; DescribedThe passivation atmosphere material of Passivation Treatment consists of: methacrylaldehyde 0.1vol%～0.5vol%, the volume ratio of methacrylaldehyde/oxygenFor 1:1～1:3, steam 5vol%～30vol%, all the other are nitrogen; Passivation temperature is 300 DEG C～400 DEG C, bluntThe change time is 0.1hr～24hr, and passivation load is 1hr-1～100hr-1。
9. a using method for the described catalyst of one of claim 1～7,
Methacrylaldehyde and water, after evaporator evaporation gasification, enter gas mixer with nitrogen, oxygen simultaneously and mixClose; Mixed gas enters the reactor for oxidation reactions of loading described catalyst;
The reaction pressure of described oxidation reaction is 10kPa～90kPa, and reaction temperature is 240 DEG C～300 DEG C, air speedFor 1hr-1～2000hr-1, temperature runaway is set as 400 DEG C.
10. preparation method according to claim 9, is characterized in that:
Described reaction pressure is 20kPa～50kPa.
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| JP2006015330A (en) * | 2004-06-02 | 2006-01-19 | Nippon Shokubai Co Ltd | Catalyst for producing acrylic acid and method for producing acrylic acid using this |
| CN1583261A (en) * | 2004-06-11 | 2005-02-23 | 谷育英 | Composite metal oxide for unsaturated aldehyde selective oxidation and preparing method thereof |
| CN102039143A (en) * | 2010-11-18 | 2011-05-04 | 中国海洋石油总公司 | Preparation method of catalyst for acrylic acid by oxidizing acraldehyde |
| CN102989474A (en) * | 2011-09-08 | 2013-03-27 | 中国石油天然气股份有限公司 | Unsaturated aldehyde oxidation catalyst and preparation method thereof |
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