CN102989480A - Composite multi-metal oxide catalyst and preparation method thereof - Google Patents
Composite multi-metal oxide catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a composite multi-metal oxide catalyst and a preparation method thereof. The catalyst is characterized in that the composition of the catalyst can be represented by the general formula (I): MoaVbWcNidAeBfSigOx (I), wherein Mo is molybdenum, V is vanadium, W is tungsten, Ni is nickel, and Si is silicon. Si is a carrier added in the catalyst. A is at least one element selected from copper, cobalt, and manganese. B is at least one element selected from zirconium, strontium, magnesium, and titanium. With the catalyst provided by the invention, single-pipe reactor local heat accumulation can be effectively reduced, and hot spot formation can be inhibited. The catalyst has the characteristics of high reaction activity, high selectivity, long service life, and the like.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method of compound poly-metal deoxide, be used for catalyzing propone formoxy-acrylic acid processed.
Background technology
Industrial main employing propylene two-step oxidizing process prepares acrylic acid at present, and at first the propylene catalytic gas phase oxidation generates methacrylaldehyde, and methacrylaldehyde is reoxidised into acrylic acid.The acrolein oxidation reaction is strong exothermal reaction, in beds, can produce focus, the heat that moment is gathered is constantly accumulated, to cause the catalyst activity component loss, come off, to such an extent as to catalyst activity reduction, the lost of life, and cause aggravating the formation of accessory substance because of over oxidation reaction, even cause and runaway reaction make sintering of catalyst.
The appearance of " progress of oxidation acrylic acid synthesizing process and catalyst " (petrochemical industry, the 7th phase of the 39th volume in 2010) social focus also can make the catalyst damage evil, shortens the service life of catalyst.Take 80,000 ton/years of acroleic acid devices as example, propylene oxidation prepares and needs more than 2.5 ten thousand tubulation in the acrolein reaction device, and acrolein oxidation prepares also needs more than 2.5 ten thousand tubulation in the acrylic acid reactor, load altogether more than 100 ton of methacrylaldehyde, acrylic acid catalyst.More than 50,000 reaction tube, the filling of catalyst guarantee not fill empty certain difficulty that has, if because focus is crossed the very fast sintering of high catalyst, again change in a short time agent, it is huge can envisioning its economic loss again; In addition, carry out under cryogenic conditions as much as possible for methacrylaldehyde, acrylic acid production, because the reaction needed salt bath heating, its energy resource consumption of keeping production also is huge spending; Because the generation of focus is high temperature resistant to the requirement of reaction tube tubing, for up to ten thousand reaction tubes, the tubing expense is exactly a very large cost.Therefore, if the generation of establishment beds focus can bring huge economic benefit to large-scale industrial production.
At present, there is several different methods can reduce or avoid gathering and peroxidization of focus, can considers from the improvement of reaction unit and improvement two aspects of catalyst.Aspect catalyst, as: Japanese patent laid-open 04-217932 has proposed a kind of method that suppresses the appearance of focus or the hot polymerization collection on the focus, namely by preparing multiple catalyst with different possessive volumes, and the mode from the unstripped gas inlet side to the minimizing of outlet one side catalyst possessive volume, fill successively reaction tube, but the possessive volume of catalyst is subjected to the restriction of reaction tube diameter, and it is also very difficult that multiple catalysts is filled into reaction tube.Japan special permission disclose 10614/1972, to sneak into heat resistanceheat resistant point formation catalyst in catalyst be inert substance to US200421442A with catalyst dilution, and Japanese Patent Publication 36739/1987 is made catalyst the method for tubulose.The Catalyst packing that the unstrpped gas porch reduces with active component is arranged again.CN200510007929.8 provides a kind of catalyzing propone aldehyde gaseous oxidation system acrylic acid catalyst, described catalyst comprises molybdenum and vanadium, also comprise at least a volatile catalyst toxic component, its amount is 10 to 100ppb quality through ion chromatography measurement, this catalyst can reduce the temperature of hot spot, and suppresses the reduction of the reaction efficiency of thermal degradation.Specific practice is, comprises and originally has in the highly active catalyst by the volatility toxic component that makes specified quantitative, and catalytic activity descends momently, can reduce the temperature of hot spot.CN97104224.1 by catalytic active component is divided be loaded on the carrier after, calcine the generation that the catalyst of load sharing suppresses focus, the average grain diameter of catalyst is 4～16mm, the average grain diameter of carrier is 3～12mm, calcining heat is 500～600 ℃.CN01111960.8 provides the catalyst of a kind of Mo-W-Bi-Fe of containing, this catalyst by changing possessive volume calcining heat and/or alkali metal kind and/or quantity and according to catalyst activity from the inlet side of unstripped gas to the mode that outlet one side increases, fill successively reaction zone with described multiple types catalyst.Catalyst reaction tube axially on be divided at least two-layerly, this catalyst is the multiple types catalyst with different activities level, can be by changing calcining heat and/or wherein kind and/or the quantity of alkali metal obtain.The appearance of focus or the hot polymerization collection on the focus are by establishment.CN00122609.6 provides a kind of PROPENE IN GAS PHASE OXIDATION to produce methacrylaldehyde and acrylic acid, use contains the oxide catalyst of Mo-Bi-Fe compound, described catalyst is filled in the multitubular reactor of fixed bed, and the method can generate methacrylaldehyde and acrylic acid with high stable yield in long-time.The method is characterized in that each distinguishes the filling different catalysts in each tubular reactor that disposes vertically two or more reaction zones, the ratio of namely filling out Bi the catalyst and/or Fe content and Mo content from the gas access end to gas outlet end reduces.US2009415167A discloses a kind of method of producing unsaturated aldehyde and unsaturated acids, two or more catalyst layer of in reactor, packing into, each catalyst layer by different holes density and or aperture size the catalyst of catalytic active component moulding fill, particular table area from reactor inlet to the outlet catalytic active component increase gradually with control hole density and or aperture size, and then inhibitory reaction focus.Even CN200410007263.1 provides a kind of and is forming under the condition of focus, active, selective, the life-span is all good, demonstrates for a long time the catalyst of stability, and the method for producing acrylic acid that uses this catalyst.Said catalyst is following general formula (1) Mo
aV
bW
cCu
dA
eB
fC
gO
xExpression.A is at least a for what select from cobalt, nickel, iron, lead, bismuth, B is at least a for what select from antimony, niobium, tin, C is at least a for what select from silicon, aluminium, titanium, zirconium, a, b, c, d, e, f, g, x represent respectively the atomic ratio of Mo, V, W, Cu, A, B, C, O, during a=12,2≤b≤15,0＜c≤10,0＜d≤6,0＜e≤30,0≤f≤6,0≤g≤60, the x numerical value that the state of oxidation of each element determines of serving as reasons.This catalyst can not establishment beds focus emerge.Reaction unit requires to have superpower resistance to elevated temperatures under higher focus condition, and the reaction later separation, to absorb the process operations expense also very high.CN200410048021.7 discloses a kind of gas and a kind of gas of molecule-containing keto for containing unsaturated aldehyde and carries out the O composite metallic oxide catalyst of selective oxidation reaction in gas phase, particularly relates to the O composite metallic oxide catalyst of a kind of methacrylaldehyde or the corresponding acrylic or methacrylic acid of MAL vapor phase catalytic oxidation production.Catalyst is by 1. molybdenum, vanadium, copper main active component and 2. requisite at least by the stable component of antimony and titanium and the 3. composite oxides that form of nickel, iron, silicon, aluminium, alkali metal, alkaline-earth metal.Wherein 2. and 3. be can be in 120 ℃ to 900 ℃ scopes the composite oxides of roasting preparation.This catalyst shows the permanent stability under high activity and the good selectivity.CN 03121882.2 discloses a kind of compound multi-metal-oxide catalyst and preparation method, is specially adapted to methacrylaldehyde vapor phase catalytic oxidation acrylic acid processed, and its catalyst consists of Mo
aV
bCu
cTe
dX
1 eX
2 fX
3 gX
4 hX
5 iO
x, X
1A kind of element that is selected from least tungsten and niobium, X
2A kind of element that is selected from least magnesium, calcium, strontium and barium, X
3A kind of element of chosen from Fe, cobalt and nickel at least, X
4A kind of element that is selected from least silicon, aluminium and titanium, X
5It is a kind of element that is selected from least antimony, tin and bismuth, catalyst contains molybdenum, vanadium and copper at least, adding necessary tellurium stablizes catalyst main active component molybdenum oxide and molybdic acid copper crystal again, when carrying out catalytic reaction, have lasting high activity and high selectivity, delay the inactivation that catalyst runs off and causes because of molybdenum.CN03148701.7 provides a kind of supported catalyst, and this catalyst carrier has multidimensional structure, with the self supporting type multidimensional carrier structure of preformed (such as foam, overall structure, fabric or other) or comprise Nb
2O
5, cordierite, partially stabilized zirconia, ceramic fibre or its mixture carrier, in succession described carrier deposition comprise any order at least one molybdenum-containing layer, at least one contains the vanadium layer, at least one contains the carbon monoxide-olefin polymeric that tellurium layer and at least one contain the X layer and forms the load carrier, after roasting supported catalyst.Be oxidized to unsaturated carboxylic acid for alkane and become unsaturated nitrile with ammoxidation of paraffins, enough conversion ratios are provided and are fit to selective.
All there is a problem in the method that above-mentioned inhibition focus produces, the catalyst that is filled in the reaction tube all has been diluted with various forms from the inlet to the outlet, active decline also can not change thinner ratio after both having made the catalyst runs some cycles, catalyst also can't provide higher activity again, not only loading, dismantle, separate, reclaim catalyst makes troubles, and can reduce the reactivity of catalyst, especially industrial long-term operation catalyst activity reduction is faster, affects catalyst life.Therefore, need the high activated catalyst of a kind of energy of exploitation establishment focus, to satisfy industrial propylene high-speed, highly selective oxidation acrolein, acrylic acid needs.In addition, under hot conditions, part active component molybdenum loses because of distillation from catalyst surface in the catalyst.The mixed airflows such as methacrylaldehyde, air (oxygen), nitrogen and steam wash away the loss of active component that also can make in the catalyst.For the loss that suppresses the molybdenum distillation causes active decay, CN1121504 can suppress dissipation effect and the over reduction of molybdenum composition by mixing copper component and zirconium and/or Titanium and/or Cerium with specified particle diameter and specific area; CN1445020 adds a small amount of tellurium and plays stable free molybdenum trioxide and the effect of molybdic acid copper crystal structure, and sublimation and the over reduction of molybdenum suppress to some extent; CN1583261 is take molybdenum, vanadium, copper, tungsten and/or niobium as key component, and the composite oxides or its hopcalite that consist of with other element form the loss that catalyst suppresses molybdenum.
The invention provides a kind ofly for the acrylic acid Catalysts and its preparation method of methacrylaldehyde selective oxidation system, in the acrolein oxidation process, can under low temperature, high-load condition, react.
Summary of the invention
The purpose of this invention is to provide compound multi-metal-oxide catalyst of a kind of methacrylaldehyde or the corresponding unsaturated acids of MAL selective oxidation production and preparation method thereof.Different from the method for above-mentioned reduction focus, the present invention makes catalyst granules have gradient difference to exterior active combination of components substrate concentration internally, can effectively reduce the reactor localized heat and gather, and suppresses emerging of focus.This catalyst has the characteristics of reactivity and selective height, good stability, long service life.
The present invention relates to a kind of compound multi-metal-oxide catalyst, the chief component of this catalyst is represented by following general formula (I)
Mo
aV
bW
cNi
dA
eB
fSi
gO
x (I)
Wherein: Mo is molybdenum, and V is vanadium, and W is tungsten, and Ni is nickel, and A is at least a element that is selected from copper, cobalt, the manganese; B is at least a element in selected among zirconium, strontium, lanthanum, magnesium and the titanium; Si is silicon, and silicon is the carrier that adds, and O is oxygen; A, b, c, d, e, f, g represent respectively each element atomic ratio, and wherein when a=12 was benchmark, b was a number of 3～10, preferred 3～7; C is a number of 0.5～5, preferred 1～3; D is a number of 1～5, preferred 1.5～3; E is a number of 0～3, f is a number of 0～3, g is a number of 0.5～30, x is the numerical value by the oxygen decision of each oxide, described compound multi-metal-oxide catalyst has multilayer structure, outer double-layer structure namely, every layer of catalyst chief component is identical, but the total content of one or more in silica, aluminium oxide or the carborundum is different, the total content of one or more in outer silica, aluminium oxide or the carborundum is than the height of internal layer parent, in molar content, each constituent content concentration ratio internal layer parent of catalyst outer layer is low.
Catalyst of the present invention is multilayer structure, mainly be achieved concentration difference by add the materials such as different amount silica, aluminium oxide, carborundum at ectonexine, that is to say, the total content of one or more in outer silica, aluminium oxide or the carborundum is higher than internal layer parent, in molar content, outer each constituent content is than this constituent content of internal layer low 0.5～30%, preferred 0.5～18%.Catalyst inner layer of the present invention also can not add silicon.
Methacrylaldehyde selective oxidation acrylic acid processed since reaction temperature more than 270 ℃, long period is under such pyroreaction condition, the active component molybdenum in the catalyst is easy to run off because of distillation.A in the catalyst of the present invention is copper preferably, and B is strontium and/or lanthanum, and strontium can be regulated catalyst surface acidity, and the chief component of catalyst represents that with general formula (II) wherein e is a number of 0.5～3, and f is a number of 0.05～3.Lanthanum and molybdenum, nickel, copper etc. can both form stable crystal phase structure, are conducive to suppress part active component molybdenum lose because of distillation from catalyst surface, and active component molybdenum content is substantially constant before and after the catalyst reaction, delays active deterioration rate, and catalyst stability is good.
Mo
aV
bW
cNi
dCu
eB
fSi
gO
x (II)
Active component comprises Mo, V, W, Ni in the catalyst of the present invention, also can add in cobalt, manganese, zirconium, strontium, magnesium and the titanium one or more, be conducive to improve dispersiveness and the tack of active component on the carriers such as silica, and then improve the selective of catalyst.E is a number of 0.1～2 in the catalyst composition general formula (I), and f is a number of 0.05～2.The catalyst granules that the present invention has multilayer structure reduces successively to exterior active combination of components substrate concentration internally, effectively reduce the single tube reactor localized heat and gather, suppress emerging of focus, catalyst is easy-sintering not, reactivity is stable, can bear the long period steady running.
The present invention has double-decker, and internal layer also can be called the internal layer parent.
Compound multi-metal-oxide catalyst of the present invention adopts common preparation method to get final product, as adopting following step preparation.
At first, Kaolinite Preparation of Catalyst internal layer parent:
Compound and the middle A of general formula (I) that will contain Mo, V, W, Ni
eB
fEach the elemental constituent compound that relates to dissolving and mix, carry out forming internal layer parent slurries after the co-precipitation, oven dry, moulding, roasting get the catalyst inner layer parent;
Secondly, method according to Kaolinite Preparation of Catalyst internal layer parent slurries prepares the outer layer catalyst slurries, add one or more of the materials such as silica, aluminium oxide, carborundum in the outer layer catalyst slurries preparation process, so that each concentration of element is lower than the concentration of this element of internal layer in the outer layer catalyst slurries;
At last, the outer layer catalyst for preparing is coated on the catalyst inner layer parent successively, after roasting, gets finished catalyst.
The present invention also can adopt a kind of multi-metal-oxide catalyst (III), and chief component is represented by following formula (III): Mo
aV
bNi
cCu
dNb
eSr
fM
gN
hSi
iO
x(III), wherein: Mo is molybdenum, and V is vanadium, and Ni is nickel, and Cu is copper, and Nb is niobium, and Sr is strontium, and M is at least a element that is selected from cobalt, iron, the manganese; N is at least a element that is selected from zinc, lanthanum, magnesium and the boron; O is oxygen; Si is silicon, silicon is the carrier that adds, a, b, c, d, e, f, g, h, i represents respectively each element atomic ratio, wherein when a=12 is benchmark, b is a number of 3～8, c is a number of 0.5～6, d is a number of 0.5～3, e is a number of 0.05～2, f is a number of 0.05～1.5, g is a number of 0.05～2, and h is a number of 0.05～1.5, and i is a number of 0.5～10, x is the numerical value by the oxygen decision of each oxide, described compound multi-metal-oxide catalyst has multilayer structure, namely in outer double-layer structure, every layer of catalyst chief component is identical, but silica, the total content of one or more in aluminium oxide or the carborundum is different, outer silica, the total content of one or more in aluminium oxide or the carborundum is than the height of internal layer parent, and in molar content, each constituent content concentration ratio internal layer parent of catalyst outer layer is low.In molar content, outer each constituent content is than this constituent content of internal layer low 0.5～30%.The preferred lanthanum of N in the formula (III), lanthanum and nickel, copper etc. can both form stable crystal phase structure, being conducive to suppress part active component molybdenum loses because of distillation from catalyst surface, active component molybdenum content is substantially constant before and after the catalyst reaction, delay active deterioration rate, catalyst activity and good stability.
The present invention can also adopt a kind of multi-metal-oxide catalyst (IV), and chief component is represented by following formula (IV): Mo
aV
bW
cNi
dSb
eA
fB
gSi
iO
x(IV) wherein: wherein: Mo is molybdenum, and V is vanadium, and W is tungsten, and Ni is nickel, and Sb is antimony, and Si is silicon, and silicon is the carrier that adds, and A is at least a element that is selected from strontium, iron, the bismuth; B is at least a element in selected among zirconium, lanthanum, magnesium and the phosphorus; O is oxygen; A, b, c, d, e, f, g, i represents respectively each element atomic ratio, wherein when a=12 is benchmark, b is a number of 1～6, c is a number of 0.5～5, d is a number of 0.5～5, e is a number of 0.05～2, f is a number of 0.05～2, g is a number of 0.05～2, i is a number of 0.5～10, and x is that described compound multi-metal-oxide catalyst has multilayer structure by the numerical value of the oxygen decision of each oxide, outer double-layer structure namely, every layer of catalyst chief component is identical, but silica, the total content of one or more in aluminium oxide or the carborundum is different, outer silica, the total content of one or more in aluminium oxide or the carborundum is than the height of internal layer parent, in molar content, each constituent content concentration ratio internal layer parent of catalyst outer layer is low.In molar content, outer each constituent content is than this constituent content of internal layer low 0.5～35%, preferred 1～25%.(IV) the preferred lanthanum of B in, lanthanum and antimony, nickel etc. can both form stable crystal phase structure, are conducive to suppress part active component molybdenum lose because of distillation from catalyst surface, and active component molybdenum content is substantially constant before and after the catalyst reaction, delay active deterioration rate, catalyst activity and good stability.
The present invention can also use a kind of multi-metal-oxide catalyst (V), and chief component is represented by following formula (V): Mo
aV
bCu
cCe
dA
gB
hSi
iO
x(V) wherein: Mo is molybdenum, and V is vanadium, and Cu is copper, and Ce is cerium, and Si is silicon, and silicon is the carrier that adds, and A is at least a element that is selected from strontium, antimony, tungsten, the nickel; B is at least a element that is selected from lanthanum, magnesium and the phosphorus; O is oxygen; A, b, c, d, g, h represents respectively each element atomic ratio, wherein when a=12 is benchmark, b is a number of 1～6, c is a number of 0.5～4, d is a number of 0.05～3, g is a number of 0～2, h is a number of 0～2, i is a number of 0.5～10, x is the numerical value by the oxygen decision of each oxide, described compound multi-metal-oxide catalyst has multilayer structure, namely in outer double-layer structure, every layer of catalyst chief component is identical, but silica, the total content of one or more in aluminium oxide or the carborundum is different, outer silica, the total content of one or more in aluminium oxide or the carborundum is than the height of internal layer parent, and in molar content, each constituent content concentration ratio internal layer parent of catalyst outer layer is low.In molar content, outer each constituent content is than this constituent content of internal layer low 0.5～35%, preferred 1～25%.The component cerium is conducive to component molybdenum, vanadium, the high degree of dispersion of copper on carrier silica, thereby improves the utilization rate of active component, but the addition of cerium is unsuitable too high, and too high and vanadium, copper are competed molybdenum, and activity descends on the contrary, satisfies (b+c)/d＞5.The preferred tungsten of A and/or nickel in the formula (V), the preferred lanthanum of B, g is a number of 0.05～2, h is a number of 0.05～2, lanthanum and nickel, copper etc. can both form stable crystal phase structure, are conducive to suppress part active component molybdenum lose because of distillation from catalyst surface, and active component molybdenum content is substantially constant before and after the catalyst reaction, delay active deterioration rate, catalyst activity and good stability.
Above-mentioned catalyst (III), (IV) and (V) adopt common preparation method get final product also can adopt above-mentioned preparation method to prepare.
Catalyst inner layer parent of the present invention is after the moulding and outer all need to compare not the respectively catalyst of roasting at 300～480 ℃ of lower roasting 3～10h after coating, and repeatedly roasting can improve the active and stable of catalyst.Can be that open roasting also can be enclosed roasting, calcination atmosphere can be the inert gases such as helium, nitrogen, argon gas.Catalyst layer chaps during thick roasting very much easily, for fear of be full of cracks be preferably in apply after 55～125 ℃ of oven dry, and then roasting.The outer layer catalyst bed thickness that is coated on the internal layer parent is 0.5～2.5mm, preferred 1.0～2mm.
The compound of each component of catalyst of the present invention can use nitrate, ammonium salt, sulfate, oxide, hydroxide, chloride, acetate of each element etc.
After the catalyst inner layer parent slurries of the present invention oven dry, the preferred forming methods such as extrusion molding, granulating and forming, compression molding that adopt are processed into spherical, hollow spheres, ellipticity, cylindric, hollow circuit cylinder etc., preferably hollow circuit cylinder or spherical usually.
Preferably use binding agent when catalyst of the present invention applies, make ectonexine catalyst bonding more firm.Be under the rolling condition at the internal layer parent and spray binding agent and infiltrate the surface, the outer layer catalyst powder for preparing of spraying more also can be put into the internal layer parent outer layer catalyst slurries that the prepare coating of rolling.Binding agent is selected from one or more in water, alcohols or the ethers.Alcohols such as ethanol, propyl alcohol, butanols; Ethers such as ether and butyl ether.
Each of catalyst of the present invention layer surface be uneven, rough surface preferably, is conducive to apply, and bonding is more firm between the ectonexine.
Intensity, the efflorescence degree of the present invention in order to improve catalyst can add in glass fibre, graphite, pottery or the various whisker one or more in above-mentioned outer layer catalyst.
Catalyst of the present invention can directly use, and also can be carried on the inert carrier and use.Related inert carrier can be one or more mixture of aluminium oxide, silica, carborundum etc.
The present invention also provides a kind of methacrylaldehyde selective oxidation acrylic acid processed: adopt the fixed bed single tube reactor; Reaction raw materials methacrylaldehyde, water, air enter reactor after the preheating through preheater more than 180 ℃, salt bath heating, and reaction process condition is: 245～265 ℃ of salt temperatures, preferred 250～262 ℃; Air speed 1400～2500h
-1, preferred 1500～2000h
-1, feed composition: methacrylaldehyde 7～12 volume %, steam 11～18%, air 10～18 volume %, nitrogen 60～72 volume %; Be equipped with in the reactor above-mentioned catalyst (III), (IV) or (V) in one or more.Acrolein conversion rate is between 98.2～99.5%, and acrylic acid is selectively between 88.0～91.3%.Hot(test)-spot temperature is between 279～291.
Because catalyst initial reaction activity is very high, thus be easy to produce focus or produce heat localization at the single tube reactor bed, the easy sintering of catalyst, this loses concerning suitability for industrialized production methacrylaldehyde acrylic acid is very serious.Pass into a certain amount of steam in the raw material, because specific heat of water is large, can take away a large amount of reaction heat, make active decline but the steam input greatly often makes catalyst member active component solution-off.The present invention has the compound multi-metal-oxide catalyst of multilayer structure by preparation, make catalyst granules have gradient difference to exterior active combination of components substrate concentration internally, and the every outer active component concentration of catalyst is lower than its adjacent inner layer active component concentration, like this, under the high-speed reaction condition, because the active component concentration of catalyst outer surface is low, so corresponding activity is also low, therefore can emerging of establishment focus and gathering of heat, reduce the growing amount of accessory substance (such as hydrocarbon), improve the selective of purpose product.Double-deck catalyst has good water repelling property.And when catalyst runs after a period of time, catalyst has release effects, wash away lower at mixed airflow, even the catalyst surface active component has part to run off, but because internal layer catalyst active component concentration is higher, can play additional effect, so can keep the catalyst activity lasting stability.
The evaluating catalyst performance indications are defined as follows:
The molal quantity of methacrylaldehyde * 100% in the total mole number/raw material of acrolein conversion rate (%)=acrolein reaction
Selective (the %)=methacrylaldehyde of acrylic acid is converted into the total mole number of acrylic acid molal quantity/acrolein reaction * 100%
The specific embodiment
The below illustrates compound multi-metal-oxide catalyst and preparation method thereof with specific embodiment, and this catalyst prepares catalytic performance in the acrylic acid at the methacrylaldehyde selective oxidation, but scope of the present invention is not limited to these embodiment.
Embodiment 1:
The preparation of catalyst 1
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active component slurries (a)
Under stirring condition, get 148 gram ammonium molybdates, ammonium metavanadate 24.6 grams, be dissolved in (water temperature is more than 65 ℃) in the 500ml pure water, obtain slurries (1), then get 64 the gram ammonium paratungstates, 5.5 the gram strontium nitrates, 17.9 the gram copper nitrates, 10.2 the gram cobalt nitrates be dissolved in (water temperature is more than 65 ℃) in the 500ml pure water, fully mix, obtain slurries (2).Then, slurries (1) mix with slurries (2), obtain slurries (3), obtain active component slurries (a).
(2) preparation of catalyst inner layer parent
In active component slurries (a), add 4.2 gram silica, 80 ℃ of strong stirrings carried out heat drying behind the coprecipitation reaction in 3 hours, in nitrogen with 160 ℃ of heat treatments 3 hours, then be the hollow columnar particle of φ 4.5 * 5mm through the banded extruder extrusion modling, dry rear 450 ℃ of roastings 5 hours for 110 ℃, make catalyst Precursors, this catalyst inner layer parent consists of: Mo
12V
3W
3.5Ni
4Cu
1.1Co
0.5Sr
0.3Si
1
Step 2: Kaolinite Preparation of Catalyst is outer
(1) preparation of active component slurries (a)
Preparation with active component slurries (a) in the embodiment 1 catalyst inner layer parent is identical.
(2) preparation of catalyst outer layer
Active component slurries (a) and 45 gram silicon dioxide powders are carried out coprecipitation reaction heat drying after 2.5 hours, and with 150 ℃ of heat treatments 3 hours, then 500 ℃ of roastings were 4 hours in nitrogen, processed to get the catalyst outer layer powder through pulverizing, grind, sieving.
Step 3: Kaolinite Preparation of Catalyst 1
The catalyst inner layer parent of step 1 preparation is placed round bottom container, under container rotation condition, spray ethanolic solution to catalyst Precursors, under the condition of abundant wetting catalyst inner layer parent, stop operating, put it into rapidly in the round bottom container of the outer layer catalyst powder that is placed with step 2 gained of another rotation, apply, coating layer thickness is at 1.0～2.0mm, and 105 ℃ of oven dry of gained catalyst namely got catalyst 1 in 4.5 hours by 450 ℃ of roastings.
Comparative Examples 1:
Take the internal layer parent of catalyst 1 as comparative catalyst 1, the banded extruder extrusion modling is the hollow columnar particle of φ 5 * 5mm, and reaction condition is with the appreciation condition of catalyst 1.
Comparative Examples 2:
Take the skin of catalyst 1 as comparative catalyst 2, the banded extruder extrusion modling is the hollow columnar particle of φ 5 * 5mm, and reaction condition is with the appreciation condition of catalyst 1.
Embodiment 2:
The preparation of catalyst 2
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active component slurries (a)
Under stirring condition, get 148 gram ammonium molybdates, ammonium metavanadate 40.9 grams, be dissolved in (water temperature is more than 65 ℃) in the 500ml pure water, obtain slurries (1), then get 54.8 the gram ammonium paratungstates, 61 the gram nickel nitrates be dissolved in (water temperature is more than 65 ℃) in the 500ml pure water, fully mix, obtain slurries (2).Then, slurries (1) mix with slurries (2), obtain slurries (3), obtain active component slurries (a).
(2) preparation of catalyst Precursors
In slurries (a), add 5 gram silica, 80 ℃ of strong stirrings carried out heat drying behind the coprecipitation reaction in 2 hours, in nitrogen with 160 ℃ of heat treatments 3 hours, then be the hollow columnar particle of φ 4.5 * 5mm through the banded extruder extrusion modling, dry rear 450 ℃ of roastings 4 hours for 60 ℃, make catalyst Precursors, this catalyst Precursors consists of: Mo
12V
5W
3Ni
3
Step 2: Kaolinite Preparation of Catalyst is outer
(1) preparation of active component slurries (a)
Preparation with active component slurries (a) in the embodiment 2 catalyst inner layer parents is identical.
(2) preparation of catalyst outer layer
Active component slurries (a) and 14 gram silicon dioxide powders and 4 gram graphite are carried out answering after the co-precipitation heat drying after 50 minutes, in nitrogen with 160 ℃ of heat treatments 3 hours, then 500 ℃ of roastings are 4 hours, process to get the catalyst outer layer powder through pulverizing, grind, sieving.
Step 3: Kaolinite Preparation of Catalyst 2
The catalyst inner layer parent of step 1 preparation is placed round bottom container, under container rotation condition, spray ethanolic solution to catalyst Precursors, abundant wetting catalyst inner layer parent, put it into rapidly in the round bottom container of the catalyst outer layer that is placed with step 2 gained of another rotation, apply, coating layer thickness is when 0.8～1.0mm, taking-up internal layer parent is put into another round bottom container rotation and is sprayed ethanolic solution after one to two minute again, then putting into the round bottom container that catalyst outer layer is housed continues to apply, until coating layer thickness stops to apply when 1.5～2.0mm, the oven dry of gained catalyst namely got catalyst 2 in 3 hours by 500 ℃ of roastings.
Comparative Examples 3:
Take the internal layer parent of catalyst 2 as comparative catalyst 3, the banded extruder extrusion modling is the hollow columnar particle of φ 5 * 5mm, and reaction condition is with the appreciation condition of catalyst 1.
Comparative Examples 4:
Take the skin of catalyst 2 as comparative catalyst 4, the banded extruder extrusion modling is the hollow columnar particle of φ 5 * 5mm, and reaction condition is with the appreciation condition of catalyst 1.
Embodiment 3:
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active component slurries (a)
Under stirring condition, get 148 gram ammonium molybdates, 24.6 ammonium metavanadates gram, be dissolved in (water temperature is more than 65 ℃) in the 500ml pure water, obtain slurries (1), then get 18.3 gram ammonium paratungstates, 21.2 copper nitrates, 40.7 gram nickel nitrates are dissolved in (water temperature is more than 65 ℃) in the 500ml pure water, fully mix, obtain slurries (2).Then, slurries (1) mix with slurries (2), obtain slurries (3), obtain active component slurries (a).
(2) preparation of catalyst inner layer parent
In slurries (a), add 8.4 gram silica, 80 ℃ of strong stirrings carried out heat drying behind the coprecipitation reaction in 3 hours, in nitrogen with 160 ℃ of heat treatments 3 hours, then be the hollow columnar particle of φ 4.5 * 5mm through the banded extruder extrusion modling, dry rear 350 ℃ of roastings 8 hours, make catalyst Precursors, this catalyst inner layer parent consists of: Mo
12V
3W
1Ni
2Cu
1.3
Step 2: Kaolinite Preparation of Catalyst is outer
(1) preparation of active component slurries (a)
Preparation and raw materials used identical (following examples are identical) with active component slurries (a) in the embodiment 3 catalyst inner layer parents.
(2) preparation of catalyst outer layer
Active component slurries (a) and 7.8 gram silicon dioxide powders and 5.7 gram aluminium oxide are carried out answering after the co-precipitation heat drying after 50 minutes, in nitrogen with 160 ℃ of heat treatments 3 hours, then 400 ℃ of roastings are 5 hours, process to get the catalyst outer layer powder through pulverizing, grind, sieving.
Step 3: Kaolinite Preparation of Catalyst 3
The catalyst inner layer parent of step 1 preparation is placed round bottom container, under container rotation condition, spray diethyl ether solution to catalyst Precursors, under the condition of abundant wetting catalyst inner layer parent, stop operating, put it into rapidly in the round bottom container of the catalyst outer layer that is placed with step 2 gained of another rotation, apply, coating layer thickness is at 1.5～2.0mm, and 85 ℃ of oven dry of gained catalyst namely got catalyst 3 in 4 hours by 450 ℃ of roastings.
Comparative Examples 5:
Take the internal layer parent of catalyst 3 as comparative catalyst 5, be the hollow columnar particle of φ 5 * 5mm through the banded extruder extrusion modling then, reaction condition is with the appreciation condition of catalyst 1.
Embodiment 4:
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active component slurries (a)
Under stirring condition, get 148 gram ammonium molybdates, 57.3 ammonium metavanadates gram, be dissolved in (water temperature is more than 65 ℃) in the 500ml pure water, obtain slurries (1), then get 36.6 gram ammonium paratungstates, 14.6 strontium nitrates, 30.5 gram nickel nitrates are dissolved in (water temperature is more than 65 ℃) in the 500ml pure water, add again 5.6 gram titanium dioxide, fully mix, obtain slurries (2).Then, slurries (1) mix with slurries (2), obtain slurries (3), obtain active component slurries (a).
(2) preparation of catalyst inner layer parent
In slurries (a), add 6.5 gram silica, 80 ℃ of strong stirrings carried out heat drying behind the coprecipitation reaction in 3 hours, in nitrogen with 160 ℃ of heat treatments 3 hours, then be the hollow columnar particle of φ 4.5 * 5mm through the banded extruder extrusion modling, dry rear 350 ℃ of roastings 8 hours for 120 ℃, make catalyst Precursors, this catalyst inner layer parent consists of: Mo
12V
7W
2Ni
1.5Sr
0.8Ti
1.0
Step 2: Kaolinite Preparation of Catalyst is outer
With preparation method and raw materials used identical (following examples are identical) of embodiment 4 catalyst outer layer, just add 6.3 gram silica and 20 gram carborundum.
Step 3: Kaolinite Preparation of Catalyst 4
The catalyst inner layer parent of step 1 preparation is placed round bottom container, under container rotation condition, spray ethanolic solution to catalyst, under the condition of abundant wetting catalyst inner layer parent, spray the outer layer catalyst powder of step 2 gained, apply, coating layer thickness is at 0.8～1.5mm, and 80 ℃ of oven dry of gained catalyst got catalyst 4 in 5 hours by 450 ℃ of roastings.
Comparative Examples 6:
Take the internal layer catalyst of catalyst 4 as comparative catalyst 6,300 ℃ of roastings 2.5 hours, be the hollow columnar particle of φ 5 * 5mm through the banded extruder extrusion modling, reaction condition is with the appreciation condition of catalyst 1.
Embodiment 5:
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active component slurries (a)
Under stirring condition, get 148 gram ammonium molybdates, 73.7 ammonium metavanadates gram, be dissolved in (water temperature is more than 65 ℃) in the 500ml pure water, obtain slurries (1), then get 82.3 the gram ammonium paratungstates, 14.6 the gram strontium nitrates, 29.3 the gram copper nitrates, 3.5 the gram potassium nitrate, 16.8 the gram magnesium nitrates, 20.4 the gram nickel nitrates be dissolved in (water temperature is more than 65 ℃) in the 500ml pure water, fully mix, obtain slurries (2).Then, slurries (1) mix with slurries (2), obtain slurries (3), obtain active component slurries (a).
(2) preparation of catalyst inner layer parent
In slurries (a), add 12.6 gram silica, 80 ℃ of strong stirrings carried out heat drying behind the coprecipitation reaction in 3 hours, in nitrogen with 160 ℃ of heat treatments 3 hours, then be the hollow columnar particle of φ 4.5 * 5mm through the banded extruder extrusion modling, dry rear 480 ℃ of roastings 4 hours for 120 ℃, make catalyst Precursors, this catalyst inner layer parent consists of: Mo
12V
9W
4.5Ni
1Cu
1.8K
0.5Mg
1.3
Step 2: Kaolinite Preparation of Catalyst is outer
Preparation with embodiment 5 catalyst outer layer is identical, just adds 9.7 gram silica, 6 gram graphite and 36 gram aluminium oxide.
Step 3: Kaolinite Preparation of Catalyst 5
The catalyst inner layer parent of step 1 preparation is placed round bottom container, under container rotation condition, spray distilled water to catalyst Precursors, under the condition of abundant wetting catalyst inner layer parent, spray the outer layer catalyst powder of step 2 gained, apply, coating layer thickness is at 0.8～1.2mm, and 75 ℃ of oven dry of gained catalyst got catalyst 5 in 6 hours by 450 ℃ of roastings.
Comparative Examples 7:
Take the internal layer catalyst of catalyst 5 as comparative catalyst 7, be the hollow columnar particle of φ 5 * 5mm through the banded extruder extrusion modling then, reaction condition is with the appreciation condition of catalyst 1.
Embodiment 6
Preparation process and raw material with embodiment 5 catalyst 5 are identical, just add 13.6 gram lanthanum nitrates and 5.5 gram strontium nitrates, and internal layer adds 7.3 gram silica; The outer 10.4 gram silica that add.Catalyst 6 internal layer parents consist of: Mo
12V
5W
0.7Ni
2.8Cu
0.8Sr
0.3La
0.6
Oxidation reaction
Fixed bed single tube reactor internal diameter 25mm, in establish thermocouple, the reactor above-mentioned catalyst of 45ml of packing into, salt bath heating.From above-mentioned reaction tube porch with air speed 1400h
-1Import the mist of methacrylaldehyde 9 volume %, air 12 volume %, steam 14 volume %, nitrogen 65 volume %.The performance of catalyst as shown in Table 1 and Table 2.Catalyst establishment focus, the difficult losses such as active component molybdenum, the molybdenum equal size is substantially constant before and after the catalyst reaction, and catalyst catalytic performance is stable, reacts 1000 hours rear catalysts and substantially can reach the fresh catalyst activity level, and catalyst stability is good.Comparative Examples 1～7 catalyst can not the establishment focus, and poor selectivity reacts behind 1000 hours rear catalysts that activity obviously descends under the washing away of the mixed airflows such as steam.
20 hours post-evaluation results of table 1 reaction
1000 hours post-evaluation results of table 2 reaction
Claims (15)
1. a compound multi-metal-oxide catalyst is characterized in that the chief component of this catalyst is by following
General formula (I) expression Mo
aV
bW
cNi
dA
eB
fSi
gO
x(I)
Wherein: Mo is molybdenum, and V is vanadium, and W is tungsten, and Ni is nickel, and A is at least a element that is selected from copper, cobalt, the manganese; B is at least a element in selected among zirconium, strontium, lanthanum, magnesium and the titanium; Si is silicon, and silicon is the carrier that adds, and O is oxygen; A, b, c, d, e, f, g represents respectively each element atomic ratio, wherein when a=12 is benchmark, b is a number of 3～10, c is a number of 0.5～5, d is a number of 1～5, e is a number of 0～3, f is a number of 0～3, g is a number of 0.5～30, x is that described compound multi-metal-oxide catalyst has interior outer double-layer structure, outer silica by the numerical value of the oxygen decision of each oxide, the total content of one or more in aluminium oxide or the carborundum is than the height of internal layer parent, in molar content, each constituent content concentration ratio internal layer parent of catalyst outer layer is low.
2. catalyst according to claim 1 is characterized in that b is a number of 3～7.
3. catalyst according to claim 1 is characterized in that c is a number of 1～3.
4. catalyst according to claim 1 is characterized in that d is a number of 1.5～3.
5. described catalyst according to claim 1 is characterized in that A is copper, and the composition of catalyst is by (II) expression Mo
aV
bW
cNi
dCu
eB
fSi
gO
x(II) wherein e is a number of 0.1～2.
6. described catalyst according to claim 5 is characterized in that B is strontium and/or lanthanum, and wherein f is a number of 0.05～2.
7. catalyst according to claim 1 is characterized in that for the catalyst multilayer structure, and in molar content, outer each constituent content is than this constituent content of internal layer low 0.5～30%.
8. catalyst according to claim 1 is characterized in that each constituent content of catalyst outer layer is than this constituent content of adjacent inner layer low 0.5～10%.
9. catalyst according to claim 1 is characterized in that A is at least a element that is selected from copper, cobalt, the manganese; B is at least a element in selected among zirconium, strontium, magnesium and the titanium; E is a number of 0.1～2 in the catalyst composition general formula (I), and f is a number of 0.05～2.
10. the preparation method of each described catalyst is characterized in that comprising the steps: according to claim 1～9
At first, Kaolinite Preparation of Catalyst internal layer parent:
Compound and the middle A of general formula (I) that will contain Mo, V, W, Ni
eB
fEach the elemental constituent compound that relates to dissolving and mix, carry out forming internal layer parent slurries after the co-precipitation, oven dry, moulding, roasting get the catalyst inner layer parent;
Secondly, prepare the outer layer catalyst slurries according to the method for Kaolinite Preparation of Catalyst internal layer parent slurries, add one or more of the materials such as silica, aluminium oxide, carborundum in the outer layer catalyst slurries preparation process;
At last, the outer layer catalyst for preparing is coated on the catalyst inner layer parent successively, after roasting, gets finished catalyst.
11. the preparation method of catalyst according to claim 10, it is characterized in that the internal layer parent after the moulding and outer after coating at 300～480 ℃ of lower roasting 3～10h, adopt open roasting or enclosed roasting, calcination atmosphere is helium, nitrogen or argon gas.
12. such as the preparation method of meter catalyst claimed in claim 10, it is characterized in that using binding agent when described catalyst applies, binding agent is selected from one or more in water, Ludox, the aluminium colloidal sol.
13. the preparation method of catalyst as claimed in claim 10 is characterized in that using binding agent when described catalyst applies, binding agent is selected from one or more in alcohols or the ethers.
14. such as each described catalyst of claim 1～9, it is characterized in that in each layer catalyst, adding in glass fibre, graphite, pottery or the whisker one or more.
15. a multi-metal-oxide catalyst is characterized in that the catalyst chief component is represented by following formula (III): Mo
aV
bNi
cCu
dNb
eSr
fM
gN
hSi
iO
x(III), wherein: Mo is molybdenum, and V is vanadium, and Ni is nickel, and Cu is copper, and Nb is niobium, and Sr is strontium, and M is at least a element that is selected from cobalt, iron, the manganese; N is at least a element that is selected from zinc, lanthanum, magnesium and the boron; O is oxygen; Si is silicon, silicon is the carrier that adds, a, b, c, d, e, f, g, h, i represents respectively each element atomic ratio, wherein when a=12 is benchmark, b is a number of 3～8, c is a number of 0.5～6, d is a number of 0.5～3, e is a number of 0.05～2, f is a number of 0.05～1.5, and g is a number of 0.05～2, and h is a number of 0.05～1.5, i is a number of 0.5～10, x is that described compound multi-metal-oxide catalyst has interior outer double-layer structure by the numerical value of the oxygen decision of each oxide, and every layer of catalyst chief component is identical, but silica, the total content of one or more in aluminium oxide or the carborundum is different, outer silica, the total content of one or more in aluminium oxide or the carborundum is than the height of internal layer parent, and in molar content, each constituent content concentration ratio internal layer parent of catalyst outer layer is low, in molar content, outer each constituent content is than this constituent content of internal layer low 0.5～30%.
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| CN110586119A (en) * | 2018-06-12 | 2019-12-20 | 中国石油化工股份有限公司 | Supported catalyst for preparing acrylic acid |
| CN111659408A (en) * | 2020-04-23 | 2020-09-15 | 宜兴市申生催化剂有限公司 | Preparation method of catalyst for preparing acrylic acid by acrolein oxidation |
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