CN102989472B - 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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- CN102989472B CN102989472B CN201110265245.3A CN201110265245A CN102989472B CN 102989472 B CN102989472 B CN 102989472B CN 201110265245 A CN201110265245 A CN 201110265245A CN 102989472 B CN102989472 B CN 102989472B
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Abstract
The invention relates to a composite multi-metal oxide catalyst and a preparation method thereof. The composition of the catalyst can be represented by a general formula of MoaBibFecNidSifAmBnOi, wherein Mo is molybdenum, Bi is bismuth, Fe is iron, Ni is nickel, and Si is silicon. Silicon is a carrier added in the catalyst. A is at least one element selected from cobalt, niobium, zinc, vanadium, lanthanum, and potassium. B is at least one element selected from alkaline earth metals. O is oxygen. The catalyst provided by the invention has a double-layer structure. With the catalyst, local heat accumulation in a single-pipe reactor can be effectively reduced. 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 compound multi-metal-oxide catalyst of propylene or the corresponding unsaturated aldehyde of selective isobutene oxidation production and preparation method thereof.More specifically, relate to a kind of catalyst with double-deck compound poly-metal deoxide, for catalyzing propone oxidation acrolein or isobutylene oxidation isobutylaldehyde processed.
Background technology
It is strong exothermal reaction that propylene gas phase catalytic oxidation reaction is prepared methacrylaldehyde, in reactor, moment is assembled a large amount of reaction heat, form hot localised points, if can not remove timely and effectively reaction heat, the heat that moment is gathered is constantly accumulated, by cause catalyst activity component loss, come off, to such an extent as to catalyst activity reduction, the lost of life, and cause, because over oxidation reacts the formation that aggravates accessory substance, even causing runaway reaction, make sintering of catalyst.The appearance of " progress of oxidation acrylic acid synthesizing process and catalyst " (petrochemical industry, the 39th the 7th phase of volume in 2010) social focus also can make catalyst damage evil, shortens the service life of catalyst.Taking 80,000 tons/year of acroleic acid devices as example, propylene oxidation is prepared and in acrolein reaction device, is needed more than 25000 tubulation, acrolein oxidation to prepare in acrylic acid reactor also to need more than 25000 tubulation, load altogether more than 100 ton of methacrylaldehyde, acrylic acid catalyst.More than 50000 reaction tube, the filling of catalyst ensures 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, for methacrylaldehyde, acrylic acid production, carry out as much as possible under cryogenic conditions, because reaction needed salt bath heating, its energy resource consumption that maintains production is also huge spending; Due to the generation of focus, high temperature resistant to the requirement of reaction tube tubing, for up to ten thousand reaction tubes, tubing expense is exactly a very large cost.Therefore,, if effectively suppress the generation of 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, as: Japanese patent laid-open 04-217932 has proposed the method for the hot polymerization collection on a kind of appearance or focus that suppresses focus, by preparing the multiple catalyst with different possessive volumes, and the mode reducing to outlet one side catalyst possessive volume from unstripped gas inlet side, fill successively reaction tube, but the possessive volume of catalyst is subject to the restriction of reaction tube diameter, and it is also very difficult that multiple catalysts is filled into reaction tube.CN1210511A prepares the multiple catalyst-loaded catalyst layer that arranges in reaction tube with different activities, arranges above-mentioned several catalyst-loaded according to the entrance from unstripped gas to the active order uprising of outlet.Also there is other method, for example, inert substance and catalyst mix, reduce the activity of catalyst, be loaded into reactor inlet place, Japanese Unexamined Patent Publication 10614/1972 is sneaked into heat resistanceheat resistant point to form catalyst is inert substance with by catalyst dilution in catalyst, and Japanese Patent Publication 36739/1987 is made catalyst the method for tubulose.There is again the Catalyst packing that unstrpped gas porch reduces by active component.CN01111960.8 uses fixed bed shell and tube reactor, under catalyst exists, prepare methacrylaldehyde and acrylic acid by propylene gas phase catalytic oxidation reaction, the method is the generation of focus or the hot polymerization collection on focus in inhibitory reaction district effectively, this catalyst consist of Mo
aw
bbi
cfe
da
eb
fc
gd
he
io
x, wherein the implication of Mo, W, Bi, Fe, A, B, C, D, E and O and a, b, c, d, e, f, g, h, i and x is as described in description.The feature of the method is the multiple catalysts that preparation has above-mentioned composition, but kind and/or the quantity of the temperature that (α) possessive volume, (β) calcine and/or (γ) alkali metal are different, and press the mode of catalyst activity from unstripped gas entrance to Increasing exports, catalyst is filled into reaction zone successively.CN00122609.6 provides under the condition that has the oxide catalyst that contains Mo-Bi-Fe compound, produce methacrylaldehyde and acrylic acid by vapor phase propylene oxide, described catalyst is filled in 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 in the each tubular reactor that configures vertically two or more reaction zones that each district's filling different catalysts is filled out catalyst Bi and/or Fe content and reduced with the ratio of Mo content from gas access end to gas outlet end.CN1672790A provides a kind of catalyzing propone aldehyde gaseous oxidation system acrylic acid catalyst, described catalyst comprises molybdenum and vanadium, also comprise at least one 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 that, by the volatility toxic component of specified quantitative being comprised and originally having in highly active catalyst, catalytic activity declines momently, can reduce the temperature of hot spot.CN1165055A is by after dividing catalytic active component and being loaded on carrier, calcines the generation that the catalyst of load sharing suppresses focus, and the average grain diameter of catalyst is 4～16mm, and the average grain diameter of carrier is 3～12mm, and calcining heat is 500～600 DEG C.CN1314331A provides the catalyst of a kind of Mo-W-Bi-Fe of containing, this catalyst is by the mode that changes the kind of possessive volume calcining heat and/or alkali metal and/or quantity and increase to outlet one side from the inlet side of unstripped gas according to catalyst activity, fills successively reaction zone with described multiple types catalyst.Catalyst is at least divided into two-layer in the axial direction of reaction tube, and 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.Hot polymerization collection on appearance or the focus of focus is effectively suppressed.
All there is a problem in the method that above-mentioned inhibition focus produces, the catalyst being filled in reaction tube has all been diluted with various forms from the inlet to the outlet, both after having made catalyst runs some cycles, active decline also can not change thinner ratio, catalyst also cannot 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.In addition, under hot conditions, in catalyst, part active component molybdenum loses because of distillation from catalyst surface.Washing away of propylene, air and steam mixed airflow also can make the loss of active component in catalyst.For the loss that suppresses molybdenum distillation causes active decay, CN1121504, by mixing copper component and zirconium and/or Titanium and/or the Cerium with specified particle diameter and specific area, can suppress dissipation effect and the over reduction of molybdenum composition; The effect that CN1445020 adds a small amount of tellurium to play to stablize free molybdenum trioxide and molybdic acid copper crystal structure, sublimation and the over reduction of molybdenum suppress to some extent; CN1583261 is taking molybdenum, vanadium, copper, tungsten and/or niobium as key component, and the composite oxides or its hopcalite that form with other element form the loss that catalyst suppresses molybdenum.
Summary of the invention
The object of this invention is to provide compound multi-metal-oxide catalyst of a kind of propylene or the corresponding unsaturated aldehyde of selective isobutene oxidation production and preparation method thereof.Different from the method for above-mentioned reduction focus, there is gradient difference from inside to exterior active combination of components substrate concentration in catalyst granules of the present invention, can effectively reduce fixed bed single tube reactor localized heat and gather, and suppresses emerging of focus.Catalyst is easy-sintering not, and this catalyst has the feature of reactivity and selective height, good stability.
The present invention relates to a kind of compound multi-metal-oxide catalyst, the chief component of this catalyst is by general formula (I) expression below
Mo
aBi
bFe
cNi
dSi
fA
mB
nO
i (I)
Wherein: Mo is molybdenum, Bi is bismuth, and Fe is iron, and Ni is nickel, and Si is silicon, and silicon is the carrier adding in catalyst, and A is at least one element being selected from cobalt, niobium, zinc, vanadium, lanthanum, potassium; B is at least one element being selected from alkaline-earth metal; O is oxygen; A, b, c, d, f, m and n represent respectively each element atomic ratio, and wherein a is a number of 12～14, and b is a number of 2～10, preferably 2～6; C is a number of 1～8, preferably 1～5; D is a number of 1～10, preferably 3～8; F is a number of 0.5～50, m is a number of 0.5～5, n is a number of 0～3, i is the numerical value being determined by the oxygen of each oxide, described compound multi-metal-oxide catalyst has interior outer double-layer structure, every layer of catalyst chief component is identical, but the total content difference of one or more in silica, aluminium oxide or carborundum, the total content of one or more in outer silica, aluminium oxide or carborundum is than the height of internal layer parent, in molar content, the each constituent content concentration ratio of catalyst outer layer internal layer parent is low.
Catalyst of the present invention is double-decker, there is gradient difference from inside to exterior active combination of components substrate concentration in catalyst, mainly by add the materials such as different amount silica, aluminium oxide, carborundum to be achieved concentration difference at ectonexine, that is to say, the total content of one or more in outer silica, aluminium oxide or carborundum is higher than internal layer parent, in molar content, outer each constituent content is lower by 0.5～30% than this constituent content of internal layer, and preferably 1～15%.Catalyst inner layer of the present invention also can not add silicon.
The present invention preferably adds active component lanthanum, general formula for composition (II) expression of catalyst, and in general formula (II), m is a number of 0.1～2, n is a number of 0.1～1.Lanthanum and nickel, cobalt etc. can form stable crystal phase structure, lose because of distillation from catalyst surface thereby suppress part active component molybdenum, and before and after catalyst reaction, active component molybdenum content is substantially constant, delays active deterioration rate, catalyst activity and good stability.
Mo
aBi
bFe
cNi
dSi
fLa
mB
nO
i (II)
The present invention also can add a small amount of alkaline-earth metal, and in general formula (I), m is a number of 0.1～2, and n is a number of 0.1～2.
Compound multi-metal-oxide catalyst of the present invention adopts common preparation method, as adopted following step preparation.
First, Kaolinite Preparation of Catalyst internal layer parent:
To contain Mo, Bi, A in the compound of Fe, Ni, Si and general formula (I)
mb
nthe each elemental constituent compound relating to dissolve and mix, carry out forming internal layer parent slurries after co-precipitation, dry, moulding, roasting obtains catalyst inner layer parent;
Secondly, method according to Kaolinite Preparation of Catalyst internal layer parent slurries is prepared outer layer catalyst slurries, in outer layer catalyst slurries preparation process, add one or more in silica, aluminium oxide or carborundum, make in outer layer catalyst slurries each concentration of element lower than the concentration of this element of adjacent inner layer;
Finally, the outer layer catalyst of preparation is coated on catalyst inner layer parent successively, after roasting, obtains finished catalyst.
Catalyst inner layer parent of the present invention after moulding and outer all need to be at 300～500 DEG C after coating roasting 3～10h, compare not the catalyst of roasting respectively, repeatedly roasting can improve activity and the stability of catalyst.Can be that open roasting can be also enclosed roasting, calcination atmosphere can be the inert gases such as helium, nitrogen, argon gas.
Catalyst layer easily chaps when thick roasting very much, for fear of be full of cracks be preferably in apply after 55～125 DEG C of oven dry, and then roasting.The outer layer catalyst bed thickness that is coated on internal layer parent is 1.0～2.5mm, preferably 1.5～2mm.
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.Active component is not all used nitrate as far as possible, the oxide contaminant atmosphere producing in the time of roasting, and be not easy moulding, manufacturing schedule is slow, but nitrate is easy to dissolve, and nitrate preferably uses together with other forms of compound, be easy to moulding, speed production efficiency.
After catalyst inner layer parent slurries of the present invention are dried, conventionally preferably adopt the forming methods such as extrusion molding, granulating and forming, compression molding to be processed into spherical, hollow spheres, ellipticity, cylindric, hollow circuit cylinder etc., preferably hollow circuit cylinder or spherical.
Compound multi-metal-oxide catalyst of the present invention preferably uses binding agent while coating, makes ectonexine catalyst bonding more firm.Under rolling condition, spray binding agent at internal layer parent and infiltrate surface, then the outer layer catalyst powder for preparing of spraying, also internal layer parent can be put into the outer layer catalyst slurries that the prepare coating of rolling.Binding agent is selected from one or more in water, alcohols or ethers.Alcohols is as ethanol, propyl alcohol, butanols; Ethers is as ether and butyl ether.
Preferably uneven, the rough surface of each layer of surface of catalyst of the present invention, is conducive to apply, and bonding is more firm between layers.
The present invention, in order to improve intensity, the efflorescence degree of catalyst, can add one or more in glass fibre, graphite, pottery or various whisker in above-mentioned outer layer catalyst.
The present invention has double-decker, and internal layer also can be called internal layer parent.
Composite oxide catalysts of the present invention can directly use, and also can be carried on inert carrier and use.Related inert carrier can be one or more mixture of aluminium oxide, silica, carborundum, magnesia etc.
Because catalyst initial reaction activity is very high, so be easy to produce focus or produce heat localization on fixed bed single tube reactor bed, catalyst is easy to sintering, and this loses concerning suitability for industrialized production methacrylaldehyde acrylic acid is very serious.In raw material, pass into a certain amount of steam, because specific heat of water is large, can take away a large amount of reaction heat, make active decline but steam input greatly often makes catalyst member active component solution-off.
The present invention has double-deck compound multi-metal-oxide catalyst by preparation, make catalyst granules have gradient difference from inside to exterior active combination of components substrate concentration, and catalyst outer layer active component concentration is lower than its internal layer active component concentration, like this, under high-speed reaction condition, because the active component concentration of catalyst outer surface is low, so corresponding activity is also low, therefore can effectively suppress emerging of focus and gathering of heat, reduce the growing amount of accessory substance (as hydrocarbon), improve the selective of object product.This has double-deck catalyst and has good water repelling property.And when after catalyst runs a period of time, catalyst has release effects, under mixed airflow long period washes away, even if catalyst surface active component has part to run off, but because internal layer catalyst active component concentration is higher, can play supplementary effect, so can keep catalyst activity lasting stability.
Evaluating catalyst performance indications are defined as follows:
Molal quantity × 100% of propylene in the total mole number/raw material of propylene conversion (%)=propylene reaction
Selective (the %)=propylene of methacrylaldehyde is converted into total mole number × 100% of molal quantity/propylene reaction of methacrylaldehyde
Detailed description of the invention
There is double-deck compound multi-metal-oxide catalyst and preparation method thereof with specific embodiment explanation below, and this catalyst prepares the catalytic performance of methacrylaldehyde to Propylene Selectivity oxidation, but scope of the present invention is not limited to these embodiment.The propylene that following examples adopt is the high concentration propylene of propylene content >=99.6% (volume fraction).
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 160 grams of ammonium molybdates and be dissolved in (water temperature is more than 65 DEG C) in 500ml pure water, obtain slurries (1), then get 142.5 grams of nickel nitrates, 7 grams of potassium nitrate, 113 grams of ferric nitrates and be dissolved in (water temperature is more than 65 DEG C) in 1000ml pure water, fully be uniformly mixed, obtain slurries (2).Get again 237.7 grams of bismuth nitrates, under stirring condition, be dissolved in rare nitric acid, obtain slurries (3).Then, slurries (1) mix with slurries (2), obtain slurries (4), then slurries (3) are added in slurries (4), obtain active component slurries (a).
(2) preparation of catalyst inner layer parent
In active component slurries (a), add 16 grams of silica, 80 DEG C of strong stirrings carry out heat drying after coprecipitation reaction for 2 hours, in nitrogen with 160 DEG C of heat treatments 3 hours, then be the hollow columnar particle of φ 4.5 × 5mm through banded extruder extrusion modling, dry rear 450 DEG C of roastings 4 hours for 95 DEG C, make catalyst Precursors, this catalyst inner layer parent consists of: Mo
13bi
7fe
4ni
7k
1si
3.8
Step 2: Kaolinite Preparation of Catalyst skin
(1) preparation of active component slurries (a)
Preparation with active component slurries (a) in embodiment 1 catalyst inner layer parent is identical.
(2) preparation of catalyst outer layer
Active component slurries (a) and 32 grams of silicon dioxide powders are carried out to coprecipitation reaction heat drying after 40 minutes, and in nitrogen, with 150 DEG C of heat treatments 3 hours, then 500 DEG C of roastings 4 hours, processed to obtain catalyst outer layer powder through pulverizing, grind, sieving.
Step 3: Kaolinite Preparation of Catalyst 1
Catalyst inner layer parent prepared by step 1 is placed in round bottom container, under container rotation condition, spray ethanolic solution to catalyst Precursors, under the condition of fully wetting catalyst inner layer parent, stop operating, put it into rapidly in the round bottom container of outer layer catalyst powder that is placed with step 2 gained of another rotation, apply, coating layer thickness, at 0.5～2.0mm, obtains catalyst 1 for 4 hours through 500 DEG C of roastings after 90 DEG C of oven dry of gained catalyst.
Comparative example 1:
Taking the internal layer parent of catalyst 1 as comparative catalyst 1, be then the hollow columnar particle of φ 5 × 5mm through banded extruder extrusion modling, reaction condition is with the appreciation condition of catalyst 1.
Comparative example 2:
Taking the skin of catalyst 1 as comparative catalyst 2, be then the hollow columnar particle of φ 5 × 5mm through banded extruder extrusion modling, 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 173 grams of ammonium molybdates and be dissolved in (water temperature is more than 65 DEG C) in 500ml pure water, obtain slurries (1), then get 81.4 grams of nickel nitrates, 12.9 grams of magnesium nitrates, 183.8 grams of ferric nitrates and be dissolved in (water temperature is more than 65 DEG C) in 500ml pure water, fully be uniformly mixed, obtain slurries (2).Get again 169.8 grams of bismuth nitrates, under stirring condition, be dissolved in rare nitric acid, obtain slurries (3).Then, slurries (1) mix with slurries (2), obtain slurries (4), then slurries (3) are added in slurries (4), obtain active component slurries (a).
(2) preparation of catalyst Precursors
In slurries (a), add 18 grams of silica, 80 DEG C of strong stirrings carry out heat drying after coprecipitation reaction for 2 hours, in nitrogen with 160 DEG C of heat treatments 3 hours, then be a granulated into through banded extruder extruding, rolling the ball shape that diameter is 2mm, dry rear 450 DEG C of roastings 4 hours for 65 DEG C, make catalyst Precursors, this catalyst Precursors consists of: Mo
14bi
5fe
6.5ni
4mg
1
Step 2: Kaolinite Preparation of Catalyst skin
(1) preparation of active component slurries (a)
Preparation with active component slurries (a) in embodiment 2 catalyst inner layer parents is identical.
(2) preparation of catalyst outer layer
Active component slurries (a) and 35 grams of silicon dioxide powders are carried out answering after co-precipitation heat drying after 50 minutes, and in nitrogen, with 160 DEG C of heat treatments 3 hours, then 500 DEG C of roastings 4 hours, processed to obtain catalyst outer layer powder through pulverizing, grind, sieving.
Step 3: Kaolinite Preparation of Catalyst 2
Catalyst inner layer parent prepared by step 1 is placed in round bottom container, under container rotation condition, spray ethanolic solution to catalyst Precursors, fully 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 in the time of 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 put into the round bottom container continuation coating that catalyst outer layer is housed, until coating layer thickness stops applying in the time of 0.5～2.0mm, after 95 DEG C of oven dry of gained catalyst, within 3 hours, obtain catalyst 2 through 550 DEG C of roastings.
Comparative example 3:
Taking the internal layer parent of catalyst 2 as comparative catalyst 3, make the ball that diameter is 4mm, reaction condition is with the appreciation condition of catalyst 1.
Comparative example 4:
Taking the skin of catalyst 2 as comparative catalyst 4, make the ball that diameter is 4mm, 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)
With preparation method and raw materials used identical (following examples are identical) of embodiment 1 catalyst activity component slurries (a), just add 40.7 grams of cobalt nitrates, 6.5 grams of magnesium nitrates.
(2) preparation of catalyst inner layer parent
In slurries (a), add 15 grams of silica, 80 DEG C of strong stirrings carry out heat drying after coprecipitation reaction for 2 hours, in nitrogen with 160 DEG C of heat treatments 3 hours, then be the hollow columnar particle of φ 4.5 × 5mm through banded extruder extrusion modling, dry rear 450 DEG C of roastings 4 hours for 95 DEG C, make catalyst Precursors, this catalyst inner layer parent consists of: Mo
13bi
3fe
4ni
6co
2mg
0.5
Step 2: Kaolinite Preparation of Catalyst skin
(1) preparation of active component slurries (a)
Preparation with active component slurries (a) in embodiment 1 catalyst inner layer parent is identical.
(2) preparation of catalyst outer layer
Active component slurries (a) and 62 grams of silicon dioxide powders are carried out answering after co-precipitation heat drying after 50 minutes, and in nitrogen, with 160 DEG C of heat treatments 3 hours, then 500 DEG C of roastings 4 hours, processed to obtain catalyst outer layer powder through pulverizing, grind, sieving.
Step 3: Kaolinite Preparation of Catalyst 3
Catalyst inner layer parent prepared by step 1 is placed in round bottom container, under container rotation condition, spray diethyl ether solution to catalyst Precursors, under the condition of fully 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, at 1.0～2.0mm, obtains catalyst 3 for 3 hours through 550 DEG C of roastings after 70 DEG C of oven dry of gained catalyst.
Comparative example 5:
Taking the internal layer parent of catalyst 3 as comparative catalyst 5, be then the hollow columnar particle of φ 5 × 5mm through banded extruder extrusion modling, reaction condition is with the appreciation condition of catalyst 1.
Comparative example 6:
Taking the skin of catalyst 3 as comparative catalyst 6, be then the hollow columnar particle of φ 5 × 5mm through banded extruder extrusion modling, reaction condition is with the appreciation condition of catalyst 1.
Embodiment 4:
Step 1: Kaolinite Preparation of Catalyst internal layer parent
Preparation method with embodiment 2 catalyst inner layer parents is identical, just adds 16.7 grams of zinc nitrates, 16.4 grams of cesium nitrates, adds 5.2 grams of silica, and this catalyst inner layer parent consists of:
Mo
12Bi
8Fe
1.5Ni
9Zn
0.8Cs
1.2
Step 2: Kaolinite Preparation of Catalyst skin
With the preparation method of embodiment 2 catalyst outer layer and raw materials used identical, just add 22.4 grams of silica and 15 grams of aluminium oxide.
Step 3: Kaolinite Preparation of Catalyst 4
Catalyst inner layer parent prepared by step 1 is placed in round bottom container, under container rotation condition, spray ethanolic solution to catalyst, under the condition of fully wetting catalyst inner layer parent, spray the outer layer catalyst powder of step 2 gained, apply, coating layer thickness, at 0.8～1.5mm, obtains catalyst 4 for 5 hours through 450 DEG C of roastings after 50 DEG C of oven dry of gained catalyst.
Embodiment 5:
Step 1: Kaolinite Preparation of Catalyst internal layer parent
Preparation method with embodiment 2 catalyst inner layer parents is identical, adds 7 grams of potassium nitrate, 9.1 grams of lanthanum nitrates, 10.2 grams of silica, and this catalyst inner layer parent consists of: Mo
12bi
9fe
3ni
8k
1la
0.4
Step 2: Kaolinite Preparation of Catalyst skin
Preparation with embodiment 2 catalyst outer layer is identical, just adds 38.1 grams of silica and 10.6 grams of carborundum.
Step 3: Kaolinite Preparation of Catalyst 5
Catalyst inner layer parent prepared by step 1 is placed in round bottom container, under container rotation condition, spray distilled water to catalyst Precursors, under the condition of fully wetting catalyst inner layer parent, spray the inferior outer layer catalyst powder of step 2 gained, apply, coating layer thickness, at 0.8～1.2mm, obtains catalyst 5 for 6 hours through 500 DEG C of roastings after 105 DEG C of oven dry of gained catalyst.
Comparative example 7:
Taking the internal layer catalyst of catalyst 5 as comparative catalyst 7, but do not contain lanthanum, catalyst consists of Mo
12bi
9fe
3ni
8k
1.Reaction condition is with the appreciation condition of catalyst 1.
Embodiment 6:
With the preparation method of embodiment 5 catalyst and raw materials used identical, internal layer adds 8 grams of silica, and skin adds 19.7 grams of silica, and catalyst inner layer parent consists of: Mo
12bi
5fe
3.5ni
3mg
0.5la
1.1
Embodiment 7:
The preparation of catalyst 7
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active component slurries (a)
Under stirring condition, get 160 grams of ammonium molybdates and be dissolved in (water temperature is more than 65 DEG C) in 500ml pure water, obtain slurries (1), then get 93.6 grams of nickel nitrates, 99 grams of ferric nitrates are dissolved in (water temperature is more than 65 DEG C) in 1000ml pure water, fully be uniformly mixed, obtain slurries (2).Get again 203.7 grams of bismuth nitrates, under stirring condition, be dissolved in rare nitric acid, obtain slurries (3).Then, slurries (1) mix with slurries (2), obtain slurries (4), then slurries (3) are added in slurries (4), obtain active component slurries (a).
(2) preparation of catalyst inner layer parent
In active component slurries (a), add 7 grams of silica, 80 DEG C of strong stirrings carry out heat drying after coprecipitation reaction for 2 hours, in nitrogen with 160 DEG C of heat treatments 3 hours, then be the hollow columnar particle of φ 4.5 × 5mm through banded extruder extrusion modling, dry rear 450 DEG C of roastings 4 hours for 50 DEG C, make catalyst Precursors, this catalyst inner layer parent consists of: Mo
13bi
6fe
3.5ni
4.6
Step 2: Kaolinite Preparation of Catalyst skin
(1) preparation of active component slurries (a)
Preparation with active component slurries (a) in embodiment 1 catalyst inner layer parent is identical.
(2) preparation of catalyst outer layer
Active component slurries (a) and 12 grams of silicon dioxide powders and 4 grams of graphite powders are carried out to coprecipitation reaction heat drying after 40 minutes, in nitrogen with 150 DEG C of heat treatments 3 hours, then 480 DEG C of roastings 4 hours, process to obtain catalyst outer layer powder through pulverizing, grind, sieving.
Step 3: Kaolinite Preparation of Catalyst 7
Catalyst inner layer parent prepared by step 1 is placed in round bottom container, under container rotation condition, spray ethanolic solution to catalyst Precursors, under the condition of fully wetting catalyst inner layer parent, stop operating, put it into rapidly in the round bottom container of outer layer catalyst powder that is placed with step 2 gained of another rotation, apply, coating layer thickness, at 1.5～2.0mm, obtains catalyst 7 for 4 hours through 450 DEG C of roastings after 100 DEG C of oven dry of gained catalyst.
Oxidation reaction
Fixed bed single tube reactor internal diameter 20mm, inside establishes thermocouple, and reactor feedstocks gas entrance side packs the above-mentioned catalyst of 35ml, salt bath heating into.From above-mentioned reaction tube porch with air speed 900h
-1import the mist of propylene 10 volume %, air 74 volume %, steam 16 volume %.The performance of catalyst as shown in Table 1 and Table 2.Catalyst effectively suppresses focus, and catalyst reaction front and back active component molybdenum etc. does not run off substantially, and catalyst catalytic performance is stable.After running in 500 hours, active, selectively substantially can reach fresh catalyst level, catalyst stability is good.Comparative example 1～7 catalyst can not effectively suppress focus, and poor selectivity is reacted after 500 hours rear catalysts activity under the washing away of the mixed airflows such as steam and obviously declined.
Table 1 reacts 20 hours post-evaluation results
Table 2 reacts 500 hours post-evaluation results
Claims (11)
1. a compound multi-metal-oxide catalyst, is characterized in that catalyst chief component is as shown in general formula (I): Mo
abi
bfe
cni
dsi
fa
mb
no
i(I)
Wherein: Mo is molybdenum, Bi is bismuth, and Fe is iron, and Ni is nickel, and Si is silicon, and silicon is the carrier adding in catalyst, and A is at least one element being selected from cobalt, niobium, zinc, vanadium, lanthanum, potassium; B is at least one element being selected from alkaline-earth metal; O is oxygen; A, b, c, d, f, m and n represent respectively each element atomic ratio, wherein a is a number of 12～14, b is a number of 2～10, c is a number of 1～8, d is a number of 1～10, f is a number of 0.5～50, m is a number of 0.5～5, n is a number of 0～3, i is the numerical value being determined by the oxygen of each oxide, and described compound multi-metal-oxide catalyst has interior outer double-layer structure, and the total content of outer silica is than the height of internal layer parent, in molar content, the each constituent content concentration ratio of catalyst outer layer internal layer parent is low.
2. catalyst as claimed in claim 1, is characterized in that b is a number of 2～6.
3. catalyst as claimed in claim 1, is characterized in that c is a number of 1～5.
4. catalyst as claimed in claim 1, is characterized in that d is a number of 4～8.
5. catalyst as claimed in claim 1, is characterized in that in molar content, and outer each constituent content is lower by 0.5～30% than this constituent content of adjacent inner layer.
6. catalyst as claimed in claim 1, is characterized in that the each constituent content of catalyst outer layer is lower by 1～15% than this constituent content of adjacent inner layer.
7. catalyst as claimed in claim 1, is characterized in that A is selected from lanthanum, and catalyst forms as shown in general formula (II): Mo
abi
bfe
cni
dsi
fla
mb
no
i(II) wherein m is a number of 0.1～2, and n is a number of 0.1～1.
8. catalyst as claimed in claim 1, is characterized in that in general formula (I), A is at least one element being selected from cobalt, niobium, zinc, vanadium, lanthanum, potassium; B is at least one element being selected from alkaline-earth metal, and m is a number of 0.1～2, and n is a number of 0.1～2.
9. the preparation method of the catalyst as described in claim 1～8 any one, is characterized in that comprising the steps:
First, Kaolinite Preparation of Catalyst internal layer parent:
To contain Mo, Bi, A in the compound of Fe, Ni, Si and general formula (I)
mb
nthe each elemental constituent compound relating to dissolve and mix, carry out forming internal layer parent slurries after co-precipitation, dry, moulding, roasting obtains catalyst inner layer parent;
Secondly, prepare outer layer catalyst slurries according to the method for Kaolinite Preparation of Catalyst internal layer parent slurries, in outer layer catalyst slurries preparation process, add silica;
Finally, the outer layer catalyst of preparation is coated on catalyst inner layer parent successively, after roasting, obtains finished catalyst.
10. the preparation method of catalyst as claimed in claim 9, it is characterized in that internal layer parent after moulding and outer after coating at 300～580 DEG C roasting 3～10h, adopt open roasting or enclosed roasting, calcination atmosphere is helium, nitrogen or argon gas.
The preparation method of 11. catalyst as claimed in claim 9, is characterized in that when described catalyst applies using binding agent, binding agent to be selected from one or more in alcohols or ethers.
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