CN107282062A - Catalyst of ammoxidation of propylene acrylonitrile production and preparation method thereof - Google Patents
Catalyst of ammoxidation of propylene acrylonitrile production and preparation method thereof Download PDFInfo
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- CN107282062A CN107282062A CN201610225893.9A CN201610225893A CN107282062A CN 107282062 A CN107282062 A CN 107282062A CN 201610225893 A CN201610225893 A CN 201610225893A CN 107282062 A CN107282062 A CN 107282062A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
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Abstract
The present invention relates to catalyst of ammoxidation of propylene acrylonitrile production and preparation method thereof, the catalyst choice for mainly solving to be used for present in prior art ammoxidation of propylene reaction is low, the problem of stability is poor.The present invention is using the catalyst of ammoxidation of propylene acrylonitrile production, including carrier and the active component that is represented containing below general formula：AaBbCcBidMo13.6Ox；A is selected from least one of K, Rb and Cs in formula；B is selected from least one of Ca, Mn, Fe, Co, Ni, Mg, Cr, W, P and Nb；C is selected from least one of rare earth element；Described carrier includes silica and support modification agent, and the support modification agent is selected from the scheme of at least one of aluminum oxide and diatomite, preferably resolves the problem, in the industrial production that acrylonitrile is produced available for ammoxidation of propylene.
Description
Technical field
The present invention relates to a kind of catalyst of ammoxidation of propylene acrylonitrile production and preparation method thereof.
Background technology
The industrial production that current olefin ammoxidation prepares unsaturated nitrile still generally uses fluid bed ammonia oxidation process, and catalyst is used as this
One of core technology of technique, it is studied, improves and paid attention to always.The catalyst of current industrial ammoxidation of propylene acrylonitrile production
Mainly there are two classes：Mo-Bi systems and Sb systems, wherein Mo-Bi series catalysts are occupied an leading position, and reach the 95% of olefin oxidation market,
Forefathers study and explored and are also concentrated mainly on Mo-Bi series catalysts.By introducing the metal with variable valence in the catalyst
The elements such as component such as Fe, Ce improve the oxidationreduction performance of catalyst, accelerate to recover the effective status of catalyst activity component；
By introducing metallic element of the ionic radius more than 0.8nm and less than 0.8nm, such as Cr, Ni, Mg, Mn, Zn, Al member
Element, plays structure and electronic auxiliary effect, improves the Structure and stability energy of catalyst；By introducing rare earth element, raising is urged
The Lattice Oxygen quantity of agent, improves the catalytic performance of catalyst；By introducing the elements such as Cs, Rb, P, B, Al, to catalysis
Agent carries out the regulation of surface modification and acid-base property, improves the selectivity and activity of catalyst.
The Mo-Bi series catalysts that patent CN1210033A, CN1285238A, CN1294942A, CN1751790A are proposed
Suitable for being used under higher reaction pressure and high propylene loading condiction, the characteristics of remaining to keep very high single-pass yield of acrylonitrile.
Patent CN03151170.8 and CN03151169.4 are described in catalyst preparation process, in carrier starting material Ludox
The grain diameter for adding 2~25% is 5~100 nanometers of solid silica to improve catalyst performance.
In above all of patent document, oxide catalyst is loaded on a kind of silica supports, and in such oxygen
Change in method for preparing catalyst, using Ludox as the source of silica, but the influence factor of Ludox is special more than
Do not referred in sharp document.
Patent CN1129408A proposes that the aluminium content of the Ludox added in catalyst preparation process is provided, can be notable
Ground improves the selectivity of acrylonitrile, but the content to other components does not have clear stipulaties.
Patent CN1744949A proposes that the cell size distribution by the initial particle for changing silica material to catalyst is controlled.
Catalyst in for unsaturated olefin ammoxidation, generally including containing molybdenum, bismuth, iron and it is at least one selected from potassium,
The oxide catalyst of the oxide composition of the element such as rubidium and caesium, and oxide catalyst is loaded in silica supports thereon.
The present invention is by further studying, and the selectivity and stability that the additive in discovery carrier is reacted ammoxidation of propylene have substantially
Influence.
The content of the invention
One of technical problems to be solved by the invention be ammoxidation of propylene acrylonitrile production in the prior art catalyst choice it is low,
The problem of stability is poor is there is provided a kind of catalyst of ammoxidation of propylene acrylonitrile production, and the catalyst has selectivity high, stably
The characteristics of property is good.
The two of the technical problems to be solved by the invention are to provide a kind of preparation method of one of above-mentioned technical problem catalyst.
The three of the technical problems to be solved by the invention are the ammoxidation of propylene lifes using one of the above-mentioned technical problem catalyst
Produce the synthetic method of acrylonitrile.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：
The catalyst of ammoxidation of propylene acrylonitrile production, including carrier and the active component that is represented containing below general formula：
AaBbCcBidMo13.6Ox
A is selected from least one of K, Rb and Cs in formula；B be selected from Ca, Mn, Fe, Co, Ni, Mg, Cr, W,
At least one of P and Nb；C is selected from least one of rare earth element.A span is 0.01~2.5；B's takes
It is 1~15 to be worth scope；C span is 0.01~5；D span is 0.01~3；X is each in catalyst to meet
Oxygen atom sum needed for element valence；
Described carrier include silica and support modification agent, the support modification agent in aluminum oxide and diatomite extremely
Few one kind.
In above-mentioned technical proposal, the support modification agent is simultaneously including diatomite and aluminum oxide, and now both are in raising selectivity
Acted synergistically with having in terms of stability.Both aluminum oxide and diatomite weight ratio are not particularly limited, such as, but not limited to 1：
1~10, more preferably 1：1~5.
In above-mentioned technical proposal, the silica preferably originates from Ludox.
In above-mentioned technical proposal, the consumption of carrier is not particularly limited, preferably 30~70wt% of catalyst weight.
In above-mentioned technical proposal, support modification agent content is preferably 0.1~5wt% in carrier.
To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：It is catalyzed described in one of above-mentioned technical problem
The preparation method of agent, comprises the following steps：
(a) at least one salt of the desired amount of corresponding active component element in addition to Mo is dissolved, obtains solution I；
(b) the desired amount of Ludox is mixed with support modification agent, obtains mixed liquor I I；
(c) molybdate of the aequum containing molybdenum is dissolved, and mixed with mixed liquor I I, obtain mixed liquor I II；
(d) solution I and mixed liquor I II are mixed, is that 1~7 and temperature are stirred at 20~90 DEG C in pH, obtains slurry I；
(e) slurry I is spray-dried and calcination activation obtains required catalyst for 0.2~4 hour at 520~660 DEG C.
In above-mentioned technical proposal, it will be appreciated by those skilled in the art that step (b) in order to obtain disperse more uniform mixed liquor
II, support modification agent takes fine particulate form to be mixed with Ludox, but the particle diameter of support modification agent particle is not particularly limited,
Comparable invention effect can be obtained.Therefore, as taking the form of support modification agent colloidal sol to be mixed with Ludox, or silicon is molten
Glue is mixed with support modification agent powder, can obtain expected effect of the present invention.When using Ludox and support modification agent powder
Mode mix when, the particle diameter of the support modification agent powder such as, but not limited to added is 10~200nm, preferably 10~100nm,
In order to which each embodiment and comparative example are reached in year-on-year purpose, the specific embodiment of the invention, the particle diameter of support modification agent is
20nm。
In above-mentioned technical proposal, the pH of step (d) is preferably 1~5.
In above-mentioned technical proposal, the temperature of step (d) is preferably 50~80 DEG C.
In above-mentioned technical proposal, calcination activation temperature is preferably 550~640 DEG C.
In above-mentioned technical proposal, the calcination activation time is preferably 0.5~2h.
To solve the three of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Ammoxidation of propylene produces the side of acrylonitrile
Method, in the presence of catalyst any one of technical problem one, using propylene, ammonia and air as raw material, reaction obtains propylene
Nitrile.
In above-mentioned technical proposal, under thinking of the present invention enlightenment, those skilled in the art can rationally determine the technique bar of reaction
Part is without paying creative work.
Such as, but not limited to described reaction process is：
1st, material molar ratio propylene/ammonia/air=1：1.05~1.3：9.2~9.8.
2nd, 420~440 DEG C of reaction temperature.
3rd, reaction pressure is 0.06~0.14MPa.
4th, propylene load WWH=0.06~0.10h of catalyst-1。
The key problem in technology of the present invention is include support modification agent by carrier, improve catalyst to the selectivity of acrylonitrile with
Stability.The activity examination of catalyst of the present invention is carried out in internal diameter is 38 millimeters of fluidized-bed reactor.Catalyst is filled
400 grams of the amount of filling out, is 430 DEG C, air in reaction temperature:Propylene molar ratio is 9.7:1, reaction pressure is 0.085Mpa, reaction
Load is 0.06 hour-1Under conditions of operate 1000h, acrylonitrile once through yield reaches 83% or so, obtains preferable effect.
Propylene conversion, acrylonitrile selectivity and once through yield are defined as follows in the present invention：
Below by embodiment, the present invention is further elaborated：
Embodiment
Comparative example 1
By 111.1 grams of Bi (NO3)3·5H2O, 124.8 grams of Mn (NO3)2, 517.6 grams of Ni (NO3)2·6H2O, 287.6 grams
Fe(NO3)3·9H2O, 135.5 grams of Mg (NO3)2·6H2O, 3.6 grams of KOH, 60.7 grams of Pr (NO3)3·6H2O and 21.4 gram
Cr(NO3)3·9H2After O is dissolved by heating, solution I is obtained.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water,
And the Ludox that 2500 gram weight concentration are 40% is added, mixed liquor I I is obtained, solution I and mixed liquor I I are mixed,
It is 5 in pH, temperature obtains slurry I to be stirred under the conditions of 80 DEG C.The slurry being made is carried out in spray dryer
Framboid is molded, and is finally calcined 2.0 hours in 590 DEG C in rotary roasting furnace, catalyst needed for being made.
Comparative example 2
By 111.1 grams of Bi (NO3)3·5H2O, 124.8 grams of Mn (NO3)2, 517.6 grams of Ni (NO3)2·6H2O, 287.6 grams
Fe(NO3)3·9H2O, 135.5 grams of Mg (NO3)2·6H2O, 3.6 grams of KOH, 60.7 grams of Pr (NO3)3·6H2O and 21.4 gram
Cr(NO3)3·9H2After O is dissolved by heating, solution I is obtained.By the Ludox that 2475 grams of concentration are 40%, water and 10g aluminum oxide
It is aluminum oxide containing 1wt% in 40%, carrier to be mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I.By 846.0
Gram (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, forms mixed liquor I II, by solution I and mixed
Close liquid III to be mixed, be 5 in PH, temperature obtains slurry I to be stirred under the conditions of 80 DEG C.The slurry being made is existed
Framboid shaping is carried out in spray dryer, is finally calcined 2.0 hours in 590 DEG C in rotary roasting furnace, is catalyzed needed for being made
Agent.
Comparative example 3
By 111.1 grams of Bi (NO3)3·5H2O, 124.8 grams of Mn (NO3)2, 517.6 grams of Ni (0)2·6H2O, 287.6 grams
Fe(NO3)3·9H2O, 135.5 grams of Mg (NO3)2·6H2O, 3.6 grams of KOH, 60.7 grams of Pr (NO3)3·6H2O and 21.4 gram
Cr(NO3)3·9H2After O is dissolved by heating, solution I is obtained.By the Ludox that 2425 grams of concentration are 40%, water and 30g aluminum oxide
It is aluminum oxide containing 3wt% in 40%, carrier to be mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I.By 846.0
Gram (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, forms mixed liquor I II, by solution I and mixed
Close liquid III to be mixed, be 5 in PH, temperature obtains slurry I to be stirred under the conditions of 80 DEG C.The slurry being made is existed
Framboid shaping is carried out in spray dryer, is finally calcined 2.0 hours in 590 DEG C in rotary roasting furnace, is catalyzed needed for being made
Agent.
Comparative example 4
By 111.1 grams of Bi (NO3)3·5H2O, 124.8 grams of Mn (NO3)2, 517.6 grams of Ni (NO3)2·6H2O, 287.6 grams
Fe(NO3)3·9H2O, 135.5 grams of Mg (NO3)2·6H2O, 3.6 grams of KOH, 60.7 grams of Pr (NO3)3·6H2O and 21.4 gram
Cr(NO3)3·9H2After O is dissolved by heating, solution I is obtained.By the Ludox that 2400 grams of concentration are 40%, water and 40g aluminum oxide
It is aluminum oxide containing 4wt% in 40%, carrier to be mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I.By 846.0
Gram (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, forms mixed liquor I II, by solution I and mixed
Close liquid III to be mixed, be 5 in PH, temperature obtains slurry I to be stirred under the conditions of 80 DEG C.The slurry being made is existed
Framboid shaping is carried out in spray dryer, is finally calcined 2.0 hours in 590 DEG C in rotary roasting furnace, is catalyzed needed for being made
Agent.
Comparative example 5
By 111.1 grams of Bi (NO3)3·5H2O, 124.8 grams of Mn (NO3)2, 517.6 grams of Ni (NO3)2·6H2O, 287.6 grams
Fe(NO3)3·9H2O, 135.5 grams of Mg (NO3)2·6H2O, 3.6 grams of KOH, 60.7 grams of Pr (NO3)3·6H2O and 21.4 gram
Cr(NO3)3·9H2After O is dissolved by heating, solution I is obtained.By the Ludox that 2475 grams of concentration are 40%, water and 10g diatomite
It is diatomite containing 1wt% in 40%, carrier to be mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I.By 846.0
Gram (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, forms mixed liquor I II, by solution I and mixed
Close liquid III to be mixed, be 5 in PH, temperature obtains slurry I to be stirred under the conditions of 80 DEG C.The slurry being made is existed
Framboid shaping is carried out in spray dryer, is finally calcined 2.0 hours in 590 DEG C in rotary roasting furnace, is catalyzed needed for being made
Agent.
Comparative example 6
By 111.1 grams of Bi (NO3)3·5H2O, 124.8 grams of Mn (NO3)2, 517.6 grams of Ni (NO3)2·6H2O, 287.6 grams
Fe(NO3)3·9H2O, 135.5 grams of Mg (NO3)2·6H2O, 3.6 grams of KOH, 60.7 grams of Pr (NO3)3·6H2O and 21.4 gram
Cr(NO3)3·9H2After O is dissolved by heating, solution I is obtained.By the Ludox that 2425 grams of concentration are 40%, water and 30g diatomite
It is diatomite containing 3wt% in 40%, carrier to be mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I.By 846.0
Gram (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, forms mixed liquor I II, by solution I and mixed
Close liquid III to be mixed, be 5 in PH, temperature obtains slurry I to be stirred under the conditions of 80 DEG C.The slurry being made is existed
Framboid shaping is carried out in spray dryer, is finally calcined 2.0 hours in 590 DEG C in rotary roasting furnace, is catalyzed needed for being made
Agent.
Comparative example 7
By 111.1 grams of Bi (NO3)3·5H2O, 124.8 grams of Mn (NO3)2, 517.6 grams of Ni (NO3)2·6H2O, 287.6 grams
Fe(NO3)3·9H2O, 135.5 grams of Mg (NO3)2·6H2O, 3.6 grams of KOH, 60.7 grams of Pr (NO3)3·6H2O and 21.4 gram
Cr(NO3)3·9H2After O is dissolved by heating, solution I is obtained.By the Ludox that 2400 grams of concentration are 40%, water and 40g diatomite
It is diatomite containing 4wt% in 40%, carrier to be mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I.By 846.0
Gram (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, forms mixed liquor I II, by solution I and mixed
Close liquid III to be mixed, be 5 in PH, temperature obtains slurry I to be stirred under the conditions of 80 DEG C.The slurry being made is existed
Framboid shaping is carried out in spray dryer, is finally calcined 2.0 hours in 590 DEG C in rotary roasting furnace, is catalyzed needed for being made
Agent.
Embodiment 1
By 111.1 grams of Bi (NO3)3·5H2O, 124.8 grams of Mn (NO3)2, 517.6 grams of Ni (NO3)2·6H2O, 287.6 grams
Fe(NO3)3·9H2O, 135.5 grams of Mg (NO3)2·6H2O, 3.6 grams of KOH, 60.7 grams of Pr (NO3)3·6H2O and 21.4 gram
Cr(NO3)3·9H2After O is dissolved by heating, solution I is obtained.By the Ludox that 2425 grams of concentration are 40%, water and 10g aluminum oxide
It is oxygen containing 1wt% in 40%, carrier to be mixed to form in mixed liquor I I, wherein mixed liquor I I vehicle weight concentration with 20g diatomite
Change aluminium and 2wt% diatomite.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I,
Form mixed liquor I II, solution I and mixed liquor I II mixed, be 5 in PH, temperature to be stirred under the conditions of 80 DEG C,
Obtain slurry I.The slurry being made is subjected to framboid shaping in spray dryer, finally in 590 DEG C in rotary roasting furnace
Roasting 2.0 hours, catalyst needed for being made.
Embodiment 2
By 111.1 grams of Bi (NO3)3·5H2O, 124.8 grams of Mn (NO3)2, 517.6 grams of Ni (NO3)2·6H2O, 287.6 grams
Fe(NO3)3·9H2O, 135.5 grams of Mg (NO3)2·6H2O, 3.6 grams of KOH, 60.7 grams of Pr (NO3)3·6H2O and 21.4 gram
Cr(NO3)3·9H2After O is dissolved by heating, solution I is obtained.By the Ludox that 2425 grams of concentration are 40%, water and 15g aluminum oxide
It is to contain 1.5wt% in 40%, carrier to be mixed to form in mixed liquor I I, wherein mixed liquor I I vehicle weight concentration with 15g diatomite
Aluminum oxide and 1.5wt% diatomite.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor
II, forms mixed liquor I II, solution I and mixed liquor I II is mixed, and is 5 in PH, and temperature is progress under the conditions of 80 DEG C
Stirring, obtains slurry I.The slurry being made is subjected to framboid shaping in spray dryer, finally in rotary roasting furnace in
590 DEG C are calcined 2.0 hours, catalyst needed for being made.
Embodiment 3
By 111.1 grams of Bi (NO3)3·5H2O, 124.8 grams of Mn (NO3)2, 517.6 grams of Ni (NO3)2·6H2O, 287.6 grams
Fe(NO3)3·9H2O, 135.5 grams of Mg (NO3)2·6H2O, 3.6 grams of KOH, 60.7 grams of Pr (NO3)3·6H2O and 21.4 gram
Cr(NO3)3·9H2After O is dissolved by heating, solution I is obtained.By the Ludox that 2425 grams of concentration are 40%, water and 7.5g oxidations
It is to contain 0.75wt% in 40%, carrier that aluminium and 22.5g diatomite, which are mixed to form in mixed liquor I I, wherein mixed liquor I I vehicle weight concentration,
Aluminum oxide and 22.5wt% diatomite.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixing
Liquid II, forms mixed liquor I II, solution I and mixed liquor I II is mixed, and is 5 in PH, and temperature is enters under the conditions of 80 DEG C
Row stirring, obtains slurry I.The slurry being made is subjected to framboid shaping in spray dryer, finally in rotary roasting furnace
It is calcined 2.0 hours in 590 DEG C, catalyst needed for being made.
Embodiment 4
By 111.1 grams of Bi (NO3)3·5H2O, 124.8 grams of Mn (NO3)2, 517.6 grams of Ni (NO3)2·6H2O, 287.6 grams
Fe(NO3)3·9H2O, 135.5 grams of Mg (NO3)2·6H2O, 3.6 grams of KOH, 60.7 grams of Pr (NO3)3·6H2O and 21.4 gram
Cr(NO3)3·9H2After O is dissolved by heating, solution I is obtained.By the Ludox that 2425 grams of concentration are 40%, water and 6g aluminum oxide
It is to contain 0.6wt% in 40%, carrier to be mixed to form in mixed liquor I I, wherein mixed liquor I I vehicle weight concentration with 24g diatomite
Aluminum oxide and 2.4wt% diatomite.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor
II, forms mixed liquor I II, solution I and mixed liquor I II is mixed, and is 5 in PH, and temperature is progress under the conditions of 80 DEG C
Stirring, obtains slurry I.The slurry being made is subjected to framboid shaping in spray dryer, finally in rotary roasting furnace in
590 DEG C are calcined 2.0 hours, catalyst needed for being made.
Embodiment 5
By 111.1 grams of Bi (NO3)3·5H2O, 124.8 grams of Mn (NO3)2, 517.6 grams of Ni (NO3)2·6H2O, 287.6 grams
Fe(NO3)3·9H2O, 135.5 grams of Mg (NO3)2·6H2O, 3.6 grams of KOH, 60.7 grams of Pr (NO3)3·6H2O and 21.4 gram
Cr(NO3)3·9H2After O is dissolved by heating, solution I is obtained.By the Ludox that 2425 grams of concentration are 40%, water and 5g aluminum oxide
It is to contain 0.5wt% in 40%, carrier to be mixed to form in mixed liquor I I, wherein mixed liquor I I vehicle weight concentration with 25g diatomite
Aluminum oxide and 2.5wt% diatomite.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor
II, forms mixed liquor I II, solution I and mixed liquor I II is mixed, and is 5 in PH, and temperature is progress under the conditions of 80 DEG C
Stirring, obtains slurry I.The slurry being made is subjected to framboid shaping in spray dryer, finally in rotary roasting furnace in
590 DEG C are calcined 2.0 hours, catalyst needed for being made.
Embodiment 6
By 111.1 grams of Bi (NO3)3·5H2O, 124.8 grams of Mn (NO3)2, 517.6 grams of Ni (NO3)2·6H2O, 287.6 grams
Fe(NO3)3·9H2O, 135.5 grams of Mg (NO3)2·6H2O, 3.6 grams of KOH, 60.7 grams of Pr (NO3)3·6H2O and 21.4 gram
Cr(NO3)3·9H2After O is dissolved by heating, solution I is obtained.By the Ludox that 2475 grams of concentration are 40%, water and 3.3g oxidations
It is to contain 0.33wt% in 40%, carrier that aluminium and 6.7g diatomite, which are mixed to form in mixed liquor I I, wherein mixed liquor I I vehicle weight concentration,
Aluminum oxide and 0.67wt% diatomite.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixing
Liquid II, forms mixed liquor I II, solution I and mixed liquor I II is mixed, and is 5 in PH, and temperature is enters under the conditions of 80 DEG C
Row stirring, obtains slurry I.The slurry being made is subjected to framboid shaping in spray dryer, finally in rotary roasting furnace
It is calcined 2.0 hours in 590 DEG C, catalyst needed for being made.
Embodiment 7
By 111.1 grams of Bi (NO3)3·5H2O, 124.8 grams of Mn (NO3)2, 517.6 grams of Ni (NO3)2·6H2O, 287.6 grams
Fe(NO3)3·9H2O, 135.5 grams of Mg (NO3)2·6H2O, 3.6 grams of KOH, 60.7 grams of Pr (NO3)3·6H2O and 21.4 gram
Cr(NO3)3·9H2After O is dissolved by heating, solution I is obtained.By the Ludox that 2450 grams of concentration are 40%, water and 6.7g oxidations
It is to contain 0.67wt% in 40%, carrier that aluminium and 13.3g diatomite, which are mixed to form in mixed liquor I I, wherein mixed liquor I I vehicle weight concentration,
Aluminum oxide and 1.33wt% diatomite.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixing
Liquid II, forms mixed liquor I II, solution I and mixed liquor I II is mixed, and is 5 in PH, and temperature is enters under the conditions of 80 DEG C
Row stirring, obtains slurry I.The slurry being made is subjected to framboid shaping in spray dryer, finally in rotary roasting furnace
It is calcined 2.0 hours in 590 DEG C, catalyst needed for being made.
Embodiment 8
By 111.1 grams of Bi (NO3)3·5H2O, 124.8 grams of Mn (NO3)2, 517.6 grams of Ni (NO3)2·6H2O, 287.6 grams
Fe(NO3)3·9H2O, 135.5 grams of Mg (NO3)2·6H2O, 3.6 grams of KOH, 60.7 grams of Pr (NO3)3·6H2O and 21.4 gram
Cr(NO3)3·9H2After O is dissolved by heating, solution I is obtained.By the Ludox that 2400 grams of concentration are 40%, water and 13.3g oxidations
It is to contain 1.33wt% in 40%, carrier that aluminium and 26.7g diatomite, which are mixed to form in mixed liquor I I, wherein mixed liquor I I vehicle weight concentration,
Aluminum oxide and 2.67wt% diatomite.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixing
Liquid II, forms mixed liquor I II, solution I and mixed liquor I II is mixed, and is 5 in PH, and temperature is enters under the conditions of 80 DEG C
Row stirring, obtains slurry I.The slurry being made is subjected to framboid shaping in spray dryer, finally in rotary roasting furnace
It is calcined 2.0 hours in 590 DEG C, catalyst needed for being made.
Obtained catalyst carries out ammoxidation of propylene life under following reaction conditions in embodiment 1~8 and comparative example 1~7
Into the reaction of acrylonitrile, 1 the results are shown in Table.
The reaction condition of above-described embodiment and comparative example is：
38 millimeters of fluidized-bed reactors of φ
430-440 DEG C of reaction temperature
Reaction pressure 0.085MPa
400 grams of loaded catalyst
Catalyst propylene load (WWH) 0.06 hour-1
Raw material proportioning (mole) C3 =/NH3/ air=1/1.25/9.7
The catalyst of table 1 is constituted and evaluation result
Claims (9)
1. the catalyst of ammoxidation of propylene acrylonitrile production, including carrier and the active component that is represented containing below general formula：
AaBbCcBidMo13.6Ox
A is selected from least one of K, Rb and Cs in formula；B is selected from Ca, Mn, Fe, Co, Ni, Mg, Cr, W, P
At least one of with Nb；C is selected from least one of rare earth element；A span is 0.01~2.5；B value model
Enclose for 1~15；C span is 0.01~5；D span is 0.01~3；X is to meet each element in catalyst
Oxygen atom sum needed for conjunction valency；
Described carrier include silica and support modification agent, the support modification agent in aluminum oxide and diatomite at least one
Kind.
2. catalyst according to claim 1, it is characterised in that the consumption of carrier is 30~70wt% of catalyst weight.
3. catalyst according to claim 1, it is characterised in that support modification agent content is 0.1~5wt% in carrier.
4. the preparation method of the catalyst described in claim 1, comprises the following steps：
(a) at least one salt of the desired amount of corresponding active component element in addition to Mo is dissolved, obtains solution I；
(b) the desired amount of Ludox is mixed with support modification agent, obtains mixed liquor I I；
(c) molybdate of the aequum containing molybdenum is dissolved, and mixed with mixed liquor I I, obtain mixed liquor I II；
(d) solution I and mixed liquor I II are mixed, is that 1~7 and temperature are stirred at 20~90 DEG C in pH, obtains slurry I；
(e) slurry I is spray-dried and calcination activation obtains required catalyst for 0.2~4 hour at 520~660 DEG C.
5. the preparation method of catalyst according to claim 4, it is characterised in that the pH described in step (d) is 1~5.
6. the preparation method of catalyst according to claim 4, it is characterised in that the temperature described in step (d) is preferably 50~
80℃。
7. the preparation method of catalyst according to claim 4, it is characterised in that calcination activation temperature is 550~640 DEG C.
8. the preparation method of the catalyst according to right, it is characterised in that the calcination activation time is 0.5~2h.
9. the method that ammoxidation of propylene produces acrylonitrile, in the presence of catalyst described in claims 1 to 3, with propylene, ammonia and sky
Gas is raw material, and reaction obtains acrylonitrile.Preferred feedstock mol ratio propylene/ammonia/air=1：1.05~1.3：9.2~9.8.It is preferred that anti-
Answer 420~440 DEG C of temperature.It is preferred that reaction pressure is 0.06~0.14MPa.Propylene load WWH=0.06~0.10 of preferred catalyst
h-1。
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| CN109876794A (en) * | 2018-12-17 | 2019-06-14 | 中南民族大学 | Ammoxidation reaction prepares the special-purpose catalyst and preparation method and purposes of m-dicyanobenzene |
| CN112705232A (en) * | 2019-10-24 | 2021-04-27 | 南通泰禾化工股份有限公司 | Catalyst for preparing salicylonitrile and preparation method and application thereof |
| CN113828337A (en) * | 2020-06-24 | 2021-12-24 | 中国石油化工股份有限公司 | Catalyst for preparing acrylonitrile by propylene ammoxidation, preparation method and application thereof |
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| CN113828337A (en) * | 2020-06-24 | 2021-12-24 | 中国石油化工股份有限公司 | Catalyst for preparing acrylonitrile by propylene ammoxidation, preparation method and application thereof |
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