CN107282064A - Catalyst for producing acrylonitrile - Google Patents
Catalyst for producing acrylonitrile Download PDFInfo
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- CN107282064A CN107282064A CN201610227771.3A CN201610227771A CN107282064A CN 107282064 A CN107282064 A CN 107282064A CN 201610227771 A CN201610227771 A CN 201610227771A CN 107282064 A CN107282064 A CN 107282064A
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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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- 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
- B01J23/70—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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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to the catalyst for producing acrylonitrile, preparation technology, 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 being used to producing the catalyst of acrylonitrile, including carrier and the active component that is represented containing below general formula：AaBbCcNidFeeBifMo13.6OxA is selected from least one of K, Rb and Cs in formula；B is selected from least one of Ca, Mn, Co, 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 zirconium oxide, 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 the catalyst for producing acrylonitrile.
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：
Catalyst for producing acrylonitrile, including carrier and the active component that is represented containing below general formula：
AaBbCcNidFeeBifMo13.6Ox
A is selected from least one of K, Rb and Cs in formula；B is selected from Ca, Mn, Co, Mg, Cr, W, P and Nb
At least one of；C is selected from least one of rare earth element；A span is 0.01~2.5；B span be 1~
15；C span is 0.01~5；D span is 1~20；E span is 1~15；F span is
0.01~3；X is the oxygen atom sum needed for meeting each element chemical valence in catalyst；
Described carrier include silica and support modification agent, the support modification agent in aluminum oxide and zirconium oxide at least
It is a kind of.
In above-mentioned technical proposal, the support modification agent is simultaneously including zirconium oxide and aluminum oxide, and now both are in raising selectivity
Acted synergistically with having in terms of stability.Both aluminum oxide and zirconium oxide 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：Urged 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 in 160 grams of water, solution I is obtained.By 846.0 grams of (NH4)6Mo7O24·4H2O exists
Dissolved in 890 grams of water, and add the Ludox that 2500 gram weight concentration are 40%, obtain mixed liquor I I, by solution I and mixed
Close liquid II 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 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 in 160 grams of water, solution I is obtained.By the Ludox that 2487 grams of concentration are 40%, 8
It is to contain 0.5wt% in 40%, carrier that gram water and 5 grams of aluminum oxide, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
Aluminum oxide.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, forms mixed liquor
III, solution I and mixed liquor I II are mixed, and are 5 in PH, temperature obtains slurry I to be stirred under the conditions of 80 DEG C.
The slurry being made is subjected to framboid shaping in spray dryer, is finally calcined 2.0 hours in 590 DEG C in rotary roasting furnace,
Catalyst needed for being made.
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 in 160 grams of water, solution I is obtained.By the Ludox that 2425 grams of concentration are 40%, 45
It is to contain in 40%, carrier that gram water and 30 grams of aluminum oxide, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
3wt% aluminum oxide.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, forms mixed
Liquid III is closed, solution I and mixed liquor I II are mixed, is 5 in PH, temperature obtains to be stirred under the conditions of 80 DEG C
Slurry I.The slurry being made is subjected to framboid shaping in spray dryer, finally in 590 DEG C of roastings in rotary roasting furnace
2.0 hours, catalyst needed for being made.
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 in 160 grams of water, solution I is obtained.By the Ludox that 2400 grams of concentration are 40%, 60
It is to contain in 40%, carrier that gram water and 40 grams of aluminum oxide, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
4wt% aluminum oxide.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, forms mixed
Liquid III is closed, solution I and mixed liquor I II are mixed, is 5 in PH, temperature obtains to be stirred under the conditions of 80 DEG C
Slurry I.The slurry being made is subjected to framboid shaping in spray dryer, finally in 590 DEG C of roastings in rotary roasting furnace
2.0 hours, catalyst needed for being made.
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 in 160 grams of water, solution I is obtained.By the Ludox that 2487 grams of concentration are 40%, 8
It is to contain 0.5wt% in 40%, carrier that gram water and 5 grams of zirconium oxides, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
Zirconium oxide.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, forms mixed liquor
III, solution I and mixed liquor I II are mixed, and are 5 in PH, temperature obtains slurry I to be stirred under the conditions of 80 DEG C.
The slurry being made is subjected to framboid shaping in spray dryer, is finally calcined 2.0 hours in 590 DEG C in rotary roasting furnace,
Catalyst needed for being made.
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 in 160 grams of water, solution I is obtained.By the Ludox that 2425 grams of concentration are 40%, 45
It is to contain in 40%, carrier that gram water and 30 grams of zirconium oxides, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
3wt% zirconium oxides.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, forms mixed
Liquid III is closed, solution I and mixed liquor I II are mixed, is 5 in PH, temperature obtains to be stirred under the conditions of 80 DEG C
Slurry I.The slurry being made is subjected to framboid shaping in spray dryer, finally in 590 DEG C of roastings in rotary roasting furnace
2.0 hours, catalyst needed for being made.
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 in 160 grams of water, solution I is obtained.By the Ludox that 2400 grams of concentration are 40%, 60
It is to contain in 40%, carrier that gram water and 40 grams of zirconium oxides, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
4wt% zirconium oxides.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, forms mixed
Liquid III is closed, solution I and mixed liquor I II are mixed, is 5 in PH, temperature obtains to be stirred under the conditions of 80 DEG C
Slurry I.The slurry being made is subjected to framboid shaping in spray dryer, finally in 590 DEG C of roastings in rotary roasting furnace
2.0 hours, catalyst needed for being made.
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 in 160 grams of water, solution I is obtained.By the Ludox that 2425 grams of concentration are 40%, 45
It is 40% that gram water and 10 grams of aluminum oxide and 20 grams of zirconium oxides, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
Aluminum oxide containing 1wt% and 2wt% zirconium oxides in carrier.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water,
And mixed liquor I I is added, mixed liquor I II is formed, solution I and mixed liquor I II are mixed, is 5 in PH, temperature is 80 DEG C
Under the conditions of be stirred, obtain slurry I.The slurry being made is subjected to framboid shaping in spray dryer, finally in rotation
It is calcined 2.0 hours in 590 DEG C in roaster, 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 in 160 grams of water, solution I is obtained.By the Ludox that 2425 grams of concentration are 40%, 45
It is 40% that gram water and 15 grams of aluminum oxide and 15 grams of zirconium oxides, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
Aluminum oxide containing 1.5wt% and 1.5wt% zirconium oxides in carrier.By 846.0 grams of (NH4)6Mo7O24·4H2O is molten in 890 grams of water
Solution, and mixed liquor I I is added, mixed liquor I II is formed, solution I and mixed liquor I II are mixed, is 5, temperature in PH
To be stirred under the conditions of 80 DEG C, slurry I is obtained.The slurry being made is subjected to framboid shaping in spray dryer, finally
It is calcined 2.0 hours in 590 DEG C in rotary roasting furnace, 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 in 160 grams of water, solution I is obtained.By the Ludox that 2425 grams of concentration are 40%, 45
Gram water and 7.5 grams of aluminum oxide and 22.5 grams of zirconium oxides are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I and are
40%, aluminum oxide containing 0.75wt% and 22.5wt% zirconium oxides in carrier.By 846.0 grams of (NH4)6Mo7O24·4H2O is 890
Dissolved in gram water, and add mixed liquor I I, formed mixed liquor I II, solution I and mixed liquor I II are mixed, are in PH
5, 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 into
Type, is finally calcined 2.0 hours in rotary roasting furnace 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 in 160 grams of water, solution I is obtained.By the Ludox that 2425 grams of concentration are 40%, 45
It is 40% that gram water and 6 grams of aluminum oxide and 24 grams of zirconium oxides, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
Aluminum oxide containing 0.6wt% and 2.4wt% zirconium oxides in carrier.By 846.0 grams of (NH4)6Mo7O24·4H2O is molten in 890 grams of water
Solution, and mixed liquor I I is added, mixed liquor I II is formed, solution I and mixed liquor I II are mixed, is 5, temperature in PH
To be stirred under the conditions of 80 DEG C, slurry I is obtained.The slurry being made is subjected to framboid shaping in spray dryer, finally
It is calcined 2.0 hours in 590 DEG C in rotary roasting furnace, 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 in 160 grams of water, solution I is obtained.By the Ludox that 2425 grams of concentration are 40%, 45
It is 40% that gram water and 5 grams of aluminum oxide and 25 grams of zirconium oxides, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
Aluminum oxide containing 0.5wt% and 2.5wt% zirconium oxides in carrier.By 846.0 grams of (NH4)6Mo7O24·4H2O is molten in 890 grams of water
Solution, and mixed liquor I I is added, mixed liquor I II is formed, solution I and mixed liquor I II are mixed, is 5, temperature in PH
To be stirred under the conditions of 80 DEG C, slurry I is obtained.The slurry being made is subjected to framboid shaping in spray dryer, finally
It is calcined 2.0 hours in 590 DEG C in rotary roasting furnace, 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 in 160 grams of water, solution I is obtained.By the Ludox that 2487 grams of concentration are 40%, 8
It is 40% that gram water and 1.7 grams of aluminum oxide and 3.3 grams of zirconium oxides, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
Aluminum oxide containing 0.17wt% and 0.33wt% zirconium oxides in carrier.By 846.0 grams of (NH4)6Mo7O24·4H2O is in 890 grams of water
Dissolving, and mixed liquor I I is added, mixed liquor I II is formed, solution I and mixed liquor I II are mixed, is 5 in PH, temperature
Spend 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, most
It is calcined 2.0 hours in 590 DEG C in rotary roasting furnace afterwards, 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 in 160 grams of water, solution I is obtained.By the Ludox that 2450 grams of concentration are 40%, 30
Gram water and 6.7 grams of aluminum oxide and 13.3 grams of zirconium oxides are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I and are
40%, aluminum oxide containing 0.67wt% and 1.33wt% zirconium oxides in carrier.By 846.0 grams of (NH4)6Mo7O24·4H2O is 890
Dissolved in gram water, and add mixed liquor I I, formed mixed liquor I II, solution I and mixed liquor I II are mixed, are in PH
5, 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 into
Type, is finally calcined 2.0 hours in rotary roasting furnace 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 in 160 grams of water, solution I is obtained.By the Ludox that 2400 grams of concentration are 40%, 60
Gram water and 13.3 grams of aluminum oxide and 26.7 grams of zirconium oxides are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I and are
40%, aluminum oxide containing 1.33wt% and 2.67wt% zirconium oxides in carrier.By 846.0 grams of (NH4)6Mo7O24·4H2O is 890
Dissolved in gram water, and add mixed liquor I I, formed mixed liquor I II, solution I and mixed liquor I II are mixed, are in PH
5, 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 into
Type, is finally calcined 2.0 hours in rotary roasting furnace 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
435 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. for producing the catalyst of acrylonitrile, including carrier and the active component that is represented containing below general formula：
AaBbCcNidFeeBifMo13.6Ox
A is selected from least one of K, Rb and Cs in formula；B is in Ca, Mn, Co, Mg, Cr, W, P and Nb
At least one；C is selected from least one of rare earth element；A span is 0.01~2.5；B span be 1~
15；C span is 0.01~5；D span is 1~20；E span is 1~15；F span is
0.01~3；X is the oxygen atom sum needed for meeting each element chemical valence in catalyst；
Described carrier include silica and support modification agent, the support modification agent in aluminum oxide and zirconium oxide 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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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1736592A (en) * | 2005-06-03 | 2006-02-22 | 营口市向阳催化剂有限责任公司 | Fluidized-bed catalyst for ammoxidation of propylene or isobutylene |
| CN101878194A (en) * | 2007-10-11 | 2010-11-03 | 伊内奥斯美国公司 | Process for the ammoxidation or oxidation of propane and isobutane |
| CN102188981A (en) * | 2010-03-03 | 2011-09-21 | 中国石油化工股份有限公司 | Preparation method of acrylonitrile fluidized bed catalyst |
| US20130072710A1 (en) * | 2011-09-21 | 2013-03-21 | James F. Brazdil | Mixed metal oxide catalysts |
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2016
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1736592A (en) * | 2005-06-03 | 2006-02-22 | 营口市向阳催化剂有限责任公司 | Fluidized-bed catalyst for ammoxidation of propylene or isobutylene |
| CN101878194A (en) * | 2007-10-11 | 2010-11-03 | 伊内奥斯美国公司 | Process for the ammoxidation or oxidation of propane and isobutane |
| CN102188981A (en) * | 2010-03-03 | 2011-09-21 | 中国石油化工股份有限公司 | Preparation method of acrylonitrile fluidized bed catalyst |
| US20130072710A1 (en) * | 2011-09-21 | 2013-03-21 | James F. Brazdil | Mixed metal oxide catalysts |
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