CN107282065A - Acrylonitrile catalyst and preparation method thereof - Google Patents
Acrylonitrile catalyst and preparation method thereof Download PDFInfo
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- CN107282065A CN107282065A CN201610227772.8A CN201610227772A CN107282065A CN 107282065 A CN107282065 A CN 107282065A CN 201610227772 A CN201610227772 A CN 201610227772A CN 107282065 A CN107282065 A CN 107282065A
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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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- 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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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Abstract
The present invention relates to acrylonitrile catalyst 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 uses acrylonitrile catalyst, including carrier and the active component that is represented containing below general formula：AaBbCcFedBieMo13.6OxA is selected from least one of K, Rb and Cs in formula；B is selected from least one of Ca, Mn, 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 titanium 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 acrylonitrile catalyst and preparation method thereof.
Background technology
The industrial production that current olefin ammoxidation prepares unsaturated nitrile still generally uses fluid bed ammonia oxidation process, catalyst
One of core technology as the technique, it is studied, improves and paid attention to always.Current industrial ammoxidation of propylene acrylonitrile production
Catalyst mainly has two classes：Mo-Bi systems and Sb systems, wherein Mo-Bi series catalysts are occupied an leading position, and reach olefin oxidation market
95%, forefathers' research and exploration are also concentrated mainly on Mo-Bi series catalysts.By introducing in the catalyst with variable valence
The element such as metal component such as Fe, Ce improve the oxidationreduction performance of catalyst, accelerate to recover the effective of catalyst activity component
State；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, catalyst is carried 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 are fitted
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, molten in carrier starting material silicon
The grain diameter that 2~25% are added in glue 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 at this
In the oxidation catalyst preparation method of sample, using Ludox as the source of silica, but the influence factor of Ludox
Do not referred in patent documents above.
Patent CN1129408A proposes that the aluminium content of Ludox added in catalyst preparation process is provided, can be with
The selectivity of acrylonitrile is significantly improved, but the content to other components does not have clear stipulaties.
Patent CN1744949A propose by change the initial particle of silica material the cell size of catalyst is distributed into
Row control.
Catalyst in for unsaturated olefin ammoxidation, generally including being selected from containing molybdenum, bismuth, iron and at least one
The oxide catalyst of the oxide composition of the elements such as potassium, rubidium and caesium, and oxide catalyst is loaded in titanium dioxide thereon
Silicon carrier.The present invention has found selectivity that the additive in carrier react ammoxidation of propylene and surely by further studying
It is qualitative to have a significant effect.
The content of the invention
One of technical problems to be solved by the invention are the catalyst choosings of ammoxidation of propylene acrylonitrile production in the prior art
The problem of selecting property is low, stability is poor has selectivity there is provided a kind of catalyst of ammoxidation of propylene acrylonitrile production, the catalyst
It is high, the characteristics of stability is good.
The two of the technical problems to be solved by the invention are to provide a kind of system of one of above-mentioned technical problem catalyst
Preparation Method.
The three of the technical problems to be solved by the invention are the propylene ammonia using one of the above-mentioned technical problem catalyst
The synthetic method of oxidation production acrylonitrile.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：
Acrylonitrile catalyst, including carrier and the active component that is represented containing below general formula：AaBbCcFedBieMo13.6Ox；
A is selected from least one of K, Rb and Cs in formula；B is selected from least one of Ca, Mn, Co, Ni, Mg, Cr, W, P and Nb；C is selected
From at least one of rare earth element.A span is 0.01~2.5；B span is 1~15；C span
For 0.01~5；D span is 1~15；E span is 0.01~3；X is to meet each element chemical valence in catalyst
Required oxygen atom sum.
Described carrier includes silica and support modification agent, and the support modification agent is in titanium oxide and diatomite
At least one.
In above-mentioned technical proposal, the support modification agent is simultaneously including diatomite and titanium oxide, and now both are in raising choosing
There is synergy in terms of selecting property and stability.Both titanium oxide and diatomite weight ratio are not particularly limited, for example but not
It is 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：Institute in one of above-mentioned technical problem
The preparation method of catalyst is stated, is comprised 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) is scattered more uniform mixed in order to obtain
Liquid II is closed, support modification agent takes fine particulate form to be mixed with Ludox, but the particle diameter of support modification agent particle is not limited especially
System, can obtain comparable invention effect.Therefore, as taking the form of support modification agent colloidal sol to be mixed with Ludox, also
It is that Ludox is mixed with support modification agent powder, can obtains expected effect of the present invention.Change when using Ludox with carrier
Property 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, support modification agent
Particle diameter 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 acrylonitrile
Method, in the presence of catalyst any one of technical problem one, using propylene, ammonia and air as raw material, reaction obtain third
Alkene nitrile.
In above-mentioned technical proposal, under thinking of the present invention enlightenment, those skilled in the art can rationally determine the work of reaction
Skill condition 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 to include support modification agent by carrier, improves selection of the catalyst to acrylonitrile
Property and stability.The activity examination of catalyst of the present invention is carried out in internal diameter is 38 millimeters of fluidized-bed reactor.Catalysis
400 grams of agent loadings, are 430 DEG C, air in reaction temperature:Propylene molar ratio is 9.7:1, reaction pressure is 0.085Mpa, instead
It is 0.06 hour to answer load-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 of 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 of 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 is in 890 grams of water
Middle dissolving, 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 carried out
Mixing, is 5 in pH, temperature obtains slurry I to be stirred under the conditions of 80 DEG C.The slurry being made is entered in spray dryer
Row 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 of 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 of Cr
(NO3)3·9H2After O is dissolved by heating in 160 grams of water, solution I is obtained.By the Ludox that 2475 grams of concentration are 40%, 15 grams of water
And it is oxygen containing 1wt% in 40%, carrier that 10 grams of titanium oxide, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
Change titanium.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, forms mixed liquor I II, will
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.By what is be made
Slurry carries out framboid shaping in spray dryer, is finally calcined 2.0 hours in 590 DEG C in rotary roasting furnace, and institute is made
Need catalyst.
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 of 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 of 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 grams of water
And it is oxygen containing 3wt% in 40%, carrier that 30 grams of titanium oxide, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
Change titanium.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, forms mixed liquor I II, will
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.By what is be made
Slurry carries out framboid shaping in spray dryer, is finally calcined 2.0 hours in 590 DEG C in rotary roasting furnace, and institute is made
Need catalyst.
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 of 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 of 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 grams of water
And it is oxygen containing 4wt% in 40%, carrier that 40 grams of titanium oxide, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
Change titanium.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, forms mixed liquor I II, will
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.By what is be made
Slurry carries out framboid shaping in spray dryer, is finally calcined 2.0 hours in 590 DEG C in rotary roasting furnace, and institute is made
Need catalyst.
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 of 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 of Cr
(NO3)3·9H2After O is dissolved by heating in 160 grams of water, solution I is obtained.By the Ludox that 2475 grams of concentration are 40%, 15 grams of water
And it is silicon containing 1wt% in 40%, carrier that 10 grams of diatomite, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
Diatomaceous earth.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, forms mixed liquor I II, will
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.By what is be made
Slurry carries out framboid shaping in spray dryer, is finally calcined 2.0 hours in 590 DEG C in rotary roasting furnace, and institute is made
Need catalyst.
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 of 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 of 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 grams of water
And it is silicon containing 3wt% in 40%, carrier that 30 grams of diatomite, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
Diatomaceous earth.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, forms mixed liquor I II, will
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.By what is be made
Slurry carries out framboid shaping in spray dryer, is finally calcined 2.0 hours in 590 DEG C in rotary roasting furnace, and institute is made
Need catalyst.
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 of 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 of 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 grams of water
And it is silicon containing 4wt% in 40%, carrier that 40 grams of diatomite, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
Diatomaceous earth.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, forms mixed liquor I II, will
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.By what is be made
Slurry carries out framboid shaping in spray dryer, is finally calcined 2.0 hours in 590 DEG C in rotary roasting furnace, and institute is made
Need catalyst.
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 of 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 of 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 grams of water
And it is 40% that 10 grams of titanium oxide and 20 grams of diatomite, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I, is carried
Titanium oxide containing 1wt% and 2wt% diatomite in body.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds
Enter mixed liquor I I, form mixed liquor I II, solution I and mixed liquor I II are mixed, be 5 in PH, temperature is under the conditions of 80 DEG C
It is stirred, obtains slurry I.The slurry being made is subjected to framboid shaping in spray dryer, finally in rotary roasting furnace
In in 590 DEG C be calcined 2.0 hours, be made needed for catalyst.
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 of 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 of 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 grams of water
And it is 40% that 15 grams of titanium oxide and 15 grams of diatomite, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I, is carried
Titanium oxide containing 1.5wt% and 1.5wt% diatomite in body.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 of bars
It is stirred under part, obtains slurry I.The slurry being made is subjected to framboid shaping in spray dryer, finally in rotation roasting
It is calcined 2.0 hours in 590 DEG C in burning stove, 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 of 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 of 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 grams of water
And it is 40% that 7.5 grams of titanium oxide and 22.5 grams of diatomite, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
Titanium oxide containing 0.75wt% and 22.5wt% diatomite 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 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 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 of 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 of 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 grams of water
And it is 40%, carrier that 6 grams of titanium oxide and 24 grams of diatomite, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
In titanium oxide containing 0.6wt% and 2.4wt% diatomite.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 is mixed, is 5 in PH, temperature is 80 DEG C of conditions
Under be stirred, obtain slurry I.The slurry being made is subjected to framboid shaping in spray dryer, finally in rotary calcination
It is calcined 2.0 hours in 590 DEG C in stove, 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 of 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 of 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 grams of water
And it is 40%, carrier that 5 grams of titanium oxide and 25 grams of diatomite, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
In titanium oxide containing 0.5wt% and 2.5wt% diatomite.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 is mixed, is 5 in PH, temperature is 80 DEG C of conditions
Under be stirred, obtain slurry I.The slurry being made is subjected to framboid shaping in spray dryer, finally in rotary calcination
It is calcined 2.0 hours in 590 DEG C in stove, 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 of 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 of Cr
(NO3)3·9H2After O is dissolved by heating in 160 grams of water, solution I is obtained.By the Ludox that 2475 grams of concentration are 40%, 15 grams of water
And it is 40% that 3.3 grams of titanium oxide and 6.7 grams of diatomite, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
Titanium oxide containing 0.33wt% and 0.67wt% diatomite 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 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 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 of 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 of 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 grams of water
And it is 40% that 6.7 grams of titanium oxide and 13.3 grams of diatomite, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I,
Titanium oxide containing 0.67wt% and 1.33wt% diatomite 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 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 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 of 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 of 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 grams of water
And 13.3 grams of titanium oxide and 26.7 grams of diatomite are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I and are
40%, titanium oxide containing 1.33wt% and 2.67wt% diatomite in carrier.By 846.0 grams of (NH4)6Mo7O24·4H2O is at 890 grams
Dissolved in water, and add mixed liquor I I, formed mixed liquor I II, solution I and mixed liquor I II are mixed, be 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.
Obtained catalyst carries out propylene ammonia oxygen under following reaction conditions in embodiment 1~8 and comparative example 1~7
Metaplasia the results are shown in Table 1 into the reaction of acrylonitrile.
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. acrylonitrile catalyst, including carrier and the active component that is represented containing below general formula：AaBbCcFedBieMo13.6Ox
A is selected from least one of K, Rb and Cs in formula；B is selected from least one of Ca, Mn, Co, Ni, Mg, Cr, W, P and Nb；
C is selected from least one of rare earth element；A span is 0.01~2.5；B span is 1~15；C value model
Enclose for 0.01~5；D span is 1~15；E span is 0.01~3；X is to meet each element chemical combination in catalyst
Oxygen atom sum needed for valency.
Described carrier include silica and support modification agent, the support modification agent in titanium oxide and diatomite extremely
Few 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 DEG C.
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
420~440 DEG C of reaction temperature.It is preferred that reaction pressure is 0.06~0.14MPa.The propylene load WWH=0.06 of preferred catalyst
~0.10h-1。
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| CN112121811A (en) * | 2019-11-15 | 2020-12-25 | 北京水木滨华科技有限公司 | Catalyst for preparing methacrylonitrile and method for preparing methacrylonitrile |
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| EP2428267A1 (en) * | 2010-09-08 | 2012-03-14 | Leibniz-Institut für Katalyse e.V. an der Universität Rostock | Catalyst, its preparation and use for the preparation of nitriles from alkyl aromatic or heteroaromatic compounds |
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| US4436671A (en) * | 1981-02-12 | 1984-03-13 | Takeda Chemical Industries, Limited | Process for producing unsaturated aliphatic dinitriles |
| CN1346702A (en) * | 2000-09-28 | 2002-05-01 | 罗姆和哈斯公司 | Cocatalytic polymetallic oxide catalyst |
| 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 |
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| CN112121811A (en) * | 2019-11-15 | 2020-12-25 | 北京水木滨华科技有限公司 | Catalyst for preparing methacrylonitrile and method for preparing methacrylonitrile |
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