CN107282092A - Catalyst for olefin ammoxidation synthesis of acrylonitrile - Google Patents

Catalyst for olefin ammoxidation synthesis of acrylonitrile Download PDF

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Publication number
CN107282092A
CN107282092A CN201610225887.3A CN201610225887A CN107282092A CN 107282092 A CN107282092 A CN 107282092A CN 201610225887 A CN201610225887 A CN 201610225887A CN 107282092 A CN107282092 A CN 107282092A
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grams
catalyst
mixed liquor
mixed
acrylonitrile
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CN107282092B (en
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李静霞
陶纯康
吴粮华
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The present invention relates to the catalyst for olefin ammoxidation synthesis of acrylonitrile, 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 for olefin ammoxidation synthesis 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 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 diatomite and the molecular sieves of ZSM 5, preferably resolves the problem, in the industrial production that acrylonitrile is produced available for ammoxidation of propylene.

Description

Catalyst for olefin ammoxidation synthesis of acrylonitrile
Technical field
The present invention relates to the catalyst for olefin ammoxidation synthesis of 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：
For the catalyst of olefin ammoxidation synthesis 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 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 includes silica and support modification agent, and the support modification agent is in diatomite and ZSM-5 molecular sieve At least one.
In above-mentioned technical proposal, the support modification agent is simultaneously including ZSM-5 molecular sieve and diatomite, and now both are in raising There is synergy in terms of selectivity and stability.Both diatomite and ZSM-5 molecular sieve 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, Si/Al mol ratios in ZSM-5 molecular sieve are not particularly limited, such as, but not limited to 20~100, In the specific embodiment of the invention, in order to year-on-year, Si/Al moles is 40.In technical solution of the present invention, ZSM-5 molecular sieve In optional Hydrogen or sodium form, the specific embodiment of the invention, in order to year-on-year, using sodium form ZSM-5 molecular sieve.
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) is in order to obtain scattered more uniform mixing Liquid 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, still Ludox 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, support modification agent Particle diameter be 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：The side of ammoxidation of propylene synthesis 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 diatomite, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I, Diatomite.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 diatomite, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I, 3wt% diatomite.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 diatomite, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I, 4wt% diatomite.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 40%, carrier that gram water and 5 grams of ZSM-5 molecular sieves, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I, In molecular sieve containing 0.5wt%ZSM-5.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed Liquid II is closed, mixed liquor I II is formed, solution I and mixed liquor I II is mixed, is 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.
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 40% that gram water and 30 grams of ZSM-5 molecular sieves, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I, is carried Molecular sieve containing 3wt%ZSM-5 in body.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed Liquid II is closed, mixed liquor I II is formed, solution I and mixed liquor I II is mixed, is 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.
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 40% that gram water and 40 grams of ZSM-5 molecular sieves, which are mixed to form vehicle weight concentration in mixed liquor I I, wherein mixed liquor I I, is carried Molecular sieve containing 4wt%ZSM-5 in body.By 846.0 grams of (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed Liquid II is closed, mixed liquor I II is formed, solution I and mixed liquor I II is mixed, is 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 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 dense that gram water and 10 grams of diatomite and 20 grams of ZSM-5 molecular sieves are mixed to form vehicle weight in mixed liquor I I, wherein mixed liquor I I Spend for 40%, diatomite containing 1wt% and 2wt%ZSM-5 molecular sieves in carrier.By 846.0 grams of (NH4)6Mo7O24·4H2O Dissolved in 890 grams of water, and add mixed liquor I I, formed mixed liquor I II, solution I and mixed liquor I II are mixed, PH is 5, and temperature obtains slurry I to be stirred under the conditions of 80 DEG C.The slurry being made is carried out in spray dryer micro- Spherolite is molded, and is finally calcined 2.0 hours in 590 DEG C in rotary roasting furnace, 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 dense that gram water and 15 grams of diatomite and 15 grams of ZSM-5 molecular sieves are mixed to form vehicle weight in mixed liquor I I, wherein mixed liquor I I Spend for 40%, diatomite containing 1.5wt% and 1.5wt%ZSM-5 molecular sieves in carrier.By 846.0 grams of (NH4)6Mo7O24·4H2O Dissolved in 890 grams of water, and add mixed liquor I I, formed mixed liquor I II, solution I and mixed liquor I II are mixed, PH is 5, and temperature obtains slurry I to be stirred under the conditions of 80 DEG C.The slurry being made is carried out in spray dryer micro- Spherolite is molded, and is finally 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 diatomite and 22.5 grams of ZSM-5 molecular sieves are mixed to form vehicle weight in mixed liquor I I, wherein mixed liquor I I Concentration is 40%, diatomite containing 0.75wt% and 22.5wt%ZSM-5 molecular sieves in carrier.By 846.0 grams (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, mixed liquor I II is formed, by solution I and mixing Liquid III is mixed, and is 5 in PH, temperature obtains slurry I to be stirred under the conditions of 80 DEG C.By the slurry being made in spray Framboid shaping is carried out in mist drier, is finally calcined 2.0 hours in 590 DEG C in rotary roasting furnace, 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 dense that gram water and 6 grams of diatomite and 24 grams of ZSM-5 molecular sieves are mixed to form vehicle weight in mixed liquor I I, wherein mixed liquor I I Spend for 40%, diatomite containing 0.6wt% and 2.4wt%ZSM-5 molecular sieves in carrier.By 846.0 grams of (NH4)6Mo7O24·4H2O Dissolved in 890 grams of water, and add mixed liquor I I, formed mixed liquor I II, solution I and mixed liquor I II are mixed, PH is 5, and temperature obtains slurry I to be stirred under the conditions of 80 DEG C.The slurry being made is carried out in spray dryer micro- Spherolite is molded, and is finally 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 dense that gram water and 5 grams of diatomite and 25 grams of ZSM-5 molecular sieves are mixed to form vehicle weight in mixed liquor I I, wherein mixed liquor I I Spend for 40%, diatomite containing 0.5wt% and 2.5wt%ZSM-5 molecular sieves in carrier.By 846.0 grams of (NH4)6Mo7O24·4H2O Dissolved in 890 grams of water, and add mixed liquor I I, formed mixed liquor I II, solution I and mixed liquor I II are mixed, PH is 5, and temperature obtains slurry I to be stirred under the conditions of 80 DEG C.The slurry being made is carried out in spray dryer micro- Spherolite is molded, and is finally 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 Gram water and 1.7 grams of diatomite and 3.3 grams of ZSM-5 molecular sieves are mixed to form vehicle weight in mixed liquor I I, wherein mixed liquor I I Concentration is 40%, diatomite containing 0.17wt% and 0.33wt%ZSM-5 molecular sieves in carrier.By 846.0 grams (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, mixed liquor I II is formed, by solution I and mixing Liquid III is mixed, and is 5 in PH, temperature obtains slurry I to be stirred under the conditions of 80 DEG C.By the slurry being made in spray Framboid shaping is carried out in mist drier, is finally calcined 2.0 hours in 590 DEG C in rotary roasting furnace, 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 diatomite and 13.3 grams of ZSM-5 molecular sieves are mixed to form vehicle weight in mixed liquor I I, wherein mixed liquor I I Concentration is 40%, diatomite containing 0.67wt% and 1.33wt%ZSM-5 molecular sieves in carrier.By 846.0 grams (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, mixed liquor I II is formed, by solution I and mixing Liquid III is mixed, and is 5 in PH, temperature obtains slurry I to be stirred under the conditions of 80 DEG C.By the slurry being made in spray Framboid shaping is carried out in mist drier, is finally calcined 2.0 hours in 590 DEG C in rotary roasting furnace, 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 diatomite and 26.7 grams of ZSM-5 molecular sieves are mixed to form carrier weight in mixed liquor I I, wherein mixed liquor I I It is diatomite containing 1.33wt% and 2.67wt%ZSM-5 molecular sieves in 40%, carrier to measure concentration.By 846.0 grams (NH4)6Mo7O24·4H2O dissolves in 890 grams of water, and adds mixed liquor I I, mixed liquor I II is formed, by solution I and mixing Liquid III is mixed, and is 5 in PH, temperature obtains slurry I to be stirred under the conditions of 80 DEG C.By the slurry being made in spray Framboid shaping is carried out in mist drier, is finally calcined 2.0 hours in 590 DEG C in rotary roasting furnace, 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 the catalyst of olefin ammoxidation synthesis 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 includes silica and support modification agent, and the support modification agent is in diatomite and ZSM-5 molecular sieve At least one.
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 for ammoxidation of propylene synthesis of 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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Publication number Priority date Publication date Assignee Title
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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
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