CN100438981C - Mixed oxide catalyst of K, Cs, Ce, Cr, Co, Ni, Fe, Bi and Mo for the manufacture of acrylonitrile - Google Patents

Mixed oxide catalyst of K, Cs, Ce, Cr, Co, Ni, Fe, Bi and Mo for the manufacture of acrylonitrile Download PDF

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Publication number
CN100438981C
CN100438981C CNB2003801048826A CN200380104882A CN100438981C CN 100438981 C CN100438981 C CN 100438981C CN B2003801048826 A CNB2003801048826 A CN B2003801048826A CN 200380104882 A CN200380104882 A CN 200380104882A CN 100438981 C CN100438981 C CN 100438981C
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catalyst
carbon monoxide
olefin polymeric
mixture
acrylonitrile
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CN1720099A (en
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克里斯托·帕帕里佐斯
斯蒂芬·C·耶夫内
迈克尔·J·西利
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O& D American Corp
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BP Corp North America Inc
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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 provides a catalyst comprising a complex of catalytic oxides comprising potassium, cesium, cerium, chromium, cobalt, nickel, iron, bismuth, molybdenum, wherein the relative ratios of these elements is represented by the following general formula Aa Kb Csc Ced Cre Cof Nig Xh Fei Bi j Mo12 Ox wherein A is Rb, Na, Li, TI, or mixtures thereof, X is P, Sb, Te, B, Ge, W, Ca, Mg, a rare earth element, or mixtures thereof, a is about O to about 1, b is about 0.01 to about 1, c is about 0.01 to about 1, d is about 0.01 to about 3, e is about 0.01 to about 2, f is about 0.01 to about 10, g is about 0.1 to about 10, h is about 0 to about 4, i is about 0.1 to about 4, j is about 0.05 to about 4, x is a number determined by the valence requirements of the other elements present, and wherein the catalyst is substantially free of manganese and zinc. The catalyst is useful in processes for the ammoxidation of an olefin selected from the group consisting of propylene, isobutylene or mixtures thereof, to acrylonitrile, methacrylonitrile and mixtures thereof, respectively.

Description

Be used to make the mixed oxide catalyst of K, Cs, Ce, Cr, Co, Ni, Fe, Bi and the Mo of acrylonitrile
The present invention relates to a kind of improvement catalyst that is used for the unsaturated hydrocarbons ammoxidation reaction is become corresponding unsaturated nitrile.Especially, the present invention relates to be used to make propylene and/or isobutene respectively ammoxidation reaction become improving one's methods of acrylonitrile and/or methacrylonitrile and catalyst.More specifically, the present invention relates to a kind of new and improved ammoxidation reaction catalyst, comprise the compound of the catalytic oxidation thing of potassium, caesium, cerium, chromium, cobalt, nickel, iron, bismuth and molybdenum, and basically without any manganese and zinc.
DESCRIPTION OF THE PRIOR ART
Contain iron, bismuth and molybdenum oxide and help the catalyst of catalysis to be used in the presence of ammonia and oxygen (normally air form) the pyrolytic conversion propylene for a long time with the manufacturing acrylonitrile with being fit to element.Especially, BP 1436475; United States Patent (USP) 4,766,232; 4,377,534; 4,040,978; 4,168,246; 5,223,469 and 4,863,891 each all relate to bismuth-molybdenum-iron catalyst, its available II of family element helps catalysis to make acrylonitrile.In addition, United States Patent (USP) 4,190,608 disclose the similar bismuth-molybdenum-iron catalyst that helps catalysis, and it is used for oxyalkylene.United States Patent (USP) 5,093,299,5212,137,5,658,842 and 5,834,394 relate to the catalyst of helping of bismuth-molybdenum, and it shows high yield to acrylonitrile.
The objective of the invention is a kind of raw catelyst, it comprises the unique combination of co-catalyst, and make propylene, isobutene or its mixture respectively catalytic ammoxidation be reacted into better performance be provided in acrylonitrile, methacrylonitrile and composition thereof.
Summary of the invention
The present invention relates to make propylene and/or isobutene respectively ammoxidation reaction become the improvement Catalyst And Method of acrylonitrile and/or methacrylonitrile.
In one embodiment, catalyst of the present invention comprises the compound of the catalytic oxidation thing that contains potassium, caesium, cerium, chromium, cobalt, nickel, iron, bismuth, molybdenum, and wherein the relative scale of these elements is represented by following general formula:
A aK bCs cCe dCr eCo fNi gX hFe iBi jMo 12O x
Wherein A is Rb, Na, Li, Tl or its mixture,
X is P, Sb, Te, B, Ge, W, Mg, rare earth element or its mixture,
A be about 0～about 1,
B be about 0.01～about 1,
C be about 0.01～about 1,
D be about 0.01～about 3,
E be about 0.01～about 2,
F be about 0.01～about 10,
G be about 0.1～about 10,
H be about 0～about 3,
I be about 0.1～about 4,
J be about 0.05～about 4,
X is the number that chemical valence determined by the element of other existence,
And wherein this catalyst is substantially free of manganese and zinc.
The present invention also relates to by under gas phase state, making reaction in the presence of the metal oxide catalyst that is mixing of described alkene and gas that contains molecular oxygen and ammonia under the high temperature and high pressure, and make the alkene that is selected from propylene, isobutene or its mixture change into the method for acrylonitrile, methacrylonitrile and composition thereof respectively, wherein this catalyst is as mentioned above.
Detailed description of the invention
The present invention is a kind of raw catelyst, and it comprises the unique combination and the ratio of co-catalyst, and make propylene, isobutene or its mixture respectively catalytic ammoxidation be reacted into better performance be provided in acrylonitrile, methacrylonitrile and composition thereof.
The present invention relates to a kind of ammoxidation reaction catalyst, it comprises the compound of the catalytic oxidation thing that contains potassium, caesium, cerium, chromium, cobalt, nickel, iron, bismuth, molybdenum, and wherein the relative scale of these elements is represented by following general formula:
A aK bCs cCe dCr eCo fNi gX hFe iBi jMo 12O x
Wherein A is Rb, Na, Li, Tl or its mixture,
X is P, Sb, Te, B, Ge, W, Ca, Mg, rare earth element or its mixture,
A be about 0～about 1,
B be about 0.01～about 1,
C be about 0.01～about 1,
D be about 0.01～about 3,
E be about 0.01～about 2,
F be about 0.01～about 10,
G be about 0.1～about 10,
H be about 0～about 4,
I be about 0.1～about 4,
J be about 0.05～about 4,
X is the number that chemical valence determined by the element of other existence,
And wherein this catalyst is substantially free of manganese and zinc.
Subscript in the top general formula is represented the possible proportion of various elements with respect to molybdenum.Those skilled in the art should know and understand, and for any catalyst was formed, with regard to each oxidation state of metallic element, its total amount must keep balance with molybdenum.
An embodiment, the amount of cerium chromatize (by atom) is greater than the amount (i.e. " b "+" c " is greater than " g ") of bismuth.In another embodiment, the amount of cerium (by atom) is greater than the amount (promptly " b " is greater than " c ") of chromium.In other embodiments, " a " be about 0.05～about 0.5, " b " be about 0.01～about 0.3, " c " be about 0.01～about 0.3, " d " be about 0.01～about 3, " f+g " be about 4～about 10, " h " be about 0～about 3, " i " be about 1～about 3, " j " is about 0.1～about 2.
Basic catalyst as herein described is formed the compound of the catalytic oxidation thing that is potassium, caesium, cerium, chromium, cobalt, nickel, iron, bismuth and molybdenum.Except the element of clearly getting rid of, can comprise other elements or co-catalyst.An embodiment, this catalyst can comprise one or more in rubidium, sodium, lithium, thallium, phosphorus, antimony, tellurium, boron, germanium, tungsten, calcium, magnesium and the rare earth element (refer among La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm or the Yb any) here.In another embodiment, this catalyst contains carbamate additives for low phosphorus, and (promptly " X " is P at least, and " h " is greater than 0), this wearability to this catalyst has advantageous effect.In another embodiment, this catalyst contains magnesium (promptly " X " is Mg at least, and " h " is greater than 0); In this embodiment, preferred " h " is about 1～about 3.In another embodiment, this catalyst is substantially free of magnesium, but contains at least a " X " element (promptly " X " is at least a in P, Sb, Te, B, Ge, W, the rare earth element, and " h " is greater than 0); In this embodiment, preferred " h " is about 0.1～about 2.In another embodiment, this catalyst contains rubidium (promptly " A " is Rb at least, and " a " is greater than 0).In another embodiment, this catalyst is substantially free of rubidium.In another embodiment, this catalyst contains lithium (promptly " A " is Li at least, and " a " is greater than 0).In another embodiment, this catalyst contains lithium, and the ratio of lithium and molybdenum is about 0.01: 12～about 1: 12 (promptly as " A " when only being Li, " a " is about 0.1～about 1).For comprising iron, bismuth and molybdenum and being used to make ammoxidation of propylene to be reacted into for the mixed oxide catalyst system of acrylonitrile, cobalt and provide more total amount nitrile, for example acrylonitrile, acetonitrile and hydrogen cyanide (being also referred to as formonitrile HCN) as the combination of the lithium of additional promoters.In another embodiment, this catalyst is substantially free of strontium, and does not preferably contain strontium.Herein, for any element, " being substantially free of " refers to that this catalyst is substantially devoid of the sort of element.
In addition, for propylene, ammonia and oxygen are changed into for the acrylonitrile, comprise some element be considered to be unfavorable for to be improved catalyst of acrylonitrile productive rate.These elements are manganese and zinc.Comprise that in this catalyst manganese and zinc reduce catalyst activity, and the acrylonitrile productive rate reduces.Therefore, catalyst of the present invention is substantially free of manganese and zinc.Herein, for manganese, " being substantially free of " refers to that atomic ratio with molybdenum was less than 0.1: 12.Herein, for zinc, " being substantially free of " refers to that atomic ratio with molybdenum was less than 1: 12.Preferably, this catalyst does not contain manganese and/or zinc.
Catalyst of the present invention can support or not be supported on (promptly this catalyst can comprise carrier) on the carrier.If the use carrier, carrier mixes with the metal oxide that comprises this catalyst usually so, and perhaps carrier material can be immersed in the metal oxide.Suitable carrier is silica, aluminium oxide, zirconium, titanium oxide or its mixture.Carrier is used as the adhesive of catalyst usually, thereby obtains harder and more wear-resisting catalyst.Then, be that commerce uses, the suitable blend of activated state thing (being the compound of above-mentioned catalytic oxidation thing) and carrier is for making this catalyst have acceptable activity and hardness (wear-resisting) is important to the pass.Following trend is arranged, and any increase of activated state thing all can improve catalyst activity, but can reduce catalyst hardness.Usually carrier accounts for 40～60wt.% of the catalyst of support.In one embodiment of the invention, carrier can account for the catalyst of support less to about 30wt.%.In another embodiment of the invention, carrier can account for the about 70wt.% of catalyst as many as of support.
In one embodiment, silicon dioxide gel supports this catalyst.If the average colloidal particle diameter of described silicon dioxide gel is too small, its surface area of the catalyst that makes so will increase, and this catalyst selectivity reduces.If colloidal particle size is excessive, its scuff resistance of the catalyst that makes so is relatively poor.Usually, the average colloidal particle diameter of silicon dioxide gel is about 15nm～about 50nm.In one embodiment of the invention, the average colloidal particle diameter of silicon dioxide gel is about 10nm, can be low to moderate about 8nm.In another embodiment of the invention, the average colloidal particle diameter of silicon dioxide gel is about 100nm.In another embodiment of the invention, the average colloidal particle diameter of silicon dioxide gel is about 20nm.
Catalyst of the present invention can be prepared by multiple method for preparing catalyst, and this is known for those skilled in the art.For example, this catalyst can be by preparing with the heterogeneity co-precipitation.Then, the co-precipitation piece is dried, and grinds to form suitable size.Selectively, the co-precipitation material can be made slurry and spray-dried according to conventional methods.But this catalyst ball up or form bar-shapedly in oil, this is being known in the art.Particular procedures for this catalyst of preparation sees also United States Patent (USP) 5,093,299; 4,863,891 and 4,766,232, be incorporated herein these patents as a reference.In one embodiment, this catalyst component can mix with the carrier of slurry form, and dry then, perhaps this catalyst component can be immersed on silica or other carriers.
Bismuth can oxide or is added in this catalyst through the salt that calcining can produce oxide.Disperseing still easily, the water soluble salt through adding the thermosetting steady oxide is preferred.The preferred especially source of introducing bismuth is a bismuth nitrate.
Can produce the ferrous components that the iron compound of oxide obtains through calcining and can be added to this catalyst from any.Similar to other elements, water soluble salt is preferred, and they can be equably dispersedly in this catalyst.Ferric nitrate most preferably.
The molybdenum composition of this catalyst can obtain from any molybdenum oxide, as dioxide, and trioxide, pentoxide or heptoxide.Yet preferably hydrolyzable or decomposable molybdenum salt are as the molybdenum source.Most preferred raw material is an ammonium heptamolybdate.
Other compositions that need of this catalyst and selectable co-catalyst (for example Ni, Co, Mg, Cr, P, Sn, Te, B, Ge, Zn, In, Ca, W, or its mixture) can come from any suitable source.For example, can use nitrate that cobalt, nickel and magnesium are added in this catalyst.In addition, magnesium can be added to this catalyst with magnesium through the insoluble carbonate or the hydroxide of heating generation oxide.Phosphorus can alkali metal salt or alkali salt or ammonium salt be added in this catalyst, but preferably add with phosphoric acid.
This catalyst need with selectable alkali composition (for example Rb, Li, Na, K, Cs, Tl, or its mixture) can oxide or be added in this catalyst through the salt that calcining can produce oxide.Preferably, use and to obtain easily and the salt of dissolving easily such as nitrate and this element is added in this catalyst.
Usually mix with silicon dioxide gel by the aqueous solution with ammonium heptamolybdate and prepare this catalyst, adding in this colloidal sol has slurry, this slurry to contain the preferably compound of other element nitrate.Make solid material drying, denitrogenation and calcining then.Preferred this catalyst spray-dried under 110 ℃～350 ℃ temperature, preferred 110 ℃～250 ℃, most preferably 110 ℃～180 ℃.Denitrification temperature can be 100 ℃～500 ℃, preferred 250 ℃～450 ℃.Last calcining heat is 300 ℃～700 ℃, preferred 350 ℃～650 ℃.
Catalyst of the present invention is used for by making described alkene under the high temperature and high pressure and contain reacting of the gas of molecular oxygen and ammonia in the presence of this catalyst under gas phase state, and the alkene that is selected from propylene, isobutene or its mixture is changed into respectively in the ammoxidation reaction method of acrylonitrile, methacrylonitrile and composition thereof.
Preferably, ammoxidation reaction is reflected in the fluidized-bed reactor and carries out, although the reactor of other types such as transmission pipeline reactor also can use.Fluidized-bed reaction is used to make that acrylonitrile is known in the art.For example United States Patent (USP) 3,230, and the reactor design described in 246 is fit to, and is incorporated herein this patent as a reference.
The condition that the ammoxidation reaction reaction takes place also is known in the prior art, as United States Patent (USP) 5,093,299; 4,863,891; 4,767,878 and 4,503,001 is described; Be incorporated herein these patents as a reference.Usually, the ammoxidation reaction method is undertaken by in the presence of ammonia and oxygen propylene or isobutene are contacted with high temperature fluidized bed catalyst, thereby makes acrylonitrile or methacrylonitrile.Can use any oxygen source.Yet, consider from economic angle, preferably use air.Usually the mol ratio of oxygen and alkene is 0.5: 1～4: 1 in material, preferred 1: 1～3: 1.
The mol ratio of ammonia and alkene can be 0.5: 1～2: 1 in reaction mass.Do not have the upper limit for ammonia-olefin ratios, but be no more than 2: 1 from economic angle consideration ratio usually.Be used for from the suitable material ratio of the catalyst of the present invention of propylene production acrylonitrile be: ammonia is 0.9: 1～1.3: 1 with the propylene ratio, and air is 8.0: 1～12.0: 1 with the propylene ratio.Catalyst of the present invention obtains the acrylonitrile of high yield under relatively low ammonia and propylene material ratio (about 1: 1～about 1.05: 1).These " low ammonia conditions " help to reduce unreacted ammonia in the reactor effluent, and this situation is called " ammonia penetrates ", helps the refuse in the minimizing process subsequently.Particularly, unreacted ammonia must be removed from reactor effluent before recover acrylonitrile.Unreacted ammonia is removed by reactor effluent is contacted with sulfuric acid to generate ammonium sulfate usually, remove by reactor effluent is contacted with acrylic acid to generate ammonium acrylate, all generate the waste stream that needs processing and/or discard under the both of these case during the course.
Be reflected under about 260 ℃～600 ℃ temperature and carry out, preferably 310 ℃～500 ℃, especially preferably 350 ℃～480 ℃.Although be not crucial time of contact, normally 0.1～50 second, be 1～15 second preferred time of contact.
Can use the known any method of those skilled in the art to reclaim and the purification reaction product.A kind of method comprises the eluting gas with cold water or suitable cleaning by solvent reactor, to remove product, then by the distillation purifying product.
The main application of catalyst of the present invention is to make ammoxidation of propylene be reacted into acrylonitrile.Yet catalyst of the present invention also can be used for making propylene oxidation become acrylic acid.This method generally includes two phase process, wherein changes into methacrylaldehyde in phase I propylene major part in the presence of catalyst, changes into acrylic acid in second stage methacrylaldehyde major part in the presence of catalyst.Catalyst as herein described is applicable to and makes propylene oxidation become methacrylaldehyde in the phase I.
Specific embodiments
For illustrating the present invention, prepare catalyst of the present invention and similar catalyst (omitted in these elements one or more or also comprise the element that is unfavorable for the acrylonitrile preparation), under similar reaction condition, assess then.These embodiment only are exemplary.
Preparation of Catalyst
Embodiment 1:50wt%Cs 0.1K 0.1Ce 0.75Cr 0.3Co 4.3Ni 4.4Fe 2.0Bi 0.5Mo 14.425O 57.775+ 50wt%SiO 2Preparation of Catalyst as follows: under～70 ℃ in the 1000ml beaker with following metal nitrate CsNO 3(1.535g), KNO 3(0.796g), Fe (NO 3) 39H 2O (63.643g), Ni (NO 3) 26H 2O (100.778g), Co (NO 3) 26H 2O (98.572g), Bi (NO 3) 35H 2O (19.104g), (NH 4) 2Ce (NO 3) 6(64.773g, 50% solution) mixes.(AHM) (200.603g) is dissolved in the 310ml distilled water with ammonium heptamolybdate.In this solution, add the CrO that is dissolved in the 20ml water 3(2.363g).Add silica (625g, 40%SiO then 2Colloidal sol), motlten metal nitrate then.The yellow slurry that obtains of spray-dried then.The material that obtains carries out denitrogenation (290 ℃/3 hours and 425 ℃/3 hours), air calcination (570 ℃/3 hours) then.
Embodiment 2: use the preparation process in the foregoing description 1,50wt%Cs 0.1K 0.1Li 0.3Ce 0.58Cr 0.12Co 5.3Ni 3.1Fe 1.8Bi 0.62Mo 13.744O 54.852+ 50wt%SiO 2Preparation of Catalyst is as follows: under～70 ℃ in the 1000ml beaker with following metal nitrate CsNO 3(12.877g), KNO 3(6.679g), LiNO 3(13.665g), Fe (NO 3) 39H 2O (480.431g), Ni (NO 3) 26H 2O (595.542g), Co (NO 3) 26H 2O (1019.059g), Bi (NO 3) 35H 2O (198.691g), (NH 4) 2Ce (NO 3) 6(420.146g, 50% solution) mixes.(AHM) (1603.142g) is dissolved in the 1760ml distilled water with ammonium heptamolybdate.In this solution, add the CrO that is dissolved in the 20ml water 3(7.928g).Add silica (5000g, 40%SiO then 2Colloidal sol), motlten metal nitrate then.The yellow slurry that obtains of spray-dried then.The material that obtains carries out denitrogenation (290 ℃/3 hours and 425 ℃/3 hours), air calcination (570 ℃/3 hours) then.
Comparative examples A (not containing Ni): use the preparation process in the foregoing description 1,50wt%Cs 0.1K 0.1Ce 0.75Cr 0.3Co 8.7Fe 2.0Bi 0.5Mo 14.425O 57.775+ 50wt%SiO 2Preparation of Catalyst is as follows: under～70 ℃ in the 1000ml beaker with following metal nitrate CsNO 3(1.535g), KNO 3(0.796g), Fe (NO 3) 39H 2O (63.623g), Co (NO 3) 26H 2O (199.375g), Bi (NO 3) 35H 2O (19.098g), (NH 4) 2Ce (NO 3) 6(64.753g, 50% solution) mixes.Ammonium heptamolybdate (AHM) (200.603g) is dissolved in the 310ml distilled water.In this solution, add the CrO that is dissolved in the 20ml water 3(2.362g).Add silica (625g, 40%SiO then 2Colloidal sol), motlten metal nitrate then.
Comparative example B (not containing K): use the preparation process in the foregoing description 1,50wt%Cs 0.2Ce 0.75Cr 0.3Co 4.3Ni 4.4Fe 2.0Bi 0.5Mo 14.425O 57.775+ 50wt%SiO 2Preparation of Catalyst is as follows: under～70 ℃ in the 1000ml beaker with following metal nitrate CsNO 3(3.061g), Fe (NO 3) 39H 2O (63.456g), Ni (NO 3) 26H 2O (100.481g), Co (NO 3) 26H 2O (98.282g), Bi (NO 3) 35H 2O (19.047g), (NH 4) 2Ce (NO 3) 6(64.582g, 50% solution) mixes.Ammonium heptamolybdate (AHM) (200.603g) is dissolved in the 310ml distilled water.In this solution, add the CrO that is dissolved in the 20ml water 3(2.356g).Add silica (625g, 40%SiO then 2Colloidal sol), motlten metal nitrate then.
Comparative example C (containing Mn): use the preparation process in the foregoing description 1,50wt%Cs 0.1K 0.1Ce 0.75Cr 0.3Co 4.3Ni 4.4Mn 0.5Fe 2.0Bi 0.5Mo 14.425O 57.775+ 50wt%SiO 2Preparation of Catalyst is as follows: under～70 ℃ in the 1000ml beaker with following metal nitrate CsNO 3(1.485g), KNO 3(0.77g), Fe (NO 3) 39H 2O (61.559g), Ni (NO 3) 26H 2O (97.478g), Co (NO 3) 26H 2O (95.345g), Mn (NO 3) 2(13.34g, 51.1% solution), Bi (NO 3) 35H 2O (18.478g), (NH 4) 2Ce (NO 3) 6(62.653g, 50% solution) mixes.Ammonium heptamolybdate (AHM) (200.761g) is dissolved in the 310ml distilled water.In this solution, add the CrO that is dissolved in the 20ml water 3(2.286g).Add silica (625g, 40%SiO then 2Colloidal sol), motlten metal nitrate then.
Comparative Example D (containing Zn): use the preparation process in the foregoing description 1,50wt%Cs 0.1K 0.1Ce 0.75Cr 0.3Co 4.3Ni 2.2Zn 2.0Fe 2.0Bi 0.5Mo 14.425O 57.775+ 50wt%SiO 2Preparation of Catalyst is as follows: under～70 ℃ in the 1000ml beaker with following metal nitrate CsNO 3(1.55g), KNO 3(0.804g), Fe (NO 3) 39H 2O (64.244g), Ni (NO 3) 26H 2O (50.865g), Co (NO 3) 26H 2O (99.503g), Zn (NO 3) 26H 2O (47.301g), Bi (NO 3) 35H 2O (19.284g), (NH 4) 2Ce (NO 3) 6(65.385g, 50% solution) mixes.Ammonium heptamolybdate (AHM) (199.759g) is dissolved in the 310ml distilled water.In this solution, add the CrO that is dissolved in the 20ml water 3(2.385g).Add silica (625g, 40%SiO then 2Colloidal sol), motlten metal nitrate then.
Catalyst test
All tests are carried out in the 40cc fluidized-bed reactor.Propylene is added in the reactor with the speed of 0.06WWH (be propylene weight/catalyst weight/hour).Pressure in the reactor remains on 10psig.Reaction temperature is 430 ℃.Stable after～20 hours, the collecting reaction product sample.Reactor effluent is collected in the bubble-type scrubbers that contains cold HCl solution.Use the quantitative instrumentation amount of soap-film outgassing rate, use the gas chromatograph for determination waste gas that branch fluidization tower gas analyzer is installed to form when experiment finishes.When reclaiming the experiment end, whole wash liquids are diluted to about 200gms with distilled water.The 2-butanone of having weighed is as the interior mark of～50 gram dilute solution samples.Analyze 2 μ l samples with the GC that flame ionization detector and Carbowax post are installed.By measuring NH with excessive NaOH solution titration free HCl 3Amount.The following examples have been illustrated the present invention.
Table 1
Embodiment Active phase composition Total C 3=conversion ratio Change into the conversion ratio of acrylonitrile Change into the ratio of acrylonitrile
1 Cs 0.1K 0.1Ce 0.75Cr 0.3Co 4.3Ni 4.4Fe 2.0Bi 0.5Mo 14.425O 57.775 98.5 82.6 83.9
2 Cs 0.1K 0.1Li 0.3Ce 0.58Cr 0.12Co 5.3Ni 3.1Fe 1.8Bi 0.62Mo 13.744O 54.852 98.8 81.9 82.9
A Cs 0.1K 0.1Ce 0.75Cr 0.3Co 8.7Fe 2.0Bi 0.5Mo 14.425O 57.775 95.8 80.6 84.4
B Cs 0.2Ce 0.75Cr 0.3Co 4.3Ni 4.4Fe 2.0Bi 0.5Mo 14.425O 57.775 96.6 80.5 83.3
C Cs 0.1K 0.1Ce 0.75Cr 0.3Co 4.3Ni 4.4Mn 0.5Fe 2.0Bi 0.5Mo 14.425O 57.775 99.4 81.6 82.0
D Cs 0.1K 0.1Ce 0.75Cr 0.3Co 4.3Ni 2.2Zn 2.0Fe 2.0Bi 0.5Mo 14.425O 57.775 96.4 81.0 84.0
Annotate: 1. the carbon monoxide-olefin polymeric of all tests all contains 50% activated state thing and 50%SiO 2
2. " total C 3" each propylene changes into the mole percent of all products to=conversion ratio.
3. " changing into the conversion ratio of acrylonitrile " is the mole percent that each propylene changes into acrylonitrile.
4. " change into the ratio of acrylonitrile " and be the ratio of the acrylonitrile molal quantity that makes and the propylene molal quantity of conversion, represent with percentage.
Embodiment 3: use the preparation process in the foregoing description 2, prepare several catalyst (50% activated state thing and 50%SiO that also comprise lithium 2).The activated state thing is composed as follows:
Cs 0.1K 0.1Li 0.3Ce 1.0Cr 0.12Co 5.3Ni 3.1Fe 1.8Bi 0.62Mo 14.44O 57.78
Cs 0.1K 0.1Li 0.3Ce 0.8Cr 0.12Co 5.3Ni 3.1Fe 1.8Bi 0.62Mo 14.074O 56.282
Cs 0.1K 0.1Li 0.3Ce 0.8Cr 0.12Co 4.2Ni 4.2Fe 1.8Bi 0.62Mo 14.074O 56.282
Cs 0.1K 0.1Li 0.3Ce 1.0Cr 0.12Co 1.0Ni 7.4Fe 1.8Bi 0.62Mo 14.374O 57.532
Cs 0.1K 0.1Li 0.3Ce 1.0Cr 0.12Co 5.3Ni 3.1Fe 1.8Bi 0.62Mo 14.074O 57.582
Cs 0.1K 0.1Li 0.3Ce 0.8Cr 0.5Co 5.3Ni 3.1Fe 1.8Bi 0.62Mo 13.969O 55.862
Cs 0.1K 0.1Li 0.3Na 0.2Ce 1.0Cr 0.12Co 1.0Ni 7.4Fe 1.8Bi 0.62Mo 14.374O 57.982
Cs 0.1K 0.1Li 0.1Ce 1.0Cr 0.12Co 4.2Ni 4.2Fe 1.8Bi 0.62Mo 14.26O 57.14
Cs 0.1K 0.1Li 0.3Ce 1.0Cr 0.12Co 4.2Ni 4.2Fe 1.8Bi 0.62Mo 14.16O 56.94
Cs 0.1K 0.1Li 0.3Na 0.2Ce 0.8Cr 0.12Co 4.2Ni 4.2Fe 1.8Bi 0.62Mo 14.16O 56.64
Cs 0.1K 0.1Li 0.1Ce 1.0Cr 0.12Co 2.0Ni 5.0Fe 1.8Bi 0.62Mo 12.86O 51.54
Cs 0.1K 0.1Li 0.1Ce 1.0Cr 0.12Co 3.2Ni 4.2Fe 2.0Bi 0.62Mo 14.26O 54.04
Cs 0.1K 0.1Li 0.1Na 0.2Ce 1.0Cr 0.12Co 4.2Ni 4.2Fe 1.8Bi 0.62Mo 14.36O 57.54
Cs 0.1K 0.1Li 0.3Ce 0.8Cr 0.12Co 4.2Ni 4.2Fe 2.2Bi 0.62Mo 14.76O 59.34
According to above-mentioned detecting catalyst composition.The total conversion (being the mole percent that each propylene changes into acrylonitrile, acetonitrile and hydrogen cyanide) that above-mentioned catalyst changes into nitrile is generally about 86%～about 88%.
Catalyst of the present invention is formed and be it is characterized in that it comprises potassium, caesium, cerium, chromium, cobalt, nickel, iron, bismuth and molybdenum, and does not have manganese and zinc basically.This element combinations was not in the relative proportions described used in single ammoxidation reaction catalyst before this.As shown in table 1, for ammoxidation of propylene is reacted into for the acrylonitrile, to compare with the catalyst that comprises similar (but inaccuracy) element combinations in the existing patent, catalyst of the present invention has more performance.More specifically, when with this catalyst in the presence of ammonia and air at high temperature during the ammoxidation reaction propylene, compare with the catalyst that does not belong to the scope of the invention, comprise potassium, caesium, cerium, chromium, cobalt, nickel, iron, bismuth and molybdenum and do not have the catalyst of manganese or zinc to show higher total conversion basically and than the high acrylonitrile conversion ratio.
Although top explanation and above-mentioned embodiment are generally used for implementing the present invention, it should be understood that, those skilled in the art according to specification make multiple choices, modifications and variations are obvious.Therefore, intention comprises all these selections, modifications and variations, and falls within the spirit of claims and widely in the scope.

Claims (16)

1. carbon monoxide-olefin polymeric, it comprises by potassium, caesium, cerium, chromium, cobalt, nickel, iron, bismuth, molybdenum, and the compound of the catalytic oxidation thing of one or more compositions in the non-essential rubidium, sodium, lithium, thallium, wherein the relative scale of these elements is represented by following general formula:
A aK bCs cCe dCr eCo fNi gFe iBi jMo 12O x
Wherein
A is Rb, Na, Li, Tl or its mixture,
A is 0～1,
B is 0.01～1,
C is 0.01～1,
D is 0.01～3,
E is 0.01～2,
F is 0.01～10,
G is 0.1～10,
I is 0.1～4,
J is 0.05～4,
X is that the chemical valence by the element of other existence requires the number that determined.
2. carbon monoxide-olefin polymeric as claimed in claim 1, wherein said carbon monoxide-olefin polymeric comprises the phosphorus of oxide form in addition.
3. carbon monoxide-olefin polymeric as claimed in claim 1, wherein said carbon monoxide-olefin polymeric comprises the magnesium of oxide form in addition.
4. carbon monoxide-olefin polymeric as claimed in claim 1, wherein f+g is 4～10.
5. carbon monoxide-olefin polymeric as claimed in claim 1, wherein said carbon monoxide-olefin polymeric comprises the carrier that is selected from silica, aluminium oxide, zirconium, titanium oxide or its mixture.
6. carbon monoxide-olefin polymeric as claimed in claim 5, wherein said carrier accounts for 30～70wt.% of described carbon monoxide-olefin polymeric.
7. carbon monoxide-olefin polymeric as claimed in claim 1, wherein said carbon monoxide-olefin polymeric comprise that average colloidal particle diameter is the silica of 8nm～100nm.
8. carbon monoxide-olefin polymeric, it comprises by potassium, caesium, lithium, cerium, chromium, cobalt, nickel, iron, bismuth, molybdenum, and the compound of the catalytic oxidation thing of one or more compositions in the non-essential rubidium, sodium, thallium, wherein the relative scale of these elements is represented by following general formula:
A aLi a’K bCs cCe dCr eCo fNi gFe iBi jMo 12O x
Wherein
A is Rb, Na, Tl or its mixture,
A is 0～1,
A ' is 0.01～1,
B is 0.01～1,
C is 0.01～1,
D is 0.01～3,
E is 0.01～2,
F is 0.01～10,
G is 0.1～10,
I is 0.1～4,
J is 0.05～4,
X is that the chemical valence by the element of other existence requires the number that determined.
9. carbon monoxide-olefin polymeric as claimed in claim 8, wherein f+g is 4～10.
10. one kind by making alkene and the gas and the ammonia that contain molecular oxygen react in the presence of catalyst under the gas phase high temperature and high pressure, make the alkene that is selected from propylene, isobutene or its mixture change into the method for acrylonitrile, methacrylonitrile and composition thereof respectively, described catalyst comprises by potassium, caesium, cerium, chromium, cobalt, nickel, iron, bismuth, molybdenum, and the compound of the catalytic oxidation thing of one or more compositions in rubidium, sodium, lithium, the thallium optionally, wherein the relative scale of these elements is represented by following general formula:
A aK bCs cCe dCr eCo fNi gFe iBi jMo 12O x
Wherein A is Rb, Na, Li, Tl or its mixture,
A is 0～1,
B is 0.01～1,
C is 0.01～1,
D is 0.01～3,
E is 0.01～2,
F is 0.01～10,
G is 0.1～10,
I is 0.1～4,
J is 0.05～4,
X is that the chemical valence by the element of other existence requires the number that determined.
11. method as claimed in claim 10, wherein said catalyst comprises the phosphorus of oxide form in addition.
12. method as claimed in claim 10, wherein said catalyst comprises the magnesium of oxide form in addition.
13. method as claimed in claim 10, wherein f+g is 4～10.
14. method as claimed in claim 10, wherein said catalyst comprises the carrier that is selected from silica, aluminium oxide, zirconium, titanium oxide or its mixture.
15. method as claimed in claim 14, wherein said carrier accounts for 30～70wt.% of described catalyst.
16. method as claimed in claim 10, wherein said catalyst comprise that average colloidal particle diameter is the silica of 8nm～100nm.
CNB2003801048826A 2002-12-02 2003-11-19 Mixed oxide catalyst of K, Cs, Ce, Cr, Co, Ni, Fe, Bi and Mo for the manufacture of acrylonitrile Expired - Lifetime CN100438981C (en)

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US8258073B2 (en) * 2010-03-23 2012-09-04 Ineos Usa Llc Process for preparing improved mixed metal oxide ammoxidation catalysts
US9433929B2 (en) * 2011-09-21 2016-09-06 Ineos Europe Ag Mixed metal oxide catalysts
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