CN1061165A - The catalyst system of alkane ammoxidation - Google Patents
The catalyst system of alkane ammoxidation Download PDFInfo
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- CN1061165A CN1061165A CN91111300A CN91111300A CN1061165A CN 1061165 A CN1061165 A CN 1061165A CN 91111300 A CN91111300 A CN 91111300A CN 91111300 A CN91111300 A CN 91111300A CN 1061165 A CN1061165 A CN 1061165A
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Abstract
C
3To C
5No cycloalkane and NH
3And O
2Ammoxidation reaction, adopt (1) alkane: NH
3Molar ratio range be 2-16, alkane: O
2Molar ratio range be the granulate mixture of 1-10 and (2) two kinds of catalyst components, wherein first catalyst component to promote alkane and generate unsaturated nitrile and alkene effective especially, and second catalyst component is effective especially to promoting that alkene is converted into unsaturated nitrile.Effective catalyst composition in this method is disclosed.
Description
The alkane ammoxidation that the invention relates to the alkane that contains 3-5 carbon atom, a particularly 3-4 carbon atom is the catalyst system of α, alpha, beta-unsaturated nitriles.The ammoxidation that the most important thing is iso-butane is converted into methacrylonitrile, and the ammoxidation of propane is converted into acrylonitrile, and the latter is particularly important.
Because propylene and propane have price difference, so, be attractive economically for developing the feasible catalysis process that propane is converted into acrylonitrile.
For the exploitation propane ammoxidation is converted into the effective ways of acrylonitrile, the effort of in the past being made of prior art, its result is not that yield is not high, must add halogen catalyst exactly in charging.Add halogen and not only require the reactor should be, but also require the quantitative recovery co-catalyst by special resistant material manufacturing.So additional cost has just been offset the superiority of propane/propylene price difference.
Therefore, the purpose of this invention is to provide and alkane ammoxidation is converted into a kind of of unsaturated nitrile improves one's methods.
Further purpose of the present invention is to provide new catalyst system for the method.
Another purpose of the present invention provides a kind of improved catalytic ammoxidation method by lower paraffin hydrocarbon production unsaturated nitrile of not using halogen catalyst.
Other purposes of the present invention and characteristic, characteristics and advantage etc. can be understood by following open explanation and claim.
The present invention above-mentioned and other purposes realize by method of the present invention.Method of the present invention has two main features.First characteristics are to adopt with respect to NH
3With molecular oxygen excessive alkane charging.Second characteristic is to adopt C
3To C
5Alkane is to NH
3And O
2The a high proportion of while, use composite catalyst, i.e. catalyst mixture, first catalyst component to promote alkane and generate unsaturated nitrile and alkene effective especially, and second catalyst component is effective especially to promoting that alkene is converted into unsaturated nitrile.This mixture is exactly the subject matter of claim proposed by the invention.
" alkane " is meant non-cycloalkane in this application.
British patent specification 1,336,135 and 1,336,136 disclose employing propane or iso-butane for ammonia and oxygen at high proportion, but have only used single ammoxidation catalyst, and the yield of acrylonitrile is extremely low.United States Patent (USP) 3,860,534 also disclose and have adopted at high proportion thisly, and applied catalyst only contains the oxide of vanadium and antimony.Yet catalyst need wash 24 hours with water and carry out drying, troublesome poeration after calcining.People such as A.N.Shatalova are at Neftekhimiya; 8, NO.4 609-612(1968) has described the reaction of propane and oxygen and ammonia, adopts a large amount of excessive propane and uses two kinds of mixture of catalysts, and wherein a kind of catalyst is described as be in the metal oxide that has the dehydrogenation characteristic under 550 and 600 ℃.Under 500 ℃, almost there is not acrylonitrile to produce.During every generation 1 mol propylene nitrile, also there are quite a large amount of propionitrile and methacrylaldehyde to produce.The conversion per pass that propane generates acrylonitrile is generally 2-4%, and the selectivity that generate acrylonitrile this moment is 12-33%.
When this method is applied to propane ammoxidation, propylene generation is in a small amount arranged, this is relevant with unreacted propane in the effluent.This propane effluent that contains propylene, wherein the propylene amount can reach the 8%(mole of propylene and propane summation), and be not more than the 6%(mole usually), it can form the base stock of this method.The C of this method in general
3To C
5Paraffinic feedstock can contain one or more plants C
3To C
5Alkene.To C in this method for ammoxidation raw material
3To C
5The content of alkene can be from 0 to 8%(mole), be benchmark with alkane in the charging and alkene molal quantity sum, and this raw material can be from any source.Though in basic paraffinic feedstock, relatively large C may occur
3To C
5Alkene, but content commonly used is as mentioned above, and also alkene is corresponding with the specific alkane that is added to this method reaction zone usually.
The invention provides C
3To C
5Alkane ammoxidation generates α; the method of alpha, beta-unsaturated nitriles; it comprises makes in the reaction zone and ammonia, molecular oxygen and the gas phase alkane that mixes mutually of a kind of inert gas diluent of adding of choosing arbitrarily; contact with the tight granulate mixture of first catalyst component and second catalyst component, described reaction zone feeds contains: alkane: NH
3Molar ratio range from 2 to 16(common 3-7) and alkane: O
2Molar ratio range from 1 to 10(common 1.5-5).Described first catalyst component contains 10-99%(weight) diluent/carrier and 90-1%(weight) component in the catalyst of the ratio shown in the following empirical formula:
VSb
mA
aB
bC
cT
tO
xFormula (1)
Wherein A is one or more among W, Sn, Mo, B, P and the Ge;
B is one or more among Fe, Co, Ni, Cr, Pb, Mn, Zn, Se, Te, Ga, In and the As;
C is one or more among alkali metal and the Tl;
T is one or more among Ca, Sr and the Ba; Wherein m is 0.01-20; A is 0.2-10; B is 0-20; C is the common 0-1 of 0-20(); T is 0-20; (a+b+c+t): ratio (l+m) is 0.01-6; The x value is decided by the oxidation state of other elements in the formula, and in the formula average valence of Sb be higher than+3 and the average valence of V be lower than+5.Described second catalyst component contains 0-99%(weight) diluent/carrier and 100-1%(weight) component in the catalyst of the ratio shown in the following empirical formula:
Fe
10Sb
dTe
eMe
fG
gO
hR
iO
xFormula (2)
In the formula
Me is V, Mo, W or their composition;
G is one or more alkali metals;
Q is one or more among Cu, Mg, Zn, La, Ce, Cr, Mn, Co, Ni, Bi, the Sn;
R is one or both among P, the B
And d=10-60, e=0-10, f=0-6, g=0-5, h=0-10, i=0-5, the numerical value of x is decided by the valence state requirement of existing other elements, is 0.001 to 2.5 at first catalyst component described in the described mixture to the scope of the weight ratio of described second catalyst component.
In a kind of especially effectively catalyst of formula (1), m is the number (normally 2-10, more commonly 3-7) greater than 1.
" granulate mixture " used herein is meant the solid particle of first catalyst component or the particle of segmentation again, a kind of mixture of forming with the particle that separates and vary in size of second catalyst component.The particle size of using in fluidized-bed reactor is about 40 to 90 microns usually, and more oarse-grained certainly catalyst can be applicable to fixed bed or gravity flow catalytic bed.
The O of reaction zone feed in all embodiments of this method
2To NH
3The scope of ratio be generally 1 to 10(and more commonly usedly be 1-5), inert gas diluent to the ratio of alkane be generally 0 to 5(more common be 0 to 3).
The diluent or carrier of each of these two kinds of catalyst components is fire-resistant metal oxide or mixture, as silica, silica-alumina etc.
When enforcement was of the present invention usually, the carriers/diluents of formula (1) catalyst was not the oxide of specified element in the formula (1).And, usually implementing when of the present invention, the carriers/diluents of formula (2) catalyst neither formula (2) in the oxide of specified element.
In catalyst component of the present invention, the empirical formula of catalyst (1) and (2) of course not refer to any specific compound, do not represent that these elements are to exist with hopcalite form separately yet, still exist with the composite oxides form, or exist with discrete crystalline phase or solid solution form.Analogue is as the name of some oxide of carrier or diluent, as " silica " or " aluminium oxide " or SiO
2Or Al
2O
3, only be the custom call of continuing to use in the inorganic oxide catalyst technical field, these titles typically refer to the compound that is called carrier in catalyst technical field.Yet this name does not also mean that the element that is comprised really occurs with the simple oxide form.In fact these elements usually be with formula (1) or formula (2) in a kind of, several and exist to the forms that whole elements form composite oxides, this composite oxides are to form in the precipitation of preparation catalyst component or gelling, drying and calcination process.
Method of the present invention is specially adapted to the ammoxidation of propane or iso-butane.
According to the present invention, above-mentioned first catalyst component is that the average oxidation state of vanadium is lower than under 5 the condition and prepares in making the ultimate constituent.
A kind of method for preparing first catalyst component is to make antimonious compound (as Sb
2O
3) and the compound of pentavalent vanadium (as V
2O
5) between carry out redox reaction, antimony is oxidized and vanadium is reduced between the stage of reaction.
Above-mentioned redox reaction is once by Birchall and Sleight(Inorganic.Chem., 15,868-70 (1976)) and by people such as Berry (J.Chem.Soc.Dalton Trans., 1983,9-12) described, they are by finishing this reaction with the drying composite of above-mentioned reactant about the heating more than 600 ℃.This product has cubic rutile-type crystal structure, its characteristic X-ray diffractogram.
Yet having now found that can be successfully in aqueous medium and realize that more easily this redox reaction, its method are to heat under 80 ℃ of-200 ℃ of temperature, for example with V
5+Compound is (as NH
4VO
3Or V
2O
5) the water dispersion, with Sb
3+Compound heat together, for example with Sb
2O
3And NH
4VO
3(or V
2O
5) react.This step is then evaporated afterwards, drying, then product is calcined in containing the atmosphere of molecular oxygen (as air), and temperature is 350 ℃ to 700 or 750 ℃, is generally 400-650 ℃.Calcination time can be from 30 minutes to 12 hours, yet gratifying catalyst normally obtained at this temperature lower calcination in 1 to 5 hour.
When in containing the atmosphere of molecular oxygen (as air), calcining, has the excessive trivalent antimony compound of part at least (as Sb
2O
3) be oxidized to Sb
2O
4
After finishing above-mentioned redox reaction, first catalyst component can suitably mix other components except that vanadium and antimony (also having partial oxygen certainly).Additive A, B, C and/or T(are if any), can after redox reaction, join in the slurries, after perhaps the solid particle that contains vanadium and antimony useful component can being separated from aqueous medium, the any suitable stage before catalyst is calcined at last, be coated with method known in the art and be covered with or flood these additives, the oxide of available these elements, hydroxide, acid, salt (particularly organic salt, as acetate) and other compounds mix.
Footnote a generally is at least 0.4 or 0.5 in formula (1).In formula (1), whenever have an atom V generally to have 0.2 atom W at least, and if W and Sn(Sn is arranged) summation of atomicity generally is at least 0.4.Whenever there is an atom V to contain 0.4 atom W at least in the preferred catalyst component of formula (1).Particularly when W exists, every atom V will be effective especially as 0.4 atom P is arranged at least again except that W.Diluent/carrier described in this catalyst component includes 20-100%(weight) aluminium oxide and 80-0%(weight) silica, then this catalyst component particularly suitable.
The catalyst component of formula (1) expression, wherein A comprises 1 atom W at least, a was at least 1 o'clock, then particularly suitable.
Catalyst carrier in first catalyst component (formula (1)) not only makes the mechanical strength of catalyst improve, and catalytic activity is significantly improved, and is especially true when using aluminium oxide and silica-alumina.Outside alumina and the silica-alumina, adaptable other carriers have silica, titanium oxide, silica-titanium oxide, Nb
2O
5, silica-niobium oxide, silica-zirconia, zirconia and magnesia etc.
In first catalyst component, not only can improve mechanical strength, and can improve the carrier material of present the best of required nitrile yield, be to be selected from following compounds: silica-alumina and aluminium oxide, wherein contain 20-100%(weight) aluminium oxide, be generally 50-100%, preferably 60-100%(weight) aluminium oxide; Silica-titanium oxide and titanium oxide wherein contain 20-100%(weight) titanium oxide; Silica-zirconia and zirconia wherein contain 80-100%(weight) zirconia; And silica-niobium oxide and niobium oxide, wherein contain 30-100%(weight) niobium oxide.
During preparation formula (2) second catalyst components, metal oxide together blend or generate respectively after mix again, perhaps generate at the scene respectively or jointly.If any the co-catalyst oxide, when it is mixed iron-antimony-based catalyst, preferably before calcining, sneak in the gel, perhaps before calcining, sneak in the catalyst matrix of oven dry.The method for optimizing that mixes promoter elements is a water soluble salt of selecting promoter elements, prepares the aqueous solution of this salt, and this solution is mixed with the aqueous solution or the suspension liquid phase of basic catalyst elements or its salt.Also can be by using solubility double salt or compound, promoter elements is mixed with required basic element, each element will provide desirable ratio in the catalyst of making when calcining.
For iron is introduced in the catalyst, will produce the compound of any iron of oxide in the time of can using calcining.The same with other elements, preferably adopt water soluble salt, these elements are evenly dispersed in the catalyst.Ferric nitrate is best.Can in kind introduce cobalt and nickel.
Antimony is with Sb
2O
3Be introduced as suitablely, maybe can use Sb
2O
5Colloidal sol.Also the metallic antimony of pulverizing can be added in the red fuming nitric acid (RFNA), then boil these slurries residue nitric acid is decomposed, stay the slurries of sb oxide.
Those skilled in the art also can select other initiation material for use, and are particularly especially true when the initiation material of above pointing out is unwell to large-scale production economically.In general, any compound that contains the required component of catalyst all can use, and needs only when heating in the disclosed hereinafter temperature range, and the oxide that can produce this catalyst gets final product.
Second catalyst component is prepared easily by the slurries technology, at first preparation includes the aqueous slurry of the whole elements of this catalyst, afterwards the water in the slurries is removed to form pre-catalyst precipitation or powder, then in oxygen-containing gas (as air), calcine this pre-catalyst under the high temperature, thereby be made into catalyst.Outside dewatering, other liquid are (as C
1To C
8Alcohols) also can be used for forming the pre-catalyst slurries.
Carrier can be any common vector in second catalyst component, as silica, aluminium oxide, silica-alumina, titanium oxide, zirconia and Nb
2O
5
Ammoxidation reaction of the present invention is to carry out in gas phase, the mixture of alkane, ammonia and molecular oxygen and inert diluent (if any) is in the fixed bed of catalyst mixture or gravity flowing bed, fluid bed or contact successfully in the transfer reaction apparatus fast.
The example of applicable inert diluent is N in the reaction
2, He, CO
2, H
2O and Ar.
The variable range of reaction temperature is 350-700 ℃, but normally 430-520 ℃.Latter's temperature range is specially adapted to the occasion that propane ammoxidation is an acrylonitrile.
Average contact time generally is 0.01-10 second, but 0.02-10 second normally, more usually 0.1-5 second.
The scope of reaction pressure is 2-45 pound/inch normally
2(absolute pressure).The most frequent pressure is a little more than atmospheric pressure.
Following embodiments of the invention are exemplary, and never should regard certain restriction as.
Embodiment 1
A kind of 50%(of containing weight) empirical formula is VSb
5WO
XWith 50%(weight) Al
2O
3The method for preparing catalyst of carrier is as follows:
Be equipped with in the flask of stirring 5.4 gram NH can adding hot reflux
4VO
3Be dissolved in 150 milliliters of hot water.In this hot water, add 33.6 gram Sb
2O
3, and this slurries boiling reflux spent the night in 16-18 hour.Have ammonia to emit, and the vanadium-antimony oxide mixture become celadon.
During another is operated separately, with 59.0 gram Catapal SB(hydrated aluminas) and 200 milliliters of H
2O(is cold) add that 23.0 gram acetic acid (10% solution) mix, and stir until this suspension gelling.Use 3 hours approximately, this gels-soft and even, its denseness is the super cream shape.
At this moment, vanadium antimony slurries are transferred in the beaker.Then with 12.5 gram ammonium metatungstate and about 25 milliliters of H
2The solution that O forms adds, and is stirring (magnetic force) adding alumina gel down subsequently.After the part evaporation, this mixture becomes very thick so that can not stir.Then it is transferred in the evaporating dish, in 110-120 ℃ of baking oven, continues evaporation, then dried overnight.This dried material 350 ℃ of following precalcinings 5 hours, is crossed 20/35 mesh sieve, calcined 3 hours down at 610 ℃ afterwards.
Embodiment 2
A kind of 50%(of containing weight) empirical formula is VSb
3.5P
0.5WC
XWith 50%(weight) Al
2O
3The method for preparing catalyst of carrier is as follows:
Can add hot reflux one and be equipped with in the flask of stirring, with 3.81 gram NH
4VO
3Be dissolved in 90 milliliters of hot water.In this hot solution, add 16.6 gram Sb
2O
3, and this slurries boiling reflux spent the night in 16-18 hour.Have ammonia to emit this moment, and this vanadium antimony mixture becomes celadon.
In another operation, with 35.5 gram Catapal SB(hydrated aluminas) and 127.2 milliliters of H
2O(is cold) and 14.1 gram acetic acid (10% solution) mixing, and stir suspension gelling so far.Need 3 hours approximately, this gels-soft and even, its denseness is the super cream shape.
At this moment, vanadium antimony slurries are transferred in the beaker.Then add by 8.80 gram ammonium metatungstate and about 20 milliliters of H
2The solution that O forms, and add by 1.77 gram (NH
4)
2HPO
4Solution in water is stirring (magnetic force) adding alumina gel down subsequently.After the part evaporation, this mixture becomes very thick so that can not stir.Then it is transferred in the evaporating dish, in 110-120 ℃ of baking oven, continues evaporation, dried overnight thereupon.This dried material 350 ℃ of following precalcinings 5 hours, is crossed 20/35 mesh sieve, calcined 3 hours down at 610 ℃ afterwards.
Embodiment 3
With 88.36 gram Fe(NO
3)
39H
2O under agitation is dissolved in 170 ml waters, and this solution is under agitation added to 687.86 gram 12%(weight) Sb
2O
5In the colloidal sol.Generate a kind of light brown gel of muddiness, can be broken under stirring fast.This dispersion heating is concentrated, in evaporating dish, be placed on dried overnight in 130 ℃ of baking ovens afterwards.Then with it 290 ℃ of following heat treated 3 hours, and 425 ℃ of following heat treated 3 hours, afterwards 610 ℃ of following heating and calcinings 3 hours.This catalyst by levigate to 20-35 order granularity.This catalyst consist of Fe
3Sb
7O
X
Embodiment 4
A kind of experimental group becomes 60%(weight) Fe
10Sb
20Cu
32Te
1.36Mo
0.57W
0.083V
0.15O
XWith 40%(weight) SiO
2Catalyst solution 1: with 38.4 pounds of deionized water (D.I.H
2O) add in the container and be heated to 80 ℃.Afterwards wherein, be reduced to and with temperature and be about 50-60 ℃ 88.9 gram ammonium paratungstates dissolvings.Then 72.8 gram ammonium metavanadates are dissolved in this solution, temperature is reduced to 35-40 ℃ subsequently.Then with 406 the gram ammonium paramolybdates be dissolved in this solution, and with adjustment to 30-35 ℃.
Solution 2: in another container, add 120 pounds of metal nitrate aqueous solution, wherein contain (percetage by weight): 4.27%Fe, 1.49%Cu, 1.30%Te and 23.7%-NO
3Adding 70.2%(weight in this solution) HNO
3808 pounds.
Having one and to add 71.8 pounds of deionized waters and 40%(weight in 50 gallon container of reflux condenser and agitator) Ludox (uses NH
3Stabilisation) 71.8 pounds.When stirring, complete soln 2 is added and stirred 5 minutes.Add Sb afterwards
2O
326.3 pound then adds complete soln 1 and continue and stirred 5 minutes.
After this, through 50-60 minute, add 14.7%(weight) 45.8 pounds of ammoniacal liquor, maintain the temperature at 32-38 ℃ simultaneously.Measuring the pH value down at about 40 ℃ is 2.35.
Then these slurries are heated to backflow (about 100 ℃) through more than 1 hour, refluxed thereafter 4 hours.After this, slurries partly are transferred in the evaporating dish, and in baking oven, evaporate and dried overnight under 110-120 ℃.This siccative is 290 ℃ of down heating 3 hours and 425 ℃ of heating 3 hours down, then levigate to the 20-35 order, and 825 ℃ of following heating and calcinings 3 hours.
When the ammoxidation operation test of following embodiment, it is in the 3/8 inch tubular type stainless steel fixed bed reactors that catalyst or catalyst mixture are in internal diameter.When using the particulate catalytic agent composition (as embodiments of the invention), two kinds of catalyst components of requirement are placed a bottle, and before the catalyst component of this aequum is put into reactor, sway until being uniformly dispersed.Reactor is equipped with pre-hot leg pipe and is immersed in the molten salt bath of controllable temperature.Gas feed enters reactor bottom through pre-hot leg pipe again by the mass flow controller metering.With syringe pump water is introduced through the dividing plate at pre-hot leg pipe top.Charging is sent into catalyst and was carried out one hour before collecting product; Each embodiment moves and continues 30 minutes, collects product during this period to analyze.
Embodiment 5
Catalyst in the present embodiment is the mixture of catalysts of catalyst and the embodiment 4 of embodiment 1, and the weight ratio of the former with the latter is 0.20.Reaction temperature is 470 ℃, and raw materials components mole ratio is 5 propane/1NH
3/ 2O
2/ 1H
2O.Be 1.8 seconds time of contact.The analysis showed that of reactor effluent: conversion of propane is 12.0%; Yield and selectivity that propane generates acrylonitrile are respectively 2.8% and 23.3%; The selectivity that generates propylene is 38.3%.
Comparative examples A
Reaction temperature is 470 ℃ in this example, and molar feed ratio is 5 propane/1NH
3/ 2O
2/ 1H
2O.Catalyst is the catalyst of single embodiment 1.Be 0.2 second time of contact.The analysis showed that of reactor effluent: conversion of propane is 16.9%; Yield and selectivity that propane generates acrylonitrile are respectively 3.3% and 19.5%; The selectivity that generates propylene is 50.6%.
Embodiment 6
Catalyst in the present embodiment is embodiment 2 catalyst and embodiment 3 mixture of catalysts, and the weight ratio of the former with the latter is 0.15.Reaction temperature is 470 ℃, and molar feed ratio is 5 propane/1NH
3/ 2O
2/ 1H
2O.Be 2.2 seconds time of contact.The analysis showed that of reactor effluent: conversion of propane is 14.5%; Yield and selectivity that propane generates acrylonitrile are respectively 5.3% and 36.5%; The selectivity that generates propylene is 27.4%.
Comparative example B
Reaction temperature is 470 ℃ in this example, and molar feed ratio is 5 propane/1NH
3/ 2O
2/ 1H
2O.Catalyst is the catalyst of single embodiment 2.Be 0.3 second time of contact.The analysis showed that of reactor effluent: conversion of propane is 18.3%; Yield and selectivity that propane generates acrylonitrile are respectively 3.7% and 20.4%; The selectivity that generates propylene is 52.8%.
Comparative example C
Reaction temperature is 470 ℃ in this example, and molar feed ratio is 5 propane/1NH
3/ 2O
2/ 1H
2O.Catalyst is the catalyst of single embodiment 3.Be 0.8 second time of contact.The analysis result of reactor effluent shows: conversion of propane is 2.9%; Yield and selectivity that propane generates acrylonitrile are respectively 1.2% and 42.1%; The selectivity that generates propylene is 15.9%.
Embodiment 7
Catalyst in the present embodiment is the mixture of catalysts of catalyst and the embodiment 4 of embodiment 2, and the weight ratio of the former with the latter is 0.15.Reaction temperature is 470 ℃, and molar feed ratio is 5 propane/1NH
3/ 2O
2/ 1H
2O.Be 1.5 seconds time of contact.The analysis result of reactor effluent shows: conversion of propane is 10.6%; Yield and selectivity that propane generates acrylonitrile are respectively 3.5% and 32.4%; The selectivity that generates propylene is 34.0%.
Will be obviously for those skilled in the art, only otherwise deviate from the scope of spirit and scope of the present disclosure or claim,, can make or draw various variations to the present invention according to above-mentioned open explanation and discussion.
Claims (8)
1, a kind of catalyst mixture that is suitable for propane ammoxidation generation acrylonitrile; it comprises the tight granulate mixture of being made up of first catalyst component and second catalyst component, and this first catalyst component contains the catalyst of the component of the diluent/carrier of 10-99% (weight) and 90-1% (weight) in the ratio shown in the following empirical formula:
VSb
mA
aB
bC
cT
tO
x, formula (1)
Wherein A is one or more among W, Sn, Mo, B, P and the Ge;
B is one or more among Fe, Co, Ni, Cr, Pb, Mn, Zn, Se, Te, Ga, In and the As;
C is one or more among alkali metal and the Tl;
T is one or more among Ca, Sr and the Ba; With
Wherein m is 0.01-20; A is 0.2-10; B is 0-20; C is 0-1; T is 0-20; (a+b+c+t): ratio (l+m) is 0.01-6; The x value is decided by the oxidation state of other elements in the formula, and in the formula average valence of antimony be higher than+3 and the average valence of vanadium be lower than+5,
Described second catalyst component contains the catalyst of the component of the diluent/carrier of 0-99% (weight) and 100-1% (weight) in the ratio shown in the following empirical formula:
Fe
10Sb
dTe
eMe
fGgQ
hR
iO
xFormula (2)
In the formula
Me is V, Mo, W or their composition;
G is one or more alkali metals;
Q is one or more among Cu, Mg, Zn, La, Ce, Cr, Mn, Co, Ni, Bi, the Sn;
R is one or more among P, the B
And d=10-60, e=0-10, f=0-6, g=0-5, h=0-10, i=0-5, the numerical value of x are decided by the valence state requirement of existing other elements, and first catalyst component is 0.001 to 2.5 to the weight ratio of second catalyst component in described mixture.
2, according to the mixture of claim 1, wherein A comprises whenever has an atom V to have 0.2 atom W at least, and A atom summation comprises whenever having an atom V to have 0.4(W atomicity+Sn atomicity at least).
3, according to the mixture of claim 1, wherein A comprises whenever has an atom V to have 0.2 atom W at least.
4, according to the mixture of claim 3, wherein A comprises whenever has an atom V to have 0.4 atom P at least.
5, according to the mixture of claim 1, the carrier of wherein said formula (1) catalyst is to be selected from: silica, aluminium oxide, titanium oxide, silica-niobium oxide, silica-zirconia, silica-titanium oxide, silica-alumina, Nb
2O
5And magnesia.
6, according to the mixture of claim 3, the described carrier of its Chinese style (1) catalyst is to be selected from: silica-alumina and aluminium oxide, wherein contain 20-100%(weight) aluminium oxide; Silica-titanium oxide and titanium oxide wherein contain 20-100%(weight) titanium oxide; Silica-zirconia and zirconia wherein contain 80-100%(weight) zirconia; And silica-niobium oxide and niobium oxide, wherein contain 30-100%(weight) niobium oxide (Nb
2O
5).
7, according to each mixture among the claim 1-5, wherein m is 2-10.
8, according to each mixture among the claim 1-5, wherein diluent/carrier comprises 20-100%(weight in described first catalyst component) zirconia and 80-0%(weight) silica.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/067,891 US4769355A (en) | 1987-04-20 | 1987-04-20 | Catalyst system for ammoxidation of paraffins |
| US067,891 | 1987-04-20 | ||
| CN88102108A CN1016780B (en) | 1987-04-20 | 1988-04-19 | Method for ammoxidatin of paraffins and catalyst system therefor |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88102108A Division CN1016780B (en) | 1987-04-20 | 1988-04-19 | Method for ammoxidatin of paraffins and catalyst system therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1061165A true CN1061165A (en) | 1992-05-20 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91111300A Pending CN1061165A (en) | 1987-04-20 | 1991-11-30 | The catalyst system of alkane ammoxidation |
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| Country | Link |
|---|---|
| CN (1) | CN1061165A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311492C (en) * | 2001-04-13 | 2007-04-18 | 株式会社日立制作所 | Electric contact unit and manufacturing method thereof |
-
1991
- 1991-11-30 CN CN91111300A patent/CN1061165A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311492C (en) * | 2001-04-13 | 2007-04-18 | 株式会社日立制作所 | Electric contact unit and manufacturing method thereof |
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