CN101884918B - Method for preparing antimony-containing catalyst used for ammoxidation of alkane - Google Patents
Method for preparing antimony-containing catalyst used for ammoxidation of alkane Download PDFInfo
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- CN101884918B CN101884918B CN200910057219A CN200910057219A CN101884918B CN 101884918 B CN101884918 B CN 101884918B CN 200910057219 A CN200910057219 A CN 200910057219A CN 200910057219 A CN200910057219 A CN 200910057219A CN 101884918 B CN101884918 B CN 101884918B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a method for preparing an antimony-containing catalyst used for ammoxidation of alkane, which mainly solves the problem of poor stability of the catalyst due to difficult stable combination between Sb and Mo, complex preparation process, unstable preparation environment and easy volatilization of active ingredients of the catalyst existing in the prior art. In the method, the Mo-V-Nb-Sb base is used as a main ingredient of the catalyst, and a silica carrier and a composition including the MoVaNbbSbcDdOx general formula based on an atomic ratio are contained, wherein D is one of Sn, Ti, Fe, Bi, Te and W. The preparation environment is changed by dissolving corresponding salts or oxides of Mo and Sb; then respectively adding the solution of the corresponding salts or the oxides of V and Nb into the mixture; adding a proper amount of reducing agent into the mixture; and finally adding silica sol into the mixture. The technical scheme adopting a two-stage calcination mode can better solve the problem. The method can be applied to industrial production of unsaturated nitriles by using ammoxidation of alkane.
Description
Technical field
The present invention relates to a kind of method for preparing antimony-containing catalyst that is used for alkane ammoxidation reaction.Especially about a kind of propane ammoxidation acrylonitrile production or iso-butane prepared by ammoxidation methacrylonitrile Preparation of catalysts method.
Background technology
Although the most of ammoxidation of propylene technology that adopts BP/Sohio of the production of acrylonitrile at present; But along with going deep into of petrochemical industry change of market and the research of alkane selective oxidation; Because propane and the price difference XOR iso-butane of propylene and the price variance of isobutene, come into one's own day by day by the process route of propane ammoxidation acrylonitrile production or iso-butane prepared by ammoxidation methacrylonitrile.
For obtaining the propane ammoxidation acrylonitrile production catalyst of high activity, high selectivity, people have carried out a series of improvement through constantly exploring.Previously attempt to develop a kind of propane ammoxidation is generated the effective ways of acrylonitrile, the result is that yield is not high enough, perhaps in the charging thing, must add halogen and make co-catalyst.In the charging thing, must add halogen and do in the co-catalyst method, not only require reactor to process, and require the co-catalyst quantitative recovery by extraordinary resistant material.This surcharge has been offset the advantage of propane/propylene price difference, has hindered these catalyst in industrial application.
Patent CN1029397C discloses certain O composite metallic oxide catalyst that contains V, Sb, W and some optional elements, is applied in C
3~C
4Alkane ammoxidation is produced α; The method of alpha, beta-unsaturated nitriles and alkene, wherein the average valence mumber of Sb be higher than+3, the average valence mumber of V is lower than+5; The method is used in propane ammoxidation when producing acrylonitrile; In the reactant steam need be arranged, severe reaction conditions is brought influence to later industrialized plant capacity.
Patent CN1062306A discloses the catalyst system of alkane ammoxidation; Adopt a kind of granulate mixture of two kinds of catalyst components; First kind of catalyst component is effective especially to quickening by alkane generation unsaturated nitrile and alkene; Second kind of catalyst component is effective especially to the conversion of unsaturated nitrile to quickening alkene, and the method system is complicated, and acrylonitrile yield is lower.
Patent CN1178903C discloses the vanadium-antimony-oxide substrate catalyst that the molybdenum that is used for selective paraffin ammoxidation helps catalysis; With the catalyst after the moistening equably calcining of the aqueous solution that contains molybdenum, drying is washed with isobutanol after the calcining again; The method prepares the process complicacy; In the preparation process, wash with isobutanol, and then dry, operate dangerous property.
Patent CN1087734C discloses a kind of method that is prepared acrylonitrile or methacrylonitrile by propane or iso-butane through ammoxidation; Catalyst comprises that composite oxides and load above that have the silica supports of composite oxides, and wherein composite oxides are expressed as:
Mo
1Te
aV
bNb
cX
dO
n
Wherein X is at least a element that is selected from tantalum, tungsten, chromium, titanium, zirconium, antimony, bismuth, tin, hafnium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, zinc, aluminium, gallium, indium, thallium, phosphorus and alkaline-earth metal.
Above-mentioned catalyst can obtain higher acrylonitrile yield, but contains volatile element Te in the catalyst activity component, need in reaction, add Te, and stability is bad, thereby does not have enough life-spans to make this method uneconomical.
Patent CN1174801C discloses a kind of formula Mo that contains
1V
aNb
bX
cZ
yQ
fO
n, wherein X is at least a element that is selected from Te and Sb; Y is at least a element that is selected from Al and W; Z is at least a element that is selected from the element that can be individually formed the oxide with rutile structure, and has the source use of the Z oxide of rutile structure as the Z of preparation catalyst; Q is at least a element that is selected from titanium, tin, germanium, lead, tantalum, ruthenium, rhenium, rhodium, iridium, platinum, chromium, manganese, technetium, osmium, iron, arsenic, cerium, cobalt, magnesium, nickel and zinc; And the Q compound that does not have rutile structure uses as the source of the Q of preparation catalyst.The catalyst acrylonitrile yield that this method makes is higher, but forms complicatedly, and the ingredient requirement height makes that commercial production repeatability is bad and seems uneconomical.
Patent CN1771085A discloses a kind of catalytic gas phase oxidation of propane or iso-butane or oxide catalyst of gas phase catalysis ammoxidation of being used for; It comprises with the specific atoms ratio and contains molybdenum (Mo), vanadium (V), niobium (Nb) and antimony (Sb) as the oxide of component, uses H
2O
2The percent reduction and the specific area of methods such as the oxidation state control catalyst of adjustment oxide.The catalyst that this method makes can stably be produced unsaturated carboxylic acid or unsaturated nitrile with higher yields for a long time, but the controlled condition harshness makes Catalyst Production be difficult for.
All exist corresponding salt of Sb or oxide to reflux among the existing preparation method, adopt the V of severe toxicity
2O
5Be raw material, or the catalyst activity component that makes is volatile and cause problems such as catalyst stability is bad, directly causes preparation process of preparing environment unstable at last, makes that corresponding unsaturated nitrile yield is not high or catalyst stability is bad and seem uneconomical.
The present invention alkane ammoxidation system α different from the past, the place of alpha, beta-unsaturated nitriles Preparation of catalysts method is: 1. catalyst is formed simply, and raw material is easy to get; 2. Preparation of Catalyst good reproducibility, the catalyst yield that makes is high, has good stability, and reaction temperature is low, can be used in the commercial production.
Summary of the invention
Technical problem to be solved by this invention is to overcome all to exist Sb backflow to cause complicated process of preparation and yield not high in the prior art document; Active component is volatile to cause problems such as catalyst stability is bad, and a kind of new method for preparing antimony-containing catalyst that is used for alkane ammoxidation reaction is provided.The catalyst that adopts this preparation method to make has advantages of excellent oxidation-reduction stability, and reaction temperature is low, and product cleans and can keep for a long time the advantage of higher yields.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of method for preparing antimony-containing catalyst that is used for alkane ammoxidation reaction, catalyst contain silica supports and comprise the composition of following general formula with atomic ratio measuring:
MoV
aNb
bSb
cD
dO
x
Wherein, D is selected from a kind of among Sn, Ti, Fe, Bi, Te or the W;
The span of a is 0.1~1.0;
The span of b is 0.01~1.0;
The span of c is 0.01~1.0;
The span of d is 0~1.0;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
Wherein the consumption of carrier silica is 30~70% by weight percentage in the catalyst;
This Preparation of catalysts comprises the steps:
1) with aequum Mo and corresponding salt of Sb or the oxide solution (I) of processing soluble in water;
2) with corresponding salt of aequum V or the oxide solution (II) of processing soluble in water;
3) with corresponding salt of aequum Nb or the oxide solution (III) of processing soluble in water;
4) with corresponding salt of aequum D or the oxide solution (IV) of processing soluble in water;
5) solution (II) is joined in the solution (I); Again solution (III), solution (IV) are joined wherein, add the reducing agent of aequum then, add the Ludox of aequum at last; Make the slurry of catalyst; This slurry stirs down evaporation at 80~180 ℃ and obtains viscous paste always, and is dry then, is roasting 0.5~4 hour in 200~400 ℃ the air in temperature; In 400~800 ℃ inert atmosphere, flow velocity is that roasting got the alkane ammoxidation catalyst in 0.5~8 hour under 10~90 ml/min then.
In the technique scheme; Catalyst sintering temperature preferable range in air is 250~350 ℃; The roasting time preferable range is 1~2 hour, and calcination atmosphere is preferably nitrogen in the inert gas, and the sintering temperature preferable range is 500~700 ℃; The roasting time preferable range is 1~4 hour, and the flow velocity preferable range is 20~80 ml/min.
The raw material of preparation catalyst of the present invention is:
The most handy corresponding oxide of molybdenum component in the catalyst or its ammonium salt, the most handy corresponding oxide of vanadium component or its ammonium salt, the most handy corresponding oxide of antimony component, hydroxide or its ammonium salt in the catalyst; Niobium can be used its oxide, hydroxide, nitrate or oxalates.
For reaching above-mentioned purpose and advantage; Method of the present invention also is included in gas phase makes the alkane that is selected from propane and iso-butane and molecular oxygen and ammonia carry out catalytic reaction, and wherein reactant reacts at reaction zone and catalyst, preparation α; Alpha, beta-unsaturated nitriles, acrylonitrile or methacrylonitrile; Desired molecule oxygen can be used pure oxygen from technical standpoint in the raw material components, oxygen enrichment and air, but from economy and the most handy air of security consideration.
Getting into the ammonia of fixed bed reactors and the mol ratio of propane is between 0.8~1.5, is preferably 1.0~1.3.The mol ratio of air and propane is 8~16, is preferably 9.0~14.But from security consideration, the excess of oxygen in the reacting gas can not preferably be not more than 4% greater than 7% (volume).
When catalyst of the present invention was used for fixing bed bioreactor, reaction temperature was 370~450 ℃, was preferably 390~440 ℃.
Though catalyst of the present invention is formed simple, owing to improved the Preparation of catalysts method, thus make that generating crystal between Sb, the Mo obtains good catalyst stability, the catalyst that availability can be good.Preparation method's good reproducibility of the present invention; It is good up to 29%, 720 hour stability test result that the catalyst that makes is used for propane ammoxidation reaction acrylonitrile yield, and acrylonitrile yield also remains on more than 28%; Reaction temperature is low to moderate 400 ℃, has obtained better technical effect.
Activity of such catalysts of the present invention examination is in internal diameter is 8 millimeters fixed bed reactors, to carry out.Loaded catalyst 2.0 gram, 400 ℃ of reaction temperatures, reaction pressure are normal pressure, proportioning raw materials (mole) is a propane: ammonia: air=1: 1.2: 10, catalyst time of contact is 1.2 gram-second/milliliters.
The definition of conversion of propane, acrylonitrile selectivity and once through yield is following in the present invention:
Below by embodiment the present invention is further elaborated, but the present invention is not limited by following examples.
The specific embodiment
[embodiment 1]
17.0 gram ammonium heptamolybdates and 2.4 gram antimony oxides are dissolved in the 40.0 gram hot water, process solution (I); 3.37 gram ammonium metavanadates are dissolved in the 70.0 gram hot water, process solution (II); 2.99 gram niobium oxalates are dissolved in the 9.0 gram hot water, process solution (III); Getting 3.0 gram oxalic acid is dissolved in 5 grams and processes solution (IV) in the water.Under agitation solution (I) is joined in the solution (II), add solution (III) and solution (IV) more successively, add 50 gram weight concentration at last and be 40% Ludox; Make the slurry of catalyst; This slurry is stirred evaporation down at 90 ℃ obtain viscous paste always, dry then, grind; Roasting 1 hour in 300 ℃ of air atmospheres earlier, flow velocity is that roasting can get propane ammoxidation catalyst 50%Mo in 2 hours under 60 ml/min in 600 ℃ of nitrogen atmospheres then
1V
0.3Nb
0.17Sb
0.1O
x+ 50%SiO
2, get 20~40 orders behind the compressing tablet and carry out the fixed bed micro anti-evaluation.
[comparative example 1]
17.0 gram ammonium heptamolybdates and 2.4 gram antimony oxides are dissolved in the 40.0 gram hot water, process solution (I); 3.37 gram ammonium metavanadates are dissolved in the 70.0 gram hot water, process solution (II); 2.99 gram niobium oxalates are dissolved in the 9.0 gram hot water, process solution (III), get 3.0 gram oxalic acid and be dissolved in 5 grams and process solution (IV) in the water.Under agitation solution (I) is joined in the solution (II), add solution (III) and solution (IV) more successively, add 50 gram weight concentration at last and be 40% Ludox; Make the slurry of catalyst; This slurry is stirred evaporation down at 90 ℃ obtain viscous paste always, dry then, grind; Flow velocity is roasting 2 hours under 60 ml/min in 600 ℃ of nitrogen atmospheres, can get propane ammoxidation catalyst 50%Mo
1V
0.3Nb
0.17Sb
0.1O
x+ 50%SiO
2, get 20~40 orders behind the compressing tablet and carry out the fixed bed micro anti-evaluation.
[embodiment 2~5 and comparative example 2~4]
Adopt the catalyst that has different compositions in the following table with embodiment 1 essentially identical method preparation, and under following reaction condition, carry out the reaction of propane ammoxidation generation acrylonitrile, specifically change and the results are shown in Table 1 with prepared catalyst.
The reaction condition of the foregoing description and comparative example is:
Internal diameter is 8 millimeters fixed bed reactors
400 ℃ of reaction temperatures
The reaction pressure atmospheric pressure
Loaded catalyst 2.0 grams
Catalyst gram-second/milliliter times of contact 1.2
Proportioning raw materials (mole) propane/ammonia/air=1/1.2/10
Table 1
Embodiment | Catalyst is formed | The preparation committed step | Conversion of propane % | Acrylonitrile selectivity % |
Embodiment 1 | 50%Mo 1V 0.3Nb 0.17Sb 0.1O x+50%SiO 2 | Oxalic acid is reducing agent, roasting 1 hour roasting 2 hours under 60 ml/min in the nitrogen then in the first air | 55.0 | 53.0 |
Comparative example 1 | 60%Mo 1V 0.3Nb 0.17Sb 0.1O x+40%SiO 2 | Not roasting in air before the roasting in the nitrogen | 48.6 | 35.0 |
Comparative example 2 | 40%Mo 1V 1.13Nb 0.17Sb 0.1O x+60%SiO 2 | Roasting is 2 hours in the nitrogen, and flow velocity is 5 ml/min | 18.2 | 24.6 |
Comparative example 3 | 80%Mo 1V 0.3Nb 0.2Sb 1.1O x+20%SiO 2 | Roasting 5 hours in the air before the roasting in the nitrogen | 27.6 | 38.4 |
Comparative example 4 | 20%Mo 1V 0.3Nb 0.17Sb 0.1O x+80%SiO 2 | Do not add oxalic acid or pyruvic alcohol as reducing agent | 21.8 | 25.9 |
Embodiment 2 | 50%Mo 1V 0.25Nb 0.17Sb 0.12O x+50%SiO 2 | Oxalic acid is reducing agent, and roasting is 0.5 hour in 500 ℃ of nitrogen | 45.9 | 49.6 |
Embodiment 3 | 60%Mo 1V 0.3Nb 0.19Sb 0.2O x+40%SiO 2 | Pyruvic alcohol is a reducing agent, and roasting is 8 hours in 700 ℃ of nitrogen | 48.3 | 51.4 |
Embodiment 4 | 70%Mo 1V 0.27Nb 0.17Sb 0.1W 0.02O x +30%SiO 2 | Oxalic acid is reducing agent, and roasting is 2 hours in 600 ℃ of nitrogen | 52.4 | 48.4 |
Embodiment 5 | 40%Mo 1V 0.31Nb 0.22Sb 0.23Bi 0.01Mg 0.02O x +60%SiO 2 | Oxalic acid is reducing agent, roasting 1 hour roasting 2 hours under 60 ml/min in the nitrogen then in the first air | 55.9 | 54.1 |
Embodiment 6 | 50%Mo 1V 0.3Nb 0.17Sb 0.1O x+50%SiO 2 | Embodiment 1 successive reaction is after 30 days | 54.0 | 51.9 |
The stable appraisal result of embodiment 1 and comparative example 1 is seen table 2
Table 2
Claims (1)
1. a method for preparing antimony-containing catalyst that is used for alkane ammoxidation reaction is dissolved in 17.0 gram ammonium heptamolybdates and 2.4 gram antimony oxides in the 40.0 gram hot water, processes solution (I); 3.37 gram ammonium metavanadates are dissolved in the 70.0 gram hot water, process solution (II); 2.99 gram niobium oxalates are dissolved in the 9.0 gram hot water, process solution (III), get 3.0 gram oxalic acid and be dissolved in 5 grams and process solution (IV) in the water; Under agitation solution (I) is joined in the solution (II), add solution (III) and solution (IV) more successively, add 50 gram weight concentration at last and be 40% Ludox; Make the slurry of catalyst; This slurry is stirred evaporation down at 90 ℃ obtain viscous paste always, dry then, grind; Roasting 1 hour in 300 ℃ of air atmospheres earlier; Flow velocity is roasting 2 hours under 60 ml/min in 600 ℃ of nitrogen atmospheres then, can get the propane ammoxidation catalyst, gets 20~40 orders behind the compressing tablet and carries out the fixed bed micro anti-evaluation; In the preparation process, oxalic acid is reducing agent, roasting 1 hour roasting 2 hours under 60 ml/min in the nitrogen then in the first air;
Reaction condition is:
Internal diameter is 8 millimeters fixed bed reactors
Conversion of propane is 55.0%; The acrylonitrile selectivity is 53.0%.
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CN104549224B (en) * | 2013-10-28 | 2017-09-15 | 中国石油化工股份有限公司 | Unsaturated nitrile catalyst and preparation method thereof |
CN105771959B (en) * | 2014-12-22 | 2018-12-18 | 中触媒有限公司 | A kind of O composite metallic oxide catalyst and its preparation method and application |
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CN1220258A (en) * | 1997-08-11 | 1999-06-23 | 旭化成工业株式会社 | Improved process for producing acrylonitrile or methacrylonitrile from propane or isobutane |
CN1419473A (en) * | 2000-06-15 | 2003-05-21 | 旭化成株式会社 | Catalyst for vapor-phase catalytic oxidation or vapor-phase catalytic ammoxidation of propane or isobutane |
CN101279252A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Catalysts for the ammoxidation of alkanes |
CN101306376A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Tellurium containing alkane ammoxidation reaction catalyst |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1220258A (en) * | 1997-08-11 | 1999-06-23 | 旭化成工业株式会社 | Improved process for producing acrylonitrile or methacrylonitrile from propane or isobutane |
CN1419473A (en) * | 2000-06-15 | 2003-05-21 | 旭化成株式会社 | Catalyst for vapor-phase catalytic oxidation or vapor-phase catalytic ammoxidation of propane or isobutane |
CN101279252A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Catalysts for the ammoxidation of alkanes |
CN101306376A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Tellurium containing alkane ammoxidation reaction catalyst |
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