CN101992106B - Alkane ammoxidation catalyst - Google Patents
Alkane ammoxidation catalyst Download PDFInfo
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- CN101992106B CN101992106B CN2009100577982A CN200910057798A CN101992106B CN 101992106 B CN101992106 B CN 101992106B CN 2009100577982 A CN2009100577982 A CN 2009100577982A CN 200910057798 A CN200910057798 A CN 200910057798A CN 101992106 B CN101992106 B CN 101992106B
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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
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Abstract
The invention relates to an alkane ammoxidation catalyst, which mainly solves the problem that the catalyst has pool stability because the preparation process is complex with volatile Te and the like, the preparation environment is unstable, the active components of the catalyst are volatile in the prior art. The invention solves the problem by adopting the technical scheme which comprises the following steps of: adopting the catalyst which contains a silicon dioxide carrier and comprises a composition with a general formula of MoVaNbbTecDdEeOx according to an atomic ratio, and adopting Mo-V-Nb-Te-D base as the main component of the catalyst, wherein D is selected from at least one of B or Ca, E is selected from one of Sn, Ti, Fe, Bi, Sb or W; in the preparation process, adding a reducing agent and acid to change the preparation environment, namely dissolving salts or oxides corresponding to Mo and Te first, and then respectively adding solution of acid or salts corresponding to V, Nb, D and E; adding a required amount of reducing agent and acid to adjust the pH value; and finally, adding a required amount of silica sol. The alkane ammoxidation catalyst can be used in the industrial production of preparing unsaturated nitriles through alkane ammoxidation.
Description
Technical field
The present invention relates to a kind of alkane ammoxidation reaction catalyst, especially about the catalyst of a kind of propane ammoxidation acrylonitrile production or iso-butane prepared by ammoxidation methacrylonitrile.
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 the Catalysts and its preparation method of alpha, beta-unsaturated nitriles 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 all to exist Sb to reflux in the prior art to cause complicated process of preparation and yield not high, and the volatile bad problem of catalyst stability that causes of Te provides a kind of catalyst of new alkane ammoxidation reaction.This catalyst is used for the propane ammoxidation acrylonitrile production or the reaction of iso-butane prepared by ammoxidation methacrylonitrile has advantages of excellent stability, and reaction temperature is low, can keep the advantage of higher yields for a long time, and this catalyst preparation process is simple.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of alkane ammoxidation reaction catalyst, contain silica supports and comprise the composition of following general formula with atomic ratio measuring:
MoV
aNb
bTe
cD
dE
eO
x
Wherein D is selected from least a among B or the Ca, and E is selected from a kind of among Sn, Ti, Fe, Bi, Sb 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 0.01～1.0;
The span of e 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 Te 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 the corresponding acid of aequum D or its salt and corresponding salt of E 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 respectively wherein, add the reducing agent and the acid 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, temperature be in 400～800 ℃ the inert atmosphere roasting 0.5～8 hour the alkane ammoxidation catalyst.
In the technique scheme, the value preferable range of d is 0.01～0.6, and reducing agent is preferably at least a or its mixture in oxalic acid and the pyruvic alcohol, and acid is preferably H
2SO
4And HNO
3In at least a or its mixture, catalyst sintering temperature preferable range is 500～700 ℃, calcination atmosphere is preferably nitrogen, the roasting time preferable range is 1～4 hour.
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 tellurium component, hydroxide or its ammonium salt in the catalyst; Niobium can be used its oxide, hydroxide, nitrate or oxalates, and the boron component can be used its acid or its ammonium salt, and the calcium component can be used its oxide or nitrate.
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,, improved catalyst oxidation-rate of reduction because catalyst has kept good oxidation and reducing power balance in forming; In the preparation process, regulate the oxidation state of oxide through adding reducing agent; Add acid control pH value of solution value, the existence of boron or calcium constituent makes between Te, Mo, B or the Ca and generates crystal, reduces the volatilization of tellurium element; Thereby obtain good catalyst stability, the catalyst that availability can be good.Catalyst of the present invention has to be formed simply, and needed raw material is easy to get, good reproducibility; The catalyst that makes is used for the propane ammoxidation reaction; It is good that its acrylonitrile yield reaches 33%, 720 hour stability test result, and acrylonitrile yield also remains on more than 31%; 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]
14.2 gram ammonium heptamolybdates and 4.65 gram telluric acids are dissolved in the 40.0 gram hot water, process solution (I); 3.19 gram ammonium metavanadates are dissolved in the 70.0 gram hot water, process solution (II); 6.04 gram niobium oxalates are dissolved in the 17.0 gram hot water, process solution (III); 0.49 gram boric acid is dissolved in 5.0 grams processes (IV) in the water; 2.32 gram oxalic acid are dissolved in 5 grams process solution (V) in the water; Getting the 1ml98% concentrated sulfuric acid is dissolved in 9 grams and processes solution (VI) in the water.Under agitation solution (II) is joined in the solution (I), add solution (III), solution (IV), solution (V) and solution (VI) 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 is 2 hours in 600 ℃ of nitrogen atmospheres, can get propane ammoxidation catalyst 50%Mo
1V
0.34Nb
0.24Te
0.25B
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]
14.4 gram ammonium heptamolybdates and 4.72 gram telluric acids are dissolved in the 40.0 gram hot water, process solution (I); 3.24 gram ammonium metavanadates are dissolved in the 70.0 gram hot water, process solution (II); 6.12 gram niobium oxalates are dissolved in the 17.0 gram hot water, process solution (III).Under agitation solution (II) is joined in the solution (I), add solution (III) again, 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 is 2 hours in 600 ℃ of nitrogen atmospheres, can get propane ammoxidation catalyst 50%Mo
1V
0.34Nb
0.24Te
0.25O
x+ 50%SiO
2, get 20～40 orders behind the compressing tablet and carry out the fixed bed micro anti-evaluation.
[embodiment 2～6 and comparative example 2～3]
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 one
| Embodiment | Catalyst is formed | The preparation committed step | Conversion of propane % | Acrylonitrile selectivity % |
| Embodiment 1 | 50％Mo 1V 0.34Nb 0.24Te 0.25B 0.1O x+50％SiO 2 | Reducing agent is an oxalic acid, and acid is sulfuric acid | 57.8 | 57.5 |
| Comparative example 1 | 50％Mo 1V 0.34Nb 0.24Te 0.25O x+50％SiO 2 | No reducing agent, anacidity | 41.5 | 30.4 |
| Comparative example 2 | 40％Mo 1V 0.34Nb 0.24Te 0.25B 0.01O x+60％SiO 2 | Reducing agent is an oxalic acid, anacidity, roasting in the air | 8.9 | 5.7 |
| Comparative example 3 | 20％Mo 1V 0.13Nb 0.12Te 0.25B 0.2O x+80％SiO 2 | No reducing agent, acid is nitric acid, roasting in 800 ℃ of air | 7.8 | 4.6 |
| Embodiment 2 | 50％Mo 1V 0.34Nb 0.24Te 0.25Ca 0.1O x+50％SiO 2 | Reducing agent is an oxalic acid, and acid is sulfuric acid | 58.0 | 58.5 |
| Embodiment 3 | 30％Mo 1V 0.34Nb 0.24Te 0.25Ca 0.1Bi 0.01O x +70％SiO 2 | Reducing agent is an oxalic acid, and acid is nitric acid | 49.8 | 54.3 |
| Embodiment 4 | 50％Mo 1V 0.31Nb 0.22Te 0.25B 0.08O x+50％SiO 2 | Reducing agent is a pyruvic alcohol | 55.2 | 56.8 |
| Embodiment 5 | 50％Mo 1V 0.37Nb 0.26Te 0.25Ca 0.1Sb 0.02O x +50％SiO 2 | Roasting is 2 hours in 500 ℃ of nitrogen | 54.3 | 53.5 |
| Embodiment 6 | 30％Mo 1V 0.34Nb 0.24Te 0.25B 0.1Bi 0.01O x +70％SiO 2 | Reducing agent is an oxalic acid, and acid is nitric acid | 50.2 | 53.8 |
| Embodiment 7 | 50％Mo 1V 0.34Nb 0.24Te 0.25B 0.1Ca 0.1Mg 0.02 Bi 0.01O x+50％SiO 2 | Reducing agent is an oxalic acid, and acid is nitric acid | 58.8 | 58.3 |
| Embodiment 8 | 40％Mo 1V 0.22Nb 0.15Te 0.19Ca 0.15B 0.05O x +60％SiO 2 | Roasting is 4 hours in 700 ℃ of nitrogen | 56.9 | 56.1 |
| Embodiment 9 | 60％Mo 1V 0.34Nb 0.24Te 0.25B 0.1O x+40％SiO 2 | Reducing agent is an oxalic acid, and acid is sulfuric acid, and successive reaction is after 30 days | 56.5 | 54.9 |
The stable appraisal result of embodiment 1 and comparative example 1 is seen table 2.
Table 2
Claims (7)
1. alkane ammoxidation reaction catalyst, contain silica supports and comprise the composition of following general formula with atomic ratio measuring:
MoV
aNb
bTe
cD
dE
eO
x
Wherein D is selected from least a among B or the Ca, and E is selected from a kind of among Sn, Ti, Fe, Bi, Sb 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 0.01～1.0;
The span of e is to being less than or equal to 1.0 greater than 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 Te 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 the corresponding acid of aequum D or its salt and corresponding salt of E 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 respectively wherein, add the reducing agent and the acid 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, temperature be in 400～800 ℃ the inert atmosphere roasting 0.5～8 hour the alkane ammoxidation catalyst.
2. alkane ammoxidation reaction catalyst according to claim 1, the span that it is characterized in that d is 0.01～0.6.
3. alkane ammoxidation reaction catalyst according to claim 1 is characterized in that reducing agent is at least a in oxalic acid and the pyruvic alcohol.
4. alkane ammoxidation reaction catalyst according to claim 1 is characterized in that acid is H
2SO
4And HNO
3In at least a.
5. alkane ammoxidation reaction catalyst according to claim 1 is characterized in that sintering temperature is 500～700 ℃.
6. alkane ammoxidation reaction catalyst according to claim 1 is characterized in that inert atmosphere is a nitrogen.
7. alkane ammoxidation reaction catalyst according to claim 1 is characterized in that roasting time is 1～4 hour.
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| CN115518646B (en) * | 2021-06-24 | 2024-03-26 | 中国石油化工股份有限公司 | Catalyst for low-carbon alkane oxidation/ammoxidation and preparation method thereof |
| CN114100652B (en) * | 2021-12-10 | 2023-10-13 | 北京道思克矿山装备技术有限公司 | Catalyst for producing hydrogen cyanide by methanol gas-phase catalytic ammoxidation and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101428230A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | Catalysts for the ammoxidation of alkanes |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101428230A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | Catalysts for the ammoxidation of alkanes |
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