CN104549261B - The catalyst of alkane unsaturated nitrile - Google Patents
The catalyst of alkane unsaturated nitrile Download PDFInfo
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- CN104549261B CN104549261B CN201310512660.3A CN201310512660A CN104549261B CN 104549261 B CN104549261 B CN 104549261B CN 201310512660 A CN201310512660 A CN 201310512660A CN 104549261 B CN104549261 B CN 104549261B
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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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- 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 relates to the catalyst of alkane unsaturated nitrile, preparation method and its application in low-carbon alkanes ammoxidation synthesizes unsaturated nitrile, the problem of mainly solving low catalyst operational load present in prior art, low conversion of propane and poor stability.The present invention includes the active constituent of general formula according to atomic ratio by using the catalyst of alkane unsaturated nitrile：VaA1.00OxA is at least one of Fe, Ca, Mg, Ni, Al, Zr element, and a span be 0.1~1.0, x for the total technical scheme of the oxygen atom needed for meeting each element chemical valence in catalyst, the problem is preferably solved, in the industrial production available for low-carbon alkanes ammoxidation unsaturated nitrile.
Description
Technical field
Insatiable hunger is synthesized the present invention relates to the catalyst of alkane unsaturated nitrile, preparation method and its in low-carbon alkanes ammoxidation
With the application in nitrile.
Background technology
Acrylonitrile is the important monomer of synthetic fibers, synthetic rubber and synthetic resin, is the important of basic organic industry
Raw material.By development for many years, acrylonitrile industrial production technology has reached its maturity and perfect.At present, more than the % of the whole world 95
Acrylonitrile commercial plant all use Sohio method technique of BP/Ineos companies using propylene as raw material.
In recent years, with the development and utilization of large-scale shale gas, huge price difference is formd between propane and propylene.Entirely
The main production firm of ball acrylonitrile, all actively input exploitation is closed with propane (iso-butane) for the acrylonitrile (methacrylonitrile) of raw material
Into technique, to reduce production cost, product competitiveness is improved.2 months 2013, Japanese Asahi Kasei companies were in Thailand
State builds up acrylonitrile commercial plant of global first 200,000 tons/year of the set using propane as raw material and successfully gone into operation.
At present, propane (iso-butane) ammoxidation synthesis of acrylonitrile (methacrylonitrile) catalyst mainly has Mo-V-Nb-Te
And the big catalyst system and catalyzings of Sb-V two (Sb).
([1] Robert K. Grasselli. Advances and future trends in such as Grasselli
selective oxidation and ammoxidation catalysis. Catalysis Today,1999, 49:141-
153. [2]. Robert K. Grasselli. Selectivity issues in (amm)oxidation
catalysis. Catalysis Today,2005, 99:23-31. [3]. Robert K. Grasselli, Douglas
J. Buttrey, James D. Burrington, et al. Active centers, catalytic behavior,
symbiosis and redox properties of MoV(Nb,Ta)TeO ammoxidation catalysts.
Topics in Catalysis, 2006, 38(1-3):6-16.) to Mo-V-Nb-Te (Sb)-OxCatalyst is deeply ground
Study carefully, it is believed that by club shaped structure orthorhombic phase M1, (chemical formula is Mo to the catalyst7.8V1.95Nb0.86Te1.33Ox, or { TeO }1-x
(Mo,V,Nb)10O28, { TeO } is the component inserted in skeleton duct), (chemical formula is six side phase M2 of slab construction standard
Mo1.0V0.28/0.31Nb0.08Te0.27-0.39O4.24, or { TeO }2-x (Mo,V,Nb)6O18) and trace monocline crystalline phase TeMo5O16Group
Into.Wherein M1 is that propane activates phase, and M2 is propylene activity of conversion phase, and when the two ratio is 3/2, acrylonitrile yield is reached as high as
62%, however, the preparation of simple M1 and M2 phases is complicated.
Anderson type heteropolyacid salts (NH4)6TeMo6O24·nH2O has important for improving the performance of Mo-V series catalysts
Influence, but its formation is closely related with the pH value of slurry, mixing temperature and follow-up heat treatment process in preparation process.Cause
This, Mo-V series catalysts structure that different researchers are obtained, phase composition difference are larger, cause catalyst performance difference very big.
Patent US 6063728, US 6143916 is in Mo-V-Nb-Te (Sb) catalyst XRD spectrum 2θ = 27.3°±
0.3°P1 peak intensities and 2θ = 28.2°± 0.3°P2 peak intensities analyzed, design parameter R=P1/ (P1+P2) is obtained
Go out when catalyst performance is optimal, R is 0.40< R <Between 0.75, this provides reference for the exploitation of Mo-V series catalysts.
Patent CN 1220258A disclose a kind of Mo-V catalyst containing Te, find the extension with the reaction time, catalysis
Agent activity and acrylonitrile yield are gradually reduced, and add the activator containing Mo, Te into reactor by timing, to improve catalysis
The stability of agent, this method brings adverse effect for the continuous production of industrialized unit.
Patent CN 1344584A disclose a kind of preparation method of Mo-V-Nb-Te (Sb) catalyst, although acrylonitrile is received
Rate is higher, but the catalyst preparation process is complicated, particularly the acquisition methods of Nb raw materials, and the amplification for catalyst produces band
Come difficult.
Compared with Mo-V series catalysts, Sb-V catalyst mostly uses aluminum oxide for carrier, therefore its BET specific surface area ratio
Mo-V systems are big.The VSbO with rutile structure is included in the chemical formula that Sb-V catalyst is not fixed, its crystal phase structure4With α-
Sb2O4Association phase, wherein in VSbO4In, Sb is mainly with Sb5+, V is mainly with V3+Form is present (in addition with a small amount of V4+), therefore
VSbO4(V can be used3+-V4+ )Sb1-xO4Represent.When Sb/V is more than 1.0, excessive Sb is with α-Sb2O4It is covered in VSbO4Table
In face, catalytic reaction process, Sb is from α-Sb2O4Association mutually moves to SbVO4In, form Sb5+-V3+/V4+Ammoxidation of propylene reacts
Activated centre, catalyst performance starts to lift (S. Albonetti, G. Blanchard, P. Burattin, T.J.
Cassidy, S.Masetti, F. Trifirò. Mechanism of ammoxidation of propane on a Sb/
V/O system. Catalysis Letters, 1997, 45:119-123.)。
Sb-V catalyst can be by V2O5And Sb2O3Solid phase reaction occurs at high temperature to prepare, can also be mixed by V, Sb slurry
Close and be prepared by co-precipitation, now V, Sb valence state in catalyst, crystal phase structure and catalytic performance are relevant with its preparation method,
Such as Sb/V atomic ratios, metal-modified ionic species, mixing temperature and heat treatment condition etc..
(Shahid Shaikh, Kathleen Bethke, the Edouard Mamedov. Propane such as Shaikh
ammoxidation on bulk, diluted and supported VSb oxides. Topics in Catalysis,
2006, 38(4):241-249.) by coprecipitation, Mg, Al, W and Zr ion are introduced in Sb-V catalyst.XRD is characterized
As a result show there is AlSbO in catalyst4And MgSb2O6Crystalline phase, and VSbO is not found4Phase.Zr and Mg addition is for Sb-V
The activity influence of catalyst is not obvious；And Al addition, catalyst activity is substantially increased, and Propylene Selectivity is greatly reduced,
Its reason is probably Sb and V due to Al addition so that the two is in VSbO4Isolated well in oxide structure.
In addition, the catalyst of prior art is mostly less than 0.1 h in load-1Under the conditions of operation (such as A of CN 101616732,
CN 101678326 A, CN101678327 A, CN 101878194 A, CN101970109 A and CN 102176966 A), and
The problem of there is low conversion of propane and poor stability under high-load condition.
The content of the invention
One of technical problems to be solved by the invention are the catalyst of alkane ammoxidation unsaturated nitrile in the prior art
Middle conversion of propane is low, stability is poor and the problem of low operational load there is provided a kind of catalyst of alkane unsaturated nitrile, should
The characteristics of catalyst has high conversion of propane, good stability and is suitable for high load operation condition.
The two of the technical problems to be solved by the invention are the preparation methods of the catalyst described in one of above-mentioned technical problem.
The three of the technical problems to be solved by the invention are one of above-mentioned technical problem catalyst in low-carbon alkanes ammonia
Application in oxidative synthesis unsaturated nitrile.
To solve one of above-mentioned technical problem, technical scheme is as follows：
The catalyst of alkane unsaturated nitrile, the active constituent of general formula is included according to atomic ratio：
VaA1.00Ox
A is at least one of Fe, Ca, Mg, Ni, Al, Zr element；
A span is 0.1~1.0；
X is the oxygen atom sum needed for meeting each element chemical valence in catalyst.
In order to solve the above-mentioned technical problem two, technical scheme is as follows：The technology of one of above-mentioned technical problem
The preparation method of catalyst described in scheme, comprises the following steps：
1) solution (I) is made by the corresponding salt of aequum V is soluble in water；
2) by least one of aequum Fe, Ca, Mg, Ni, Al, Zr element, corresponding salt is soluble in water that solution is made
(II)；
3) pH value that (I) solution is adjusted with inorganic acid is 1.5 ~ 5.0, and solution (II) is added in solution (I), is formed
(I) with the mixed solution of (II), then it is co-precipitated with inorganic base as precipitating reagent, pH value when precipitation ends is 3.5 ~
6.0；Obtained precipitation is dry or moist by filtering, washing, and 0.5 is calcined in temperature is 400 ~ 800 DEG C of atmosphere
~ 8 hours, so as to obtain catalyst；Wherein dry temperature is 100 ~ 150 DEG C.
In above-mentioned technical proposal, the inorganic acid is preferably inorganic middle strong acid；More preferably in sulfuric acid, nitric acid and hydrochloric acid
It is at least one.
In above-mentioned technical proposal, the inorganic base is at least one in ammoniacal liquor, potassium hydroxide and NaOH.
In above-mentioned technical proposal, drying time is preferably 0 ~ 24 hour, and optimal is 2 ~ 10 hours.
In above-mentioned technical proposal, sintering temperature is preferably 500 ~ 700 DEG C.
In above-mentioned technical proposal, roasting time is preferably 2 ~ 4 hours.
In above-mentioned technical proposal, roasting gas atmosphere is preferably at least one in ammonia, helium, nitrogen or argon gas.
To solve the three of above-mentioned technical problem, technical scheme is as follows：The technical side of one of above-mentioned technical problem
Application of the catalyst in low-carbon alkanes ammoxidation synthesizes unsaturated nitrile described in case.
One of above-mentioned preferred technical scheme, is the application in propane ammoxidation reaction synthesis of acrylonitrile.
The two of above-mentioned preferred technical scheme, are the applications in iso-butane ammoxidation reaction synthesizing methyl acrylonitrile.
In above-mentioned technical proposal, propane or iso-butane are preferably industrial gasses purity, and molecular oxygen is pure oxygen, oxygen-enriched and sky
Gas, preferably air.
The mol ratio of ammonia and propane or iso-butane is preferably between 0.8~2.0 preferably 1.0~1.5 in unstripped gas, empty
The mol ratio of gas and propane or iso-butane is preferably 8.0~16.0, and preferably 10.0~15.0.
V raw materials in catalyst are preferably corresponding sulfate or its ammonium salt, Fe, Ca, Mg, Ni, Al, Zr element at least one
It is preferably corresponding halide, nitrate or sulfate to plant corresponding salt.
The catalyst of the present invention controls the pH value of V solution in preparation process by adding inorganic acid, adds inorganic base and enters
Row is co-precipitated and controls to precipitate pH value when ending.The preparation technology is simple and required raw material is easy to get, the low-carbon prepared
Alkane ammoxidation catalyst can the stable operation under the conditions of high load operation.
Catalyst of the present invention is evaluated in internal diameter is 8 millimeters of fixed bed reactors, and loaded catalyst is 1.0
Gram, reaction temperature is 450~550 DEG C, preferably 460~500 DEG C.
The conversion ratio of propane, the selectivity of acrylonitrile and time of contact are defined as follows：
When the catalyst of the present invention is used for propane ammoxidation reaction, 0.90 h can be more than in load-1Operate, especially work as above
Load is 1.24 h-1When, conversion of propane is up to 62.9 %, and can be more than 100 hours with stable operation, achieves preferable skill
Art effect.
Below by specific embodiment, the invention will be further elaborated, but the present invention is not limited by the following examples.
Brief description of the drawings
Fig. 1 represents embodiment 1 and its on year-on-year basis the stability experiment data of comparative example.
Embodiment
【Embodiment 1】
In the water that 0.8 gram of ammonium metavanadate is dissolved in 228.0 grams 80 DEG C, obtained solution (I)；5.0 grams of aluminum nitrates (are contained nine
The crystallization water, referred to as nine water, similarly hereinafter) be dissolved in 130.0 grams 30 DEG C of water, form solution (II)；Prepare the nitric acid of 0.1 mol/L
Solution (III)；Prepare the ammonia spirit (IV) of 0.1 mol/L.
Salpeter solution (III) is added dropwise in 80 DEG C of whipping process in solution (I) so that its pH value is 1.5；Then will be molten
Liquid (II) is added in solution (I), and ammonia spirit (IV) is finally added dropwise and is co-precipitated, and pH value is 5.5 when precipitation ends,
Obtained precipitation is dried 2 hours, then in 600 DEG C of ammonia atmosphere after filtering, washing in temperature is 120 DEG C of baking oven
Middle roasting 2 hours is enclosed, V is obtained0.51Al1.00OxCatalyst.
The catalyst takes 60 ~ 80 mesh powder for propane ammoxidation reaction after compressing tablet, screening, and reaction temperature is 510
DEG C, reaction pressure is that the mol ratio of propane, ammonia and air in normal pressure, unstripped gas is 1.0/1.3/12.0, and load is 1.24
h-1, acquired results are as shown in table 1.
【Embodiment 2】
In the water that 0.8 gram of ammonium metavanadate is dissolved in 228.0 grams 80 DEG C, obtained solution (I)；By 11.0 grams of ferric nitrates (nine water)
In the water for being dissolved in 265.0 grams 30 DEG C, solution (II) is formed；Prepare the salpeter solution (III) of 0.1 mol/L；0.1 mole of preparation/
The ammonia spirit (IV) risen.
Salpeter solution (III) is added dropwise in 80 DEG C of whipping process in solution (I) so that its pH value is 2.0；Then will be molten
Liquid (II) is added in solution (I), and ammonia spirit (IV) is finally added dropwise and is co-precipitated, and pH value is 6.0 when precipitation ends,
Obtained precipitation is dried 5 hours, then in 600 DEG C of High Purity Nitrogen after filtering, washing in temperature is 110 DEG C of baking oven
Atmosphere encloses middle roasting 2 hours, obtains V0.25Fe1.00OxCatalyst.
The catalyst takes 60 ~ 80 mesh powder for propane ammoxidation reaction after compressing tablet, screening, and reaction temperature is 500
DEG C, reaction pressure is that the mol ratio of propane, ammonia and air in normal pressure, unstripped gas is 1.0/1.2/10.0, and load is 1.93
h-1, acquired results are as shown in table 1.
【Embodiment 3】
In the water that 0.8 gram of ammonium metavanadate is dissolved in 228.0 grams 80 DEG C, obtained solution (I)；By 8.2 grams of calcium nitrate (four water)
In the water for being dissolved in 340.0 grams 30 DEG C, solution (II) is formed；Prepare the sulfuric acid solution (III) of 0.1 mol/L；0.1 mole of preparation/
The potassium hydroxide solution (IV) risen.
Sulfuric acid solution (III) is added dropwise in 80 DEG C of whipping process in solution (I) so that its pH value is 3.5；Then will be molten
Liquid (II) is added in solution (I), and potassium hydroxide solution (IV) is finally added dropwise and is co-precipitated, and pH value is when precipitation ends
4.0, obtained precipitation is dried 5 hours, then in 650 DEG C of height after filtering, washing in temperature is 120 DEG C of baking oven
It is calcined 2 hours in pure helium atmosphere, obtains V0.20Ca1.00OxCatalyst.
The catalyst takes 60 ~ 80 mesh powder for propane ammoxidation reaction after compressing tablet, screening, and reaction temperature is 490
DEG C, reaction pressure is that the mol ratio of propane, ammonia and air in normal pressure, unstripped gas is 1.0/1.1/14.3, and load is 1.44
h-1, acquired results are as shown in table 1.
【Embodiment 4】
In the water that 0.8 gram of ammonium metavanadate is dissolved in 228.0 grams 80 DEG C, obtained solution (I)；By 12.0 grams of nickel nitrates (six water)
In the water for being dissolved in 375.0 grams 30 DEG C, solution (II) is formed；Prepare the hydrochloric acid solution (III) of 0.1 mol/L；0.1 mole of preparation/
The sodium hydroxide solution (IV) risen.
Hydrochloric acid solution (III) is added dropwise in 80 DEG C of whipping process in solution (I) so that its pH value is 4.5；Then will be molten
Liquid (II) is added in solution (I), and sodium hydroxide solution (IV) is finally added dropwise and is co-precipitated, and pH value is when precipitation ends
5.5, obtained precipitation is dried 2 hours, then in 550 DEG C of height after filtering, washing in temperature is 130 DEG C of baking oven
It is calcined 3 hours in pure argon atmosphere, obtains V0.17Ca1.00OxCatalyst.
The catalyst takes 60 ~ 80 mesh powder for propane ammoxidation reaction after compressing tablet, screening, and reaction temperature is 510
DEG C, reaction pressure is that the mol ratio of propane, ammonia and air in normal pressure, unstripped gas is 1.0/1.5/15.0, and load is 0.94
h-1, acquired results are as shown in table 1.
【Embodiment 5】
In the water that 0.8 gram of ammonium metavanadate is dissolved in 228.0 grams 80 DEG C, obtained solution (I)；By 15.0 grams of magnesium nitrates (six water)
In the water for being dissolved in 550.0 grams 30 DEG C, solution (II) is formed；Prepare the salpeter solution (III) of 0.1 mol/L；0.1 mole of preparation/
The sodium hydroxide solution (IV) risen.
Salpeter solution (III) is added dropwise in 80 DEG C of whipping process in solution (I) so that its pH value is 3.5；Then will be molten
Liquid (II) is added in solution (I), and sodium hydroxide solution (IV) is finally added dropwise and is co-precipitated, and pH value is when precipitation ends
4.5, obtained precipitation is dried 8 hours, then in 650 DEG C of ammonia after filtering, washing in temperature is 100 DEG C of baking oven
Atmosphere encloses middle roasting 2 hours, obtains V0.12Mg1.00OxCatalyst.
The catalyst takes 60 ~ 80 mesh powder for propane ammoxidation reaction after compressing tablet, screening, and reaction temperature is 480
DEG C, reaction pressure is that the mol ratio of propane, ammonia and air in normal pressure, unstripped gas is 1.0/1.5/14.3, and load is 1.40
h-1, acquired results are as shown in table 1.
【Embodiment 6】
In the water that 0.8 gram of ammonium metavanadate is dissolved in 228.0 grams 80 DEG C, obtained solution (I)；By 19.0 grams of zirconium nitrates (five water)
In the water for being dissolved in 440.0 grams 30 DEG C, solution (II) is formed；Prepare the salpeter solution (III) of 0.1 mol/L；0.1 mole of preparation/
The ammonia spirit (IV) risen.
Salpeter solution (III) is added dropwise in 80 DEG C of whipping process in solution (I) so that its pH value is 2.0；Then will be molten
Liquid (II) is added in solution (I), and ammonia spirit (IV) is finally added dropwise and is co-precipitated, and pH value is 3.0 when precipitation ends,
Obtained precipitation is dried 8 hours, then in 600 DEG C of High Purity Nitrogen after filtering, washing in temperature is 110 DEG C of baking oven
Atmosphere encloses middle roasting 2 hours, obtains V0.12Mg1.00OxCatalyst.
The catalyst takes 60 ~ 80 mesh powder for propane ammoxidation reaction after compressing tablet, screening, and reaction temperature is 500
DEG C, reaction pressure is that the mol ratio of propane, ammonia and air in normal pressure, unstripped gas is 1.0/1.3/12.0, and load is 1.33
h-1, acquired results are as shown in table 1.
【Comparative example 1】
As different from Example 1, nitric acid is added without in catalyst preparation process, detailed process is：
In the water that 0.8 gram of ammonium metavanadate is dissolved in 228.0 grams 80 DEG C, obtained solution (I)；By 5.0 grams of aluminum nitrates (nine water)
In the water for being dissolved in 130.0 grams 30 DEG C, solution (II) is formed；Prepare the ammonia spirit (IV) of 0.1 mol/L.
Solution (I) is slowly added to solution (II) in 80 DEG C of whipping process, and ammonia spirit (IV) progress is then added dropwise
Co-precipitation, pH value is 5.5 when precipitation ends, and obtained precipitation is done after filtering, washing in temperature is 120 DEG C of baking oven
Dry 2 hours, then it is calcined 2 hours in 600 DEG C of ammonia atmosphere, obtains V0.51Al1.00OxCatalyst.
The catalyst takes 60 ~ 80 mesh powder for propane ammoxidation reaction after compressing tablet, screening, and reaction temperature is 510
DEG C, reaction pressure is that the mol ratio of propane, ammonia and air in normal pressure, unstripped gas is 1.0/1.3/12.0, and load is 1.24
h-1, acquired results are as shown in table 1.
【Comparative example 2】
As different from Example 2, nitric acid is added without in catalyst preparation process, detailed process is：
In the water that 0.8 gram of ammonium metavanadate is dissolved in 228.0 grams 80 DEG C, obtained solution (I)；By 11.0 grams of ferric nitrates (nine water)
In the water for being dissolved in 265.0 grams 30 DEG C, solution (II) is formed；Prepare the ammonia spirit (IV) of 0.1 mol/L.
Solution (I) is slowly added to solution (II) in 80 DEG C of whipping process, and ammonia spirit (IV) progress is then added dropwise
Co-precipitation, pH value is 6.0 when precipitation ends, and obtained precipitation is done after filtering, washing in temperature is 110 DEG C of baking oven
Dry 5 hours, then it is calcined 2 hours in 600 DEG C of high pure nitrogen atmosphere, obtains V0.25Fe1.00OxCatalyst.
The catalyst takes 60 ~ 80 mesh powder for propane ammoxidation reaction after compressing tablet, screening, and reaction temperature is 500
DEG C, reaction pressure is that the mol ratio of propane, ammonia and air in normal pressure, unstripped gas is 1.0/1.2/10.0, and load is 1.93
h-1, acquired results are as shown in table 1.
【Comparative example 3】
As different from Example 3, sulfuric acid is added without in catalyst preparation process, detailed process is：
In the water that 0.8 gram of ammonium metavanadate is dissolved in 228.0 grams 80 DEG C, obtained solution (I)；By 8.2 grams of calcium nitrate (four water)
In the water for being dissolved in 340.0 grams 30 DEG C, solution (II) is formed；Prepare the potassium hydroxide solution (IV) of 0.1 mol/L.
Solution (I) is slowly added to solution (II) in 80 DEG C of whipping process, and potassium hydroxide solution (IV) is then added dropwise
It is co-precipitated, pH value is 4.0 when precipitation ends, obtained precipitation is after filtering, washing, in the baking oven that temperature is 120 DEG C
Middle drying 5 hours, is then calcined 2 hours in 650 DEG C of high-purity helium atmosphere, obtains V0.20Ca1.00OxCatalyst.
The catalyst takes 60 ~ 80 mesh powder for propane ammoxidation reaction after compressing tablet, screening, and reaction temperature is 490
DEG C, reaction pressure is that the mol ratio of propane, ammonia and air in normal pressure, unstripped gas is 1.0/1.1/14.3, and load is 1.44
h-1, acquired results are as shown in table 1.
Table 1（It is continued）
| Catalyst is constituted | Prepare committed step | |
| Embodiment 1 | V0.51Al1.00Ox | Nitric acid adjusts pH=1.5, and ammoniacal liquor adjusts pH=5.5 |
| Embodiment 2 | V0.25Fe1.00Ox | Nitric acid adjusts pH=2.0, and ammoniacal liquor adjusts pH=6.0 |
| Embodiment 3 | V0.20Ca1.00Ox | Sulfuric acid adjusts pH=3.5, and potassium hydroxide adjusts pH=4.0 |
| Embodiment 4 | V0.17Ni1.00Ox | Hydrochloric acid adjusts pH=4.5, and NaOH adjusts pH=5.5 |
| Embodiment 5 | V0.12Mg1.00Ox | Nitric acid adjusts pH=3.5, and NaOH adjusts pH=4.5 |
| Embodiment 6 | V0.15Zr1.00Ox | Nitric acid adjusts pH=2.0, and ammoniacal liquor adjusts pH=3.0 |
| Comparative example 1 | V0.51Al1.00Ox | PH is adjusted without nitric acid, ammoniacal liquor adjusts pH=5.5 |
| Comparative example 2 | V0.25Fe1.00Ox | PH is adjusted without nitric acid, ammoniacal liquor adjusts pH=6.0 |
| Comparative example 3 | V0.20Ca1.00Ox | PH is adjusted without sulfuric acid, potassium hydroxide adjusts pH=4.0 |
Table 1（It is continuous）
Claims (8)
1. the catalyst of alkane unsaturated nitrile, the active constituent of general formula is included according to atomic ratio：
V0.51Al1.00Ox
X is the oxygen atom sum needed for meeting each element chemical valence in catalyst；
The preparation method of the catalyst comprises the following steps：
1) solution (I) is made by the corresponding salt of aequum V is soluble in water；
2) solution (II) is made by the corresponding salt of aequum Al elements is soluble in water；
3) adjusted with inorganic acid (I) solution pH value be 1.5~5.0, solution (II) is added in solution (I), formed (I) with
(II) mixed solution, is then co-precipitated with inorganic base as precipitating reagent, and pH value when precipitation ends is 3.5~6.0；
The precipitation arrived is dry or moist by filtering, washing, and roasting 0.5~8 is small in temperature is 400~800 DEG C of atmosphere
When, so as to obtain catalyst；Wherein dry temperature is 100~150 DEG C.
2. catalyst according to claim 1, it is characterised in that inorganic acid is at least one in sulfuric acid, nitric acid and hydrochloric acid
Kind.
3. catalyst according to claim 1, it is characterised in that inorganic base is in ammoniacal liquor, potassium hydroxide and NaOH
At least one.
4. catalyst according to claim 1, it is characterised in that drying time is 0~24 hour.
5. catalyst according to claim 1, it is characterised in that sintering temperature is 500~700 DEG C.
6. catalyst according to claim 1, it is characterised in that roasting gas atmosphere is ammonia, helium, nitrogen or argon
At least one in gas.
7. catalyst according to claim 1, it is characterised in that roasting time is 2~4 hours.
8. application of the catalyst in low-carbon alkanes ammoxidation synthesizes unsaturated nitrile described in claim 1.
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| CN1426834A (en) * | 2001-12-21 | 2003-07-02 | 沙地基本工业公司 | Catalyst composition for ammoxidation of parafins and olefins, and preparing process and use thereof |
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| US20060122055A1 (en) * | 2004-12-06 | 2006-06-08 | Gaffney Anne M | (Amm)oxidation catalyst and catalytic (amm)oxidation process for conversion of lower alkanes |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1426834A (en) * | 2001-12-21 | 2003-07-02 | 沙地基本工业公司 | Catalyst composition for ammoxidation of parafins and olefins, and preparing process and use thereof |
Non-Patent Citations (3)
| Title |
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| Bulk and surface structures of V2O5/ZrO2 catalysts for n-butane oxidative dehydrogenation;Delia Gazzoli et al.;《Journal of Molecular Catalysis A：Chemical》;20090527;第310卷;第17-23页 * |
| Local environment of vanadium in V/Al/O-mixed oxide catalyst for propane ammoxidation：Characterization by in situ valence-to-core X-ray emission spectroscopy and X-ray absorption spectroscopy;O.V.Safonova et al.;《Journal of Catalysis》;20091021;第268卷;第156-164页 * |
| Toluene ammoxidation on α-Fe2O3-based catalysts;E.Rombi et al.;《Applied Catalysis A：General》;20040318;第266卷;第73-79页 * |
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