CN105771959B - A kind of O composite metallic oxide catalyst and its preparation method and application - Google Patents
A kind of O composite metallic oxide catalyst and its preparation method and application Download PDFInfo
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- CN105771959B CN105771959B CN201410806364.9A CN201410806364A CN105771959B CN 105771959 B CN105771959 B CN 105771959B CN 201410806364 A CN201410806364 A CN 201410806364A CN 105771959 B CN105771959 B CN 105771959B
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- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention provides a kind of O composite metallic oxide catalyst, it is with SiO2For carrier, contain the active component indicated by general formula (1): Mo1VaSbbNbcMdNeOn(1), in formula (1), at least one of M Cr, Co, Mn or Ni；N is at least one of Cs, Ca, Sr or Ba；A, b, c, d and e respectively indicate the molar ratio of vanadium (V), antimony (Sb), niobium (Nb), M and N element relative to molybdenum (Mo) element, and respectively value is as follows: 0.1≤a≤1.0,0.1≤b≤1.0,0.01≤c≤0.50,0.00001≤d≤0.00200,0.00001≤e≤0.00200, n are the sum of oxygen atom needed for meeting other element valences.For catalyst of the present invention in saturated alkane ammoxidation reaction, acrylonitrile selectivity is high, and the repeatability of catalyst synthesis is preferably.
Description
Technical field
The present invention relates to a kind of industrial catalysts, and in particular to a kind of O composite metallic oxide catalyst, more particularly to use
The O composite metallic oxide catalyst of unsaturated nitrile is produced in saturated alkane ammoxidation, and preparation method thereof.
Background technique
Propane ammoxidation synthesis of acrylonitrile catalyst mainly has three categories.The first kind is molybdate catalyst, mainly includes
Mo-Bi and Mo-V two major classes catalyst.Mo-Bi class catalyst is for ammoxidation of propylene synthesis of acrylonitrile, by improving earliest
It is used for propane ammoxidation synthesis of acrylonitrile afterwards, but selectivity not to be high, is 50~67%.Mo-V series catalysts are with Mo-V-Nb-Te
Based on, it is the hot spot of recent researches.The catalyst can obtain 60% or more acrylonitrile yield at present.
Second class is metaantimmonic acid salt catalyst, mainly V-Sb, Fe-Sb and Ga-Sb metal composite oxide.This kind of catalyst
Main active component be α-Sb2O4With the VSbO with rutile structure4、CrSbO4、FeSbO4And GaSbO4.Such catalyst
Highest acrylonitrile yield up to 59%.
Third class catalyst is vanadium aluminoxynitride, general formula VAlxOyNzHn.Although this kind of catalyst acrylonitrile selection
Property and yield it is not high, but acrylonitrile space-time yield be much higher than above-mentioned two classes catalyst, therefore, such catalyst is that one kind has
The catalyst system of development prospect.
In propane ammoxidation reaction, it is to determine the committed step of entire rate of catalysis reaction that propane, which activates dehydrogenation, therefore, I
Consider by the way that the element that dehydrogenating propane can be promoted to react, such as Cr, Ni, Co, Mn, to accelerate the dehydrogenation of propane anti-is added
It answers.In addition, the selectivity of product acrylonitrile, and reduce the deciding factor of propane unit consumption in acrylonitrile process.Pass through addition
Alkali and alkali earth metal provide alkalinity appropriate for catalyst, can be improved the selectivity of target product acrylonitrile, reduce hydrogen
The selectivity of cyanic acid, while also reducing the difficulty of post-processing.
Summary of the invention
The purpose of the present invention is mainly to improve the weight of the selectivity of acrylonitrile and catalyst synthesis in propane ammoxidation reaction
Renaturation provides a kind of highly selective, and prepares reproducible Catalyst For Propane Ammoxidation for the production of acrylonitrile.
The technical solution adopted by the invention is as follows:
A kind of O composite metallic oxide catalyst is provided, it is with SiO2For carrier, contain the work indicated by general formula (1)
Property component:
Mo1VaSbbNbcMdNeOn (1)
In formula (1), at least one of M Cr, Co, Mn or Ni；N is at least one of Cs, Ca, Sr or Ba；a,b,
C, d and e respectively indicates the molar ratio of vanadium (V), antimony (Sb), niobium (Nb), M and N element relative to molybdenum (Mo) element, and respectively asks for
It is worth as follows: 0.1≤a≤1.0,0.1≤b≤1.0,0.01≤c≤0.50,0.00001≤d≤0.00200,0.00001≤e≤
0.00200, n is the sum of oxygen atom needed for meeting other element valences.
In preferred embodiments of the present invention, a, b, c, d and e value in the formula (1) are as follows: 0.2≤a≤0.5, and 0.2
≤ b≤0.5,0.05≤c≤0.20,0.00001≤d≤0.0010,0.00001≤e≤0.0010；Preferred value is such as
Under: 0.24≤a≤0.26,0.26≤b≤0.28, c=0.09,0.0002≤d≤0.0008,0.0001≤e≤0.0006.
In preferred embodiments of the present invention, the M in the formula (1) is one or both of Cr or Ni；More preferable Ni.
In preferred embodiments of the present invention, the N in the formula (1) is one or both of Cs or Sr.
In preferred embodiments of the present invention, the addition quality of the carrier is the 30~70% of catalyst gross mass, more excellent
Select 35~65%.
In most preferably a kind of scheme of the present invention, the O composite metallic oxide catalyst is with SiO2For carrier, contain
The active component indicated by general formula (2):
Mo1VaSbbNbcNidNeOn (2)
In formula (2), N is one of Cs or Sr；A, b, c, d and e respectively indicate vanadium (V), antimony (Sb), niobium (Nb), Ni and N
Molar ratio of the element relative to molybdenum (Mo) element, and respectively value is as follows: 0.24≤a≤0.25,0.26≤b≤0.27, c=
0.09,0.0004≤d≤0.0008,0.0001≤e≤0.0006, n are that oxygen atom needed for meeting other element valences is total
Number.
The present invention also provides the methods of the preparation O composite metallic oxide catalyst, comprising the following steps:
Using the water soluble salt or oxide that can provide the metallic element as raw material, mixed salt solution is made in dissolution, with dioxy
After the mixing of SiClx carrier, revolving is dry or spray drying, then obtains after high-temperature roasting at 600~700 DEG C of the present invention
O composite metallic oxide catalyst.
The present invention also provides the O composite metallic oxide catalysts to produce unsaturated nitrile in saturated alkane ammoxidation
Application in reaction.
The reaction of the reaction preferably propane ammoxidation synthesis of acrylonitrile of unsaturated nitrile is produced in the saturated alkane ammoxidation.
Compared with prior art, the present invention is by adding various other gold in Mo-V-Sb-Nb class metal composite oxide
Belong to element, obtained a kind of new catalyst, which can significantly improve the third of propane ammoxidation synthesis of acrylonitrile reaction
Alkene nitrile selectivity, acrylonitrile yield or conversion of propane, make production process obtain significant improvement on the whole.
Specific embodiment
Below by preparation method and application of the specific embodiment to propane ammoxidation synthesis of acrylonitrile catalyst give into
One step explanation, but the present invention is not therefore subject to any restriction.
In embodiments given below, to the investigation evaluation condition of catalyst are as follows:
Reactor: fixed-bed micro-reactor, 20 millimeters of internal diameter
Loaded catalyst: 8 grams
Reaction pressure: normal pressure
Reaction temperature: 465 DEG C
Reaction time: 3 hours
Unstripped gas forms (volume ratio): propane/ammonia/oxygen=1/1/2.5
WWH:0.20 grams-propane/gram-catalyst h
Reaction product is analyzed with online gas-chromatography, and calculates Carbon balance, and Carbon balance is in (95~105%) Shi Weiyou
Imitate data.
Conversion of propane, acrylonitrile selectivity and yield is defined as:
Conversion of propane (%)=(1- unreacted propane molal quantity/enter reactor propane molal quantity) × 100%
Acrylonitrile selectivity (%)=(generating acrylonitrile carbon molal quantity/all products carbon molal quantity) × 100%
Acrylonitrile yield (%)=conversion of propane × acrylonitrile selectivity
Embodiment 1
By 36.9g (NH4)6Mo7O24·4H2O、6.1g NH4VO3With 7.9g Sb2O3It is put into 1000mL beaker, is added
400mL deionized water, heating stirring form blue suspension, are cooled to room temperature, 43.0g silica solution (SiO is added2Mass fraction
And 9.5 grams of H 30%)2O2, stir 1 hour, form slurry-A.
By 3.2 grams of Nb2O5·xH2The heating of O and 6.3g oxalic acid is dissolved in 100mL deionized water, is cooled to room temperature 4.3 grams of addition
H2O2, 9mL 5mg/mL chromium nitrate solution and 1mL 4.1mg/mL cesium nitrate solution is then added, is stirred at room temperature 10 minutes, is formed
Slurry-B.
22.4g white carbon black is put into 500mL beaker, 300mL deionized water ultrasonic disperse is added and forms dispersion liquid, forms slurry
Material-C.
Slurry-B and slurry-C is added in slurry-A to stir 10 minutes, gained slurry is packed into round evaporative flask, is taken out true
Sky distillation is put into 80 DEG C of baking oven drying to partial desiccation.
Solid extrusion after drying is 4 millimeters of diameter, long 3~5 millimeters of cylinder, then 650 DEG C of roastings in an inert atmosphere
It burns 2 hours, obtains catalyst.
Embodiment 2~14
According to the identical preparation process of embodiment 1, prepared according to the composition of 1 catalyst of table.Gained catalyst is by upper
It states investigation evaluation condition to be investigated, initial activity the results are shown in Table 2.
1 catalyst of table composition
| Catalyst composition | |
| Embodiment 1 | Mo1V0.25Sb0.26Nb0.09Cr0.0006Cs0.0001On/44%-SiO2 |
| Embodiment 2 | Mo1V0.24Sb0.26Nb0.09Cr0.0002CS0.0001On/44%-SiO2 |
| Embodiment 3 | Mo1V0.24Sb0.26Nb0.09Cr0.0004Cs0.0002On/48%-SiO2 |
| Embodiment 4 | Mo1V0.24Sb0.26Nb0.09Cr0.0004Cs0.0003On/50%-SiO2 |
| Embodiment 5 | Mo1V0.24Sb0.26Nb0.09Cr0.0002Cs0.0005On/60%-SiO2 |
| Embodiment 6 | Mo1V0.24Sb0.26Nb0.20Ni0.0002Sr0.0001On/44%-SiO2 |
| Embodiment 7 | Mo1V0.25Sb0.26Nb0.09Ni0.0004Sr0.0002On/44%-SiO2 |
| Embodiment 8 | Mo1V0.24Sb0.27Nb0.09Ni0.0006Sr0.0003On/44%-SiO2 |
| Embodiment 9 | Mo1V0.25Sb0.27Nb0.09Ni0.0008Sr0.0006On/44%-SiO2 |
| Embodiment 10 | Mo1V0.26Sb0.26Nb0.09Ni0.0010Sr0.0005On/44%-SiO2 |
| Embodiment 11 | Mo1V0.24Sb0.28Nb0.09Cr0.0006Sr0.0003On/44%-SiO2 |
| Embodiment 12 | Mo1V0.26Sb0.28Nb0.09Cr0.0006Sr0.0006On/44%-SiO2 |
| Embodiment 13 | Mo1V0.25Sb0.26Nb0.09Ni0.0004Cs0.0004On/44%-SiO2 |
| Embodiment 14 | Mo1V0.25Sb0.25Nb0.09Ni0.0008Cs0.0003On/44%-SiO2 |
2 catalyst performance test result of table
| Conversion of propane (%) | Acrylonitrile selectivity (%) | Acrylonitrile yield (%) | |
| Embodiment 1 | 88.22 | 76.18 | 67.21 |
| Embodiment 2 | 71.35 | 80.08 | 57.14 |
| Embodiment 3 | 68.91 | 82.63 | 56.94 |
| Embodiment 4 | 58.37 | 77.19 | 45.05 |
| Embodiment 5 | 52.60 | 70.33 | 36.99 |
| Embodiment 6 | 80.09 | 78.11 | 62.55 |
| Embodiment 7 | 84.05 | 80.81 | 67.92 |
| Embodiment 8 | 80.92 | 84.13 | 68.08 |
| Embodiment 9 | 85.06 | 80.99 | 68.89 |
| Embodiment 10 | 70.41 | 78.35 | 55.16 |
| Embodiment 11 | 55.38 | 66.17 | 36.64 |
| Embodiment 12 | 52.06 | 70.82 | 36.86 |
| Embodiment 13 | 88.05 | 81.39 | 71.66 |
| Embodiment 14 | 90.26 | 68.02 | 61.39 |
Claims (5)
1. a kind of O composite metallic oxide catalyst, it is with SiO2For carrier, it is characterised in that: containing by general formula (1) expression
Active component:
Mo1VaSbbNbcMdNeOn(1)
In formula (1), a, b, c, d and e respectively indicate vanadium (V), antimony (Sb), niobium (Nb), M and N element relative to molybdenum (Mo) element
Molar ratio, and respectively value is as follows: 0.24≤a≤0.26,0.26≤b≤0.28, c=0.09,0.0002≤d≤
0.0008,0.0001≤e≤0.0006, n are the sum of oxygen atom needed for meeting other element valences；
M in the formula (1) is Ni；
N in the formula (1) is one or both of Cs or Sr.
2. catalyst according to claim 1, it is characterised in that: the addition quality of the carrier is catalyst gross mass
35~65%.
3. catalyst according to claim 1, it is characterised in that: it contains the active component indicated by general formula (2):
Mo1VaSbbNbcNidNeOn(2)
In formula (2), N is one of Cs or Sr；A, b, c, d and e respectively indicate vanadium (V), antimony (Sb), niobium (Nb), Ni and N element
Relative to the molar ratio of molybdenum (Mo) element, and respectively, value is as follows: 0.24≤a≤0.25,0.26≤b≤0.27, c=
0.09,0.0004≤d≤0.0008,0.0001≤e≤0.0006, n are that oxygen atom needed for meeting other element valences is total
Number.
4. O composite metallic oxide catalyst described in claim 1 is in the reaction that unsaturated nitrile is produced in saturated alkane ammoxidation
Application.
5. application as claimed in claim 4, it is characterised in that: the reaction that unsaturated nitrile is produced in the saturated alkane ammoxidation is
The reaction of propane ammoxidation synthesis of acrylonitrile.
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| US6143690A (en) * | 1998-05-07 | 2000-11-07 | Asahi Kasei Kogyo Kabushiki Kaisha | Ammoxidation catalyst for use in producing acrylonitrile or methacrylonitrile from propane or isobutane |
| JP4530595B2 (en) * | 2000-12-13 | 2010-08-25 | 旭化成ケミカルズ株式会社 | Oxide catalyst for oxidation or ammoxidation |
| ES2357944T3 (en) * | 2003-06-09 | 2011-05-04 | Asahi Kasei Chemicals Corporation | CATALYST FOR OXIDATION OR AMOXIDATION. |
| CN104475085B (en) * | 2006-03-20 | 2019-02-22 | 旭化成株式会社 | Oxidation or ammoxydation catalyst and its manufacturing method |
| EP2205554A2 (en) * | 2007-10-11 | 2010-07-14 | Ineos USA, LLC | Process for the ammoxidation or oxidation of propane and isobutane |
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