CN103418400A - Fluidized-bed catalyst for preparing unsaturated nitrile by ammoxidation - Google Patents
Fluidized-bed catalyst for preparing unsaturated nitrile by ammoxidation Download PDFInfo
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- CN103418400A CN103418400A CN2012101504942A CN201210150494A CN103418400A CN 103418400 A CN103418400 A CN 103418400A CN 2012101504942 A CN2012101504942 A CN 2012101504942A CN 201210150494 A CN201210150494 A CN 201210150494A CN 103418400 A CN103418400 A CN 103418400A
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- catalyst
- acrylonitrile
- ammoxidation
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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
Abstract
The invention relates to a fluidized-bed catalyst for preparing unsaturated nitrile by ammoxidation, and mainly solves the problems that in the prior art the lattice oxygen content of a catalyst for acrylonitrile is low, deep oxidation of propylene is easy to occur, the acrylonitrile selectivity is low to cause the low yield of the acrylonitrile. According to the fluidized-bed catalyst for preparing the unsaturated nitrile by ammoxidation, through use of a technical scheme, the problems are well solved. The technical scheme is shown as follows: the fluidized-bed catalyst uses silica sol as a carrier, and contains an active component represented by the following general formula: Mo[12]Bi[a]Fe[b]Ni[c]X[d]Y[e]Z[f]K[g]O[x], wherein b/(a+e)=1.0-3.5. The fluidized-bed catalyst can be used in industrial production of preparation of the acrylonitrile by ammoxidation of the propylene.
Description
Technical field
The present invention relates to a kind of fluid catalyst of prepared by ammoxidation unsaturated nitrile, particularly about the fluid catalyst of propylene, butylene preparing acrylonitrile by ammoxidation, butene nitrile.
Background technology
The standby α of the prepared by ammoxidation of alkene, beta unsaturated nitrile technique are by BP company in exploitation sixties last century in last century, and the core technology of this technique is the catalyst that uses a kind of active component to contain Mo, Bi.Through constantly improving, the Mo-Bi series catalysts is very ripe at present, industrial, by preparing acrylonitrile by allylamine oxidation technique, is widely used.The improvement of catalyst in the past is mainly to carry out from activity and the stability aspect of catalyst by the design of catalyst formulation, as added transition metal to improve activity in active constituent, increases the single of product and receives; Add rare earth element to improve redox ability; Add the elements such as Na, P to improve the wearability of catalyst; Add the elements such as Fe, Co, Ni to suppress the distillation of Mo, improve stability of catalyst etc.
Patent CN 99119905.7, CN 99119906.5, CN 97106771.6 and CN 96101529.2 have all introduced the improved Mo-Bi catalyst for propylene, isobutene ammonia oxidizing unsaturated nitrile catalyst processed, the advantage of these catalyst has oxidation-reduction stability and reaction yield preferably preferably, and reacting ammonia is lower than empty ratio and reaction temperature.
Patent CN 01113194.2, CN 01113193.4 and CN 01113192.6 introduced in catalyst preparation process, get part metals and organic ligand, chelating agent or surfactant separately the method for preparation improve catalyst at low ammonia than the performance under reaction condition.
Patent CN 03151170.8 and CN 03151169.4 have introduced in catalyst preparation process, in carrier starting material Ludox, add the solid silica that 2～25% grain diameter is 5～100 nanometers to improve catalyst performance.
The conversion ratio of above patented technology to the raising catalyst, the discharge of ammonia ratio and then minimizing amine wastewater of sulphuric acid in the reduction course of reaction, there has been certain effect the aspects such as the life-span of extending catalyst; Yet the report of patent up to now, all exist acrylonitrile catalyst Lattice Oxygen content low, and deep oxidation easily occurs propylene, and acrylonitrile is selectively low, causes the problem that acrylonitrile yield is low.
Summary of the invention
One of technical problem to be solved by this invention is in prior art, to exist acrylonitrile catalyst Lattice Oxygen content low, deep oxidation easily occurs in propylene, acrylonitrile is selectively low, causes the problem that acrylonitrile yield is low, and a kind of new unsaturated nitrile fluid catalyst prepared by ammoxidation is provided.It is high that this catalyst has Lattice Oxygen content, selective high oxidation reaction occurs in the Lattice Oxygen in propylene and catalyst, and suppress it, with gas phase oxygen generation deep oxidation, reacts, and acrylonitrile is selectively high, for the reaction of prepared by ammoxidation unsaturated nitrile, the advantage that acrylonitrile yield is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of unsaturated nitrile fluid catalyst prepared by ammoxidation, take Ludox as carrier, and contain the active component that following general formula means:
Mo
12Bi
aFe
bNi
cX
dY
eZ
fK
gOx
Wherein:
X is at least one being selected from Mg, Co, Ca, Be, Cu, Zn, Pb, Mn or Te;
Y is at least one being selected from La, Ce or Sm;
Z is at least one being selected from Rb, Li or Cs;
The span of a is 0.1～6.0;
The span of b is 0.1～10.0;
The span of c is 0.1～10.0;
The span of d is 0.1～10.0;
The span of e is 0.1～9.5;
The span of b/ (a+e) is 1.0～3.5;
The span of f is > 0～0.5;
The span of g is > 0～0.2;
X meets the required oxygen atom sum of other element valence, and the consumption of carrier is catalyst weight 30～70%; Wherein the span of b/ (a+e) is 1.0～3.5.
The preferred span of b/ in technique scheme (a+e) is 1.5～2.5; The value preferable range of g is 0.01～0.1; The consumption preferable range of carrier is catalyst weight 40～60%; The calcination activation temperature preferable range of catalyst is 550～640 ℃; Calcination activation time preferable range is 0.5～2 hour.
Catalyst can be familiar with those skilled in the art coprecipitation preparation.The starting material of required metallic element is corresponding water soluble salt, make slurry with the Ludox carrier by coprecipitation, the aging rear spray drying granulation of slurry, then high-temperature roasting obtains the catalyst finished product, calcination activation temperature preferable range is 550～640 ℃, and calcination activation time preferable range is 0.5～2 hour.
In the following embodiment provided, to the investigation appreciation condition of catalyst, be:
Reactor: fluidized-bed reactor, 38 millimeters of internal diameters
Catalyst filling amount: 550 grams
Reactor top pressure: 0.084 MPa (gauge pressure)
Reaction temperature: 430 ℃
Reaction time: 4 hours
Raw material ratio: propylene/ammonia/air=1/1.1/9.5,
WWH: 0.06 hour
-1
Product absorbs with 0 ℃ of diluted acid, with gas-chromatography and chemical analysis binding analysis product.And the calculating Carbon balance, when Carbon balance, be valid data during at (95～105) %.
Propylene conversion, acrylonitrile yield and optionally be defined as:
Propylene conversion (%)=1-
* 100 %
All product C molal quantitys (comprising unreacting propylene)
Generate acrylonitrile C molal quantity
Single-pass yield of acrylonitrile (%)=
* 100 %
All product C molal quantitys (comprising unreacting propylene)
Single-pass yield of acrylonitrile
Acrylonitrile selective (%)=
* 100 %
Propylene conversion
The present invention is by optimizing the ratio of b/ (a+e) in the acrylonitrile catalyst formula, effectively improved Lattice Oxygen content in catalyst, thereby the non-selective oxidation reaction that has suppressed gas phase oxygen in propylene and unstripped gas, it is the deep oxidation reaction, and effectively increase the selective oxidation reaction of propylene and Lattice Oxygen, and then it is selective to have significantly improved acrylonitrile, acrylonitrile yield obviously improves.As shown in table 2 result: the Lattice Oxygen of catalyst is increased to the approximately 200 μ mol/g of embodiment by 65 μ mol/g of comparative example 1,1～3 times of rising ratio, and effect is remarkable; Acrylonitrile selectively is increased to 86% left and right of embodiment by 80.3% of comparative example 1, single-pass yield of acrylonitrile is increased to approximately 84% by 78.5%, has obtained technique effect preferably.
Below by embodiment, the present invention is further elaborated.
The specific embodiment
[comparative example 1]
By the Ludox of 1400 grams 40% (weight), stir 0.5 hour, obtain material A.
By 441.4 gram (NH
4)
6Mo
7O
244H
2O joins in the warm water of 70 ℃ of 330 grams, stirs and makes it all dissolve and obtain material B, A is added fast in the B of strong stirring, obtains material C.
By 213.1 gram Fe (NO
3)
39H
2O adds in 70 ℃ of hot water of 150 grams, adds 201.8 gram Bi (NO after stirring and dissolving again
3)
35H
2O, 274.8 gram Ni (NO
3)
36H
2O, 96.3 gram Mg (NO
3)
36H
2O, 72.5 gram La (NO
3)
33H
2O, 18.6 gram Sm (NO
3)
33H
2Make material D after the O stirring and dissolving.
Add 1.1 gram KNO in 20 gram water
3, 0.9 gram NaNO
3With 2.0 gram CsNO
3After dissolving, it is added in material D and form material E.
Material E is dripped under rapid stirring in material C, form catalyst pulp.In 70 ℃ of spray-dryings after aging 3 hours, by the particle of gained in rotary calciner in 580 ℃ of lower roastings 3 hours, obtain finished catalyst.
[embodiment 1～15]
The identical preparation process according to comparative example 1, form Kaolinite Preparation of Catalyst according to table 1 catalyst, by above-mentioned investigation appreciation condition, investigated, and activity rating result and Lattice Oxygen content analysis the results are shown in Table 2.
Table 1 catalyst
| ? | Catalyst forms |
| Comparative example 1 | Mo 12Bi 2.0Fe 2.5Ni 4.5Mg 1.8La 0.8Sm 0.2K 0.05Cs 0.05Na 0.05+50%SiO 2 |
| Embodiment 1 | Mo 12Bi 1.2Fe 2.5Ni 4.6Co 2.0Ce 0.7K 0.07+46%SiO 2 |
| Embodiment 2 | Mo 12Bi 0.5Fe 1.9Ni 5.8Mg 2.3La 0.8K 0.1Rb 0.08+46%SiO 2 |
| Embodiment 3 | Mo 12Bi 0.2Fe 2.0Ni 6.8Mg 0.9 Sm 0.6K 0.1Cs 0.05+50%SiO 2 |
| Embodiment 4 | Mo 12Bi 0.4Fe 1.5Ni 4.5Co 4.0La 0.5K 0.02 Cs 0.09+52%SiO 2 |
| Embodiment 5 | Mo 12Bi 0.5Fe 3.2Ni 3.0Mg 1.8La 0.8Sm 0.2K 0.05Cs 0.05+50%SiO 2 |
| Embodiment 6 | Mo 12Bi 0.2Fe 2.8Ni 5.3Mn 0.7Ce 0.8Ca 0.2K 0.11Cs 0.05+50%SiO 2 |
| Embodiment 7 | Mo 12Bi 0.9Fe 4.9Ni 3.5Mg 1.8Pb 0.2Ce 1.3 K 0.12Cs 0.13+52% SiO 2 |
| Embodiment 8 | Mo 12Bi 0.7Fe 2.5Ni 5.5Ce 0.3 K 0.15Cs 0.1Li 0.05 +47%SiO 2 |
| Embodiment 9 | Mo 12Bi 2.0Fe 3.0Ni 4.5Mg 2.3La 0.2K 0.05Cs 0.1Zr 0.03+48%SiO 2 |
| Embodiment 10 | Mo 12Bi 1.0Fe 2.5Ni 6.5Mg 1.8Ce 0.2K 0.08Rb 0.05Cs 0.05 +50%SiO 2 |
| Embodiment 11 | Mo 12Bi 0.3Fe 2.1Ni 4.3Mg 2.2Ce 0.4K 0.12Cs 0.07Li 0.03 +51%SiO 2 |
| Embodiment 12 | Mo 12Bi 0.4Fe 1.6Ni 4.8Mg 1.8La 0.2Sm 0.4K 0.15Cs 0.05+50%SiO 2 |
| Embodiment 13 | Mo 12Bi 1.1Fe 3.8Ni 3.3Mn 0.5Ce 0.3Ca 0.2K 0.11Cs 0.09 +50%SiO 2 |
| Embodiment 14 | Mo 12Bi 0.4Fe 2.0Ni 3.8Mg 1.8Ce 0.2K 0.06Rb 0.07Cs 0.08 +50%SiO 2 |
| Embodiment 15 | Mo 12Bi 0.7Fe 2..7Ni 2.0Mg 2.4Ce 0.3K 0.14Cs 0.12+51%SiO 2 |
Table 2 catalyst is investigated result
| ? | Single-pass yield of acrylonitrile (%) | Acrylonitrile selective (%) | Propylene conversion (%) | Lattice Oxygen content μ mol/g |
| Comparative example 1 | 78.5 | 80.3 | 97.8 | 65 |
| Embodiment 1 | 81.6 | 85.2 | 95.8 | 108 |
| Embodiment 2 | 82.7 | 86.1 | 96.1 | 121 |
| Embodiment 3 | 85.1 | 86.4 | 98.5 | 258 |
| Embodiment 4 | 83.5 | 86.8 | 96.2 | 176 |
| Embodiment 5 | 84.3 | 85.5 | 98.6 | 231 |
| Embodiment 6 | 84.3 | 86.1 | 97.9 | 265 |
| Embodiment 7 | 85.6 | 86.3 | 99.2 | 241 |
| Embodiment 8 | 84.7 | 87.2 | 97.1 | 256 |
| Embodiment 9 | 81.8 | 83.5 | 98.0 | 157 |
| Embodiment 10 | 83.3 | 84.1 | 99.0 | 211 |
| Embodiment 11 | 85.1 | 86.6 | 98.3 | 242 |
| Embodiment 12 | 83.5 | 85.7 | 97.4 | 172 |
| Embodiment 13 | 85.1 | 86.9 | 97.9 | 216 |
| Embodiment 14 | 84.0 | 85.4 | 98.4 | 233 |
| Embodiment 15 | 84.8 | 85.2 | 99.5 | 218 |
Claims (3)
1. a unsaturated nitrile fluid catalyst prepared by ammoxidation, take Ludox as carrier, contains the active component that following general formula means:
Mo
12Bi
aFe
bNi
cX
dY
eZ
fK
gO
x
Wherein:
X is at least one being selected from Mg, Co, Ca, Be, Cu, Zn, Pb, Mn or Te;
Y is at least one being selected from La, Ce or Sm;
Z is at least one being selected from Rb, Li or Cs;
The span of a is 0.1～6.0;
The span of b is 0.1～10.0;
The span of c is 0.1～10.0;
The span of d is 0.1～10.0;
The span of e is 0.1～9.5;
The span of b/ (a+e) is 1.0～3.5;
The span of f is > 0～0.5;
The span of g is > 0～0.2;
X meets the required oxygen atom sum of other element valence, and the consumption of carrier is catalyst weight 30～70%; Wherein the span of b/ (a+e) is 1.0～3.5.
2. unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 1, the span that it is characterized in that b/ (a+e) is 1.5～2.5.
3. unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 1, the consumption that it is characterized in that carrier is catalyst weight 40～60%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015183284A1 (en) | 2014-05-29 | 2015-12-03 | Ineos Usa, Llc | Improved selective ammoxidation catalysts |
| WO2015183283A1 (en) | 2014-05-29 | 2015-12-03 | Ineos Usa, Llc | Improved selective ammoxidation catalysts |
| WO2016100023A1 (en) | 2014-12-17 | 2016-06-23 | Ineos Europe Ag | Improved mixed metal oxide ammoxidation catalysts |
| WO2018071166A1 (en) | 2016-10-11 | 2018-04-19 | Ineos Europe Ag | Ammoxidation catalyst with selective co-product hcn production |
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| JP2005029528A (en) * | 2003-07-09 | 2005-02-03 | Daiyanitorikkusu Kk | Method for producing acrylonitrile |
| JP2006326440A (en) * | 2005-05-24 | 2006-12-07 | Daiyanitorikkusu Kk | Catalyst for acrylonitrile synthesis |
| CN101884929A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Fluid catalyst for preparing acrylonitrile by propylene ammoxidation |
| CN101992091A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Unsaturated nitrile fluid catalyst prepared by ammoxidation and preparation method thereof |
-
2012
- 2012-05-16 CN CN2012101504942A patent/CN103418400A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005029528A (en) * | 2003-07-09 | 2005-02-03 | Daiyanitorikkusu Kk | Method for producing acrylonitrile |
| JP2006326440A (en) * | 2005-05-24 | 2006-12-07 | Daiyanitorikkusu Kk | Catalyst for acrylonitrile synthesis |
| CN101884929A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Fluid catalyst for preparing acrylonitrile by propylene ammoxidation |
| CN101992091A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Unsaturated nitrile fluid catalyst prepared by ammoxidation and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015183284A1 (en) | 2014-05-29 | 2015-12-03 | Ineos Usa, Llc | Improved selective ammoxidation catalysts |
| WO2015183283A1 (en) | 2014-05-29 | 2015-12-03 | Ineos Usa, Llc | Improved selective ammoxidation catalysts |
| US9211527B1 (en) | 2014-05-29 | 2015-12-15 | Ineos Europe Ag | Selective ammoxidation catalysts |
| WO2016100023A1 (en) | 2014-12-17 | 2016-06-23 | Ineos Europe Ag | Improved mixed metal oxide ammoxidation catalysts |
| WO2018071166A1 (en) | 2016-10-11 | 2018-04-19 | Ineos Europe Ag | Ammoxidation catalyst with selective co-product hcn production |
| CN110022979A (en) * | 2016-10-11 | 2019-07-16 | 英尼奥斯欧洲股份公司 | Ammoxidation catalyst with selective co-product HCN production |
| US10626082B2 (en) | 2016-10-11 | 2020-04-21 | Ineos Europe Ag | Ammoxidation catalyst with selective co-product HCN production |
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