CN103769128B - The preparation method of unsaturated nitrile fluid catalyst prepared by ammoxidation - Google Patents
The preparation method of unsaturated nitrile fluid catalyst prepared by ammoxidation Download PDFInfo
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- CN103769128B CN103769128B CN201210393313.9A CN201210393313A CN103769128B CN 103769128 B CN103769128 B CN 103769128B CN 201210393313 A CN201210393313 A CN 201210393313A CN 103769128 B CN103769128 B CN 103769128B
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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 present invention relates to a kind of preparation method of unsaturated nitrile fluid catalyst prepared by ammoxidation, mainly solve acrylonitrile catalyst crystal grain in prior art excessive, and be easy to sintering gathering at the reaction temperatures, cause propylene conversion low, acrylonitrile selectivity is low, and decline fast, cause the problem that acrylonitrile yield is low.The present invention is carrier by adopting with Ludox, the active constituent containing following general formula represents: Mo
12bi
afe
bni
cx
dy
ek
fz
gq
ho
x, wherein Z is rare earth element or its mixture, and the technical scheme being prepared into catalyst after the Nano Solid Solution crystallite first formed with template Q again solves this problem preferably, can be used in the industrial production of ammoxidating propylene to prepare acrylonitrile.
Description
Technical field
The present invention relates to a kind of preparation method of fluid catalyst of prepared by ammoxidation unsaturated nitrile, particularly about the preparation method of the fluid catalyst of propylene, butylene preparing acrylonitrile by ammoxidation, butene nitrile.
Background technology
The prepared by ammoxidation of alkene is developed sixties last century in last century by BP company for α, beta unsaturated nitrile technique, and the core technology of this technique is the catalyst using a kind of active component to contain Mo, Bi.Through constantly improving, current Mo-Bi series catalysts is very ripe, is industrially widely used by preparing acrylonitrile by allylamine oxidation technique.The improvement of catalyst in the past is mainly carried out from the activity of catalyst and stability aspect by the design of catalyst formulation, and as added transition metal to improve activity in active constituent, the list increasing product is received; Add rare earth element and 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 CN99119905.7, CN99119906.5, CN97106771.6 and CN96101529.2 all describe the Mo-Bi catalyst for propylene, isobutene ammonia oxidizing unsaturated nitrile catalyst of improvement, the advantage of these catalyst has good oxidation-reduction stability and reaction yield preferably, reacting ammonia than empty than and reaction temperature lower.
Patent CN01113194.2, CN01113193.4 and CN01113192.6 describe and in catalyst preparation process, to get method that part metals and organic ligand, chelating agent or surfactant prepared separately to improve catalyst at low ammonia than the performance under reaction condition.
Patent CN03151170.8 and CN03151169.4 describes in catalyst preparation process, and the grain diameter adding 2 ~ 25% in carrier starting material Ludox is that the solid silica of 5 ~ 100 nanometers is to improve catalyst performance.
Above patented technology is to the conversion ratio improving catalyst, and reduce the discharge of ammonia ratio and then minimizing amine wastewater of sulphuric acid in course of reaction, there has been certain effect the aspects such as the life-span of extending catalyst; But patent report up to now, all there is acrylonitrile catalyst crystal grain excessive, and be easy to sintering gathering at the reaction temperatures, cause propylene conversion low, acrylonitrile selectivity is low, and declines fast, causes the problem that acrylonitrile yield is low.
Summary of the invention
Technical problem to be solved by this invention is that to there is acrylonitrile catalyst crystal grain in prior art excessive, and be easy to sintering gathering at the reaction temperatures, cause propylene conversion low, acrylonitrile selectivity is low, and decline fast, cause the problem that acrylonitrile yield is low, a kind of preparation method of new unsaturated nitrile fluid catalyst prepared by ammoxidation is provided.Catalyst prepared by the method has effectively can reduce catalyst crystallite dimension, improve the anti-caking power of catalyst, for the reaction of prepared by ammoxidation unsaturated nitrile, and 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 preparation method of unsaturated nitrile fluid catalyst prepared by ammoxidation, and described catalyst take Ludox as carrier, the active component containing following general formula represents:
Mo
12bi
afe
bni
cx
dy
ek
fz
gq
ho
x, be prepared into catalyst again after wherein Z and template Q first forms Nano Solid Solution crystallite,
Wherein:
X is at least one be selected from Mg, Co, Ca, Be, Cu, Zn, Pb, Mn or Te;
Y is at least one be selected from Rb, Li or Cs;
Z is at least one be selected from La, Ce, Pr, Nd or Sm;
Q is template, is selected from least one in di-n-propylamine, diisopropylamine, pyrrolidines, ethylenediamine, n-butylamine, diethylamine, triethylamine, tetrapropyl ammonium, cyclohexylamine, polyethylene glycol, methylcellulose, softex kw, kollidon or DBSA ammonium;
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 ~ 0.5;
The span of f is >0 ~ 0.2;
The span of g is 0.1 ~ 3;
The span of h is 0.001 ~ 0.5;
The span of g/h ratio is 1 ~ 100;
X is for meeting the oxygen atom sum needed for other element valence, and the consumption of carrier is 30 ~ 70% of catalyst weight.
In technique scheme, the preferred span of g/h ratio is 1 ~ 50, and optimum valuing range is 5 ~ 20.The consumption preferable range of carrier is 40 ~ 60% of catalyst weight.The slurry of catalyst is after mist projection granulating, and at 520 ~ 660 DEG C, calcination activation obtains required catalyst in 0.2 ~ 4 hour.The calcination activation temperature preferable range of catalyst is 550 ~ 640 DEG C; Calcination activation time preferable range is 0.5 ~ 2 hour.The value preferable range of e is 0.01 ~ 0.35.The value preferable range of f is 0.001 ~ 0.1.
The starting material of required metallic element is corresponding water soluble salt, and Ludox carrier coprecipitation makes slurry, and the aging rear spray drying granulation of slurry, then high-temperature roasting obtains finished catalyst.
In the following embodiment provided, to the investigation appreciation condition of catalyst be:
Reactor: fluidized-bed reactor, internal diameter 38 millimeters
Catalyst filling amount: 550 grams
Reactor top pressure: 0.084MPa (gauge pressure)
Reaction temperature: 430 DEG C
Reaction time: 4 hours
Raw material ratio: propylene/ammonia/air=1/1.1/9.5,
WWH:0.06 hour
-1
Product 0 DEG C of diluted acid absorbs, with gas-chromatography and chemical analysis binding analysis product.And calculate Carbon balance, be valid data when Carbon balance is at (95 ~ 105) %.
Propylene conversion, acrylonitrile yield and be optionally defined as:
unreacting propylene C molal quantity
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 selectivity (%)=
× 100%
Propylene conversion
The present invention makes catalyst after passing through the Nano Solid Solution crystallite first formed at acrylonitrile catalyst formula rare earth elements and template Q, due to the guide effect of template structure, achieve the crystal transformation of rare earth compound hydrocarbyl oxide to solid solution, and cause distortion of lattice because of the difference of rare-earth cation radius, catalyst crystal grain diminishes, promote that the oxidation one of body phase oxygen is reduced, thus enhancing redox property, increase the selective oxidation reaction of propylene and Lattice Oxygen, and then also significantly increasing acrylonitrile selectivity, acrylonitrile yield significantly improves.As shown in table 2 result: catalyst grain size drops to the about 5 ~ 18nm of embodiment by the 26.4nm of comparative example 1, decline about 1 times, Be very effective; Acrylonitrile selectivity is increased to about 84 ~ 86% of embodiment by 80.3% of comparative example 1, and propylene conversion is increased to about 99% of embodiment by 97.8% of comparative example 1, and single-pass yield of acrylonitrile is then increased to by 78.5% and is up to 86.5%, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[comparative example 1]
By the Ludox of 1400 gram 40% (weight), stir 0.5 hour, obtain material A.
By 441.4 grams of (NH
4)
6mo
7o
244H
2o joins in the warm water of 330 grams 70 DEG C, stirs and makes its whole dissolving obtain material B, added fast in the B of strong stirring by A, obtain material C.
By 213.1 grams of Fe (NO
3)
39H
2o adds in 70 DEG C of hot water of 150 grams, adds 201.8 grams of Bi (NO after stirring and dissolving again
3)
35H
2o, 274.8 grams of Ni (NO
3)
36H
2o, 96.3 grams of Mg (NO
3)
36H
2o, 72.5 grams of La (NO
3)
33H
2o, 18.6 grams of Sm (NO
3)
33H
2material D is made after O stirring and dissolving.
1.1 grams of KNO are added in 20 grams of water
3, 0.9 gram of NaNO
3with 2.0 grams of CsNO
3added after dissolving in material D and formed material E.
Material E is dripped under fast stirring in material C, form catalyst pulp.In 70 DEG C of spraying dry after aging 3 hours, by the roasting 3 hours at 580 DEG C in rotary calciner of the particle of gained, obtain finished catalyst.
[embodiment 1 ~ 15]
According to the preparation process that comparative example 1 is identical, according to table 1 catalyst composition Kaolinite Preparation of Catalyst, difference is only that rare earth element first forms solid solution crystallite with template, is then ground to less than 20 microns and adds.Catalyst is investigated by above-mentioned investigation appreciation condition, and Activity evaluation and catalyst crystallite Analyzing on Size the results are shown in Table 2.
Table 1
Table 2
| Single-pass yield of acrylonitrile (%) | Acrylonitrile selectivity (%) | Propylene conversion (%) | Crystallite dimension (nm) | |
| Comparative example 1 | 78.5 | 80.3 | 97.8 | 26.4 |
| Embodiment 1 | 82.6 | 84.2 | 98.1 | 18.2 |
| Embodiment 2 | 83.8 | 84.5 | 99.2 | 12.9 |
| Embodiment 3 | 85.4 | 86.3 | 98.9 | 10.5 |
| Embodiment 4 | 86.3 | 86.6 | 99.7 | 5.3 |
| Embodiment 5 | 84.0 | 84.8 | 99.1 | 9.6 |
| Embodiment 6 | 84.7 | 85.7 | 98.8 | 16.4 |
| Embodiment 7 | 84.4 | 84.8 | 99.5 | 14.2 |
| Embodiment 8 | 83.8 | 84.7 | 98.9 | 13.1 |
| Embodiment 9 | 86.5 | 86.8 | 99.7 | 7.1 |
| Embodiment 10 | 84.4 | 85.4 | 98.8 | 4.6 |
| Embodiment 11 | 86.2 | 86.5 | 99.6 | 4.9 |
| Embodiment 12 | 83.7 | 84.6 | 98.9 | 14.4 |
| Embodiment 13 | 84.0 | 84.8 | 99.1 | 17.7 |
| Embodiment 14 | 84.7 | 85.3 | 99.3 | 11.5 |
| Embodiment 15 | 84.9 | 85.6 | 99.2 | 14.1 |
Claims (8)
1. a preparation method for unsaturated nitrile fluid catalyst prepared by ammoxidation, described catalyst take Ludox as carrier, the active component containing following general formula represents:
Mo
12bi
afe
bni
cx
dy
ek
fz
gq
ho
x, be prepared into catalyst again after wherein Z and template Q first forms Nano Solid Solution crystallite,
Wherein:
X is at least one be selected from Mg, Co, Ca, Be, Cu, Zn, Pb, Mn or Te;
Y is at least one be selected from Rb, Li or Cs;
Z is at least one be selected from La, Ce, Pr, Nd or Sm;
Q is template, is selected from least one in di-n-propylamine, diisopropylamine, pyrrolidines, ethylenediamine, n-butylamine, diethylamine, triethylamine, tetrapropyl ammonium, cyclohexylamine, polyethylene glycol, methylcellulose, softex kw, kollidon or DBSA ammonium;
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 ~ 0.5;
The span of f is 0 ~ 0.2;
The span of g is 0.1 ~ 3;
The span of h is 0.001 ~ 0.5;
The span of g/h ratio is 1 ~ 100;
X is for meeting the oxygen atom sum needed for other element valence, and the consumption of carrier is 30 ~ 70% of catalyst weight;
The starting material of above-mentioned metallic element is corresponding water soluble salt, and Ludox carrier coprecipitation makes slurry, the aging rear spray drying granulation of slurry, and then high-temperature roasting obtains finished catalyst;
Described slurry is after mist projection granulating, and at 520 ~ 660 DEG C, calcination activation obtains required catalyst in 0.2 ~ 4 hour.
2. the preparation method of unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 1, is characterized in that the span of g/h ratio is 1 ~ 50.
3. the preparation method of unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 2, is characterized in that the span of g/h ratio is 5 ~ 20.
4. the preparation method of unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 1, is characterized in that the consumption of carrier is catalyst weight 40 ~ 60%.
5. the preparation method of unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 1, is characterized in that the calcination activation temperature range of catalyst is 550 ~ 640 DEG C.
6. the preparation method of unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 1, is characterized in that calcination activation time range is 0.5 ~ 2 hour.
7. the preparation method of unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 1, is characterized in that the span of e is 0.01 ~ 0.35.
8. the preparation method of unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 1, is characterized in that the span of f is 0.001 ~ 0.1.
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| CN103769128B true CN103769128B (en) | 2015-11-18 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5576469A (en) * | 1995-06-05 | 1996-11-19 | The Standard Oil Co. | Paraffin ammoxidation using vanadium antimony oxide based catalysts with halide promoters |
| CN1393286A (en) * | 2001-06-29 | 2003-01-29 | 中国石化上海石油化工股份有限公司 | Process for preparing catalyst used to prepare unsaturated nitrile by ammoxidizing propylene or isobutylene |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060199730A1 (en) * | 2005-03-02 | 2006-09-07 | Seely Michael J | Composition and method for improving density and hardness of fluid bed catalysts |
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2012
- 2012-10-17 CN CN201210393313.9A patent/CN103769128B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5576469A (en) * | 1995-06-05 | 1996-11-19 | The Standard Oil Co. | Paraffin ammoxidation using vanadium antimony oxide based catalysts with halide promoters |
| CN1393286A (en) * | 2001-06-29 | 2003-01-29 | 中国石化上海石油化工股份有限公司 | Process for preparing catalyst used to prepare unsaturated nitrile by ammoxidizing propylene or isobutylene |
| 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 |
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