CN101121130A - Ammoxidation method to manufacturing unsaturated nitrile catalyst - Google Patents
Ammoxidation method to manufacturing unsaturated nitrile catalyst Download PDFInfo
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- CN101121130A CN101121130A CNA2006100299485A CN200610029948A CN101121130A CN 101121130 A CN101121130 A CN 101121130A CN A2006100299485 A CNA2006100299485 A CN A2006100299485A CN 200610029948 A CN200610029948 A CN 200610029948A CN 101121130 A CN101121130 A CN 101121130A
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- span
- catalyst
- unsaturated nitrile
- 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 present invention relates to an unsaturated nitrile catalyst, which is produced by an ammoxidation. The present invention solves the problem in the prior art that in an olefin ammoxidation, the reduction of a reacted ammonia ratio can cause that an oxidative ability is too strong, and oxidation products are increased, and an unsaturated nitrile selectivity of target products is decreased. The present invention solves the problem well by a technical proposal that SiO2 or Al2O3 is used as a carrier, and the active components of which is a combination with the following formula: in the formula of Mo12BiaFebNicMgdNaeAfBgOx, the A is selected from at least one of K, Rb, Cs or Li; the B is selected from at least one of Co, Ca, Ba, Be, Sr, Cu, Zn, Mn, Te, Ce or La. The present invention can be used for the industrial production of acrylonitrile.
Description
Technical field
The present invention relates to a kind of ammonia oxidation and produce unsaturated nitrile catalyst, particularly produce the fluid catalyst of acrylonitrile, butene nitrile about propylene, butylene ammoxidation.
Background technology
The ammoxidation of alkene prepares α, in the exploitation sixties in last century, the core technology of this technology is to use a kind of active component to contain the catalyst of Mo, Bi to beta unsaturated nitrile technology by BP company.Through constantly improving, the Mo-Bi series catalysts is very ripe at present, is widely used by preparing acrylonitrile by allylamine oxidation technology industrial.The improvement of catalyst is in the past mainly carried out from activity of such catalysts and stable aspect, as adding transition metal to improve activity in active constituent, increases the single of product and receives; Add rare earth element and improve redox ability; Add elements such as Na, P to improve the wearability of catalyst; Add elements such as Fe, Co, Ni to suppress the distillation of Mo, improve stability of catalyst or the like.
Patent CN 99119905.7, CN 99119906.5, CN 97106771.6 and CN 96101529.2 have all introduced the improved Mo-Bi catalyst that is used for propylene, isobutene ammonia oxidizing system unsaturated nitrile catalyst, the advantage of these catalyst has oxidation-reduction stability and reaction yield preferably preferably, and reacting ammonia ratio, empty ratio and reaction temperature are lower.
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 the reaction condition.
Patent CN 03151170.8 and CN 03151169.4 have introduced in the catalyst preparation process, and the solid silica that adds 2～25% grain diameter and be 5～100 nanometers in carrier starting material Ludox improves catalyst performance.
Summary of the invention
Technical problem to be solved by this invention is that prior art is in the ammoxidation reaction of alkene, reacting ammonia can cause oxidability strong excessively than reduction, oxidation product increases, and the problem that target product unsaturated nitrile selectivity descends provides a kind of new prepared by ammoxidation unsaturated nitrile catalyst.This catalyst is compared with existing similar catalyst, has to be suitable for when moving under lower reaction temperature condition than, ammonia at lower sky, and still can keep the characteristics of the active and target product selectivity of good catalyst reaction.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of ammoxidation method to manufacturing unsaturated nitrile catalyst, and with SiO
2, Al
2O
3Or its mixture is carrier, comprises the composition that has following general formula with atomic ratio measuring:
Mo
12Bi
aFe
bNi
cMg
dNa
eA
fB
gO
x
Wherein: A is selected from least a among K, Rb, Cs or the Li;
B is selected from least a among Co, Ca, Ba, Be, Sr, Cu, Zn, Mn, Te, Ce or the La;
The span of a is 0.1～2.0;
The span of b is 0.5～4.0;
The span of c is 0.1～10;
The span of d is 0.1～5.0;
The span of e is＞0～0.5;
The span of f is＞0～0.5;
The span of e+f sum is 0.01～0.7;
The span of g is＞0～5.0;
X satisfies the required oxygen atom sum of other element valence, and the consumption of carrier is 30～70% of a catalyst weight.
The value preferable range of a is 0.2～1.0 in the technique scheme; The value preferable range of b is 1.0～2.0; The value preferable range of c is 2.0～7.0; The value preferable range of d is 0.5～3.5; The value preferable range of e is 0.01～0.5; The value preferable range of f is 0.01～0.2; The value preferable range of e+f sum is 0.01～0.4; The value preferable range of g is 0.05～2.0, and more preferably scope is 0.1～0.8; Carrier consumption preferable range is 40～60% of a catalyst weight.
Catalyst can prepare with the coprecipitation that those skilled in the art are familiar with.The starting material of required metallic element is corresponding water soluble salt, the dissolving of metallic element starting material is made mixed salt solution later, and make slurry with coprecipitation with the carrier starting material, the aging back of slurry spray drying granulation, high-temperature roasting obtains the catalyst finished product then, and sintering temperature is 500 ℃～610 ℃.
In the following embodiment that provides, be to the investigation appreciation condition of catalyst:
Reactor: fluidized-bed reactor, 38 millimeters of internal diameters
Catalyst filling amount: 550 grams
Reactor top pressure: 0.084MPa (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 is valid data during at (95～105) %.
Propylene conversion, acrylonitrile yield and optionally be defined as:
Among the present invention, owing to do not introduce acid element, as W, V, P, Cr etc., can regulate catalyst surface acid centre intensity and quantity well but introduce elements such as Na, rare earth, alkali metal, the ability that makes the catalyst ammine selective be converted into acrylonitrile strengthens, significantly improve than acrylonitrile once through yield under the condition at lower ammonia ratio, sky, obtained better technical effect.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
With 441.4 gram (NH
4)
6Mo
7O
244H
2O joins in the warm water of 70 ℃ of 330 grams, stirs and makes its whole dissolvings, and the Ludox that adds 1400 grams 40% (weight) is made material A.
With 213.1 gram Fe (NO
3)
39H
2O adds in 70 ℃ of hot water of 150 grams, adds 201.8 gram Bi (NO after the 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)
3NH
2Make material B after the O stirring and dissolving.
In 20 gram water, add 1.1 gram KNO
3, 0.9 the gram NaNO
3With 2.0 gram CsNO
3To form material C among its adding material B after the dissolving.
Material C is dripped in material A under stirring fast, form catalyst pulp.In 70 ℃ of spray-dryings after aging 3 hours, with the particle of gained in rotary calciner in 580 ℃ of following roastings 3 hours, finished catalyst.
[embodiment 2～12]
According to identical preparation process, form preparation according to table 1 catalyst.
Finished catalyst is investigated by above-mentioned investigation appreciation condition, and it the results are shown in Table 1.
Table 1 embodiment
| Embodiment | The embodiment catalyst is formed |
| 1 | Mo 12Bi 2.0Fe 2.5Ni 4.5Mg 1.8La 0.8K 0.05Cs 0.05Na 0.05+50％SiO 2 |
| 2 | Mo 12Bi 1.2Fe 2.5Ni 4.5Mg 0.5Co 1.8Ce 0.8K 0.03Na 0.1Ca 0.9+60％SiO 2 |
| 3 | Mo 12Bi 0.5Fe 1.8Ni 8.0Mg 1.8La 0.8K 0.1Cs 0.1Na 0.2Ba 0.3+40％SiO 2 |
| 4 | Mo 12Bi 0.2Fe 2.0Ni 6.8Mg 2.0Cs 0.09Na 0.04Sr 3.0+40％SiO 2+20％Al 2O 3 |
| 5 | Mo 12Bi 2.0Fe 1.5Ni 4.5Mg 4.0Co 1.0La 0.8Cu 0.6K 0.3Cs 0.05Na 0.05+25％SiO 2+35％Al 2O 3 |
| 6 | Mo 12Bi 0.8Fe 1.0Ni 3.0Mg 1.8La 0.8K 0.06Cs 0.05Na 0.2+50％SiO 2 |
| 7 | Mo 2Bi 1.2Fe 2.2Ni 5.3Mg 2.5Mn 1.8Ce 0.8Ca 0.2K 0.05Cs 0.05Na 0.5Te 0.3+40％SiO 2+10％Al 2O 3 |
| 8 | Mo 12Bi 0.3Fe 2.9Ni 4.5Mg 2.8K 0.08Cs 0.2Na 0.05+60％Al 2O 3 |
| 9 | Mo 12Bi 0.7Fe 2.5Ni 2.5Mg 1.0Zn 3.2Ce 0.3K 0.3Na 0.05+40％SiO 2+10％Al 2O 3 |
| 10 | Mo 12Bi 2.0Fe 3.0Ni 1.0Mg 2.7La 0.8Na 0.07K 0.07Cs 0.1+25％SiO 2+25％Al 2O 3 |
| 11 | Mo 12Bi 2.0Fe 0.5Ni 4.5Mg 3.5Na 0.01La 0.8Rb 0.05Cs 0.2+40％Al 2O 3 |
| 12 | Mo 12Bi 1.7Fe 2.2Ni 5.5Mg 2.5La 0.8K 0.05Cs 0.03Na 0.3+20％SiO 2+20％Al 2O 3 |
Table 2 embodiment investigates the result
| Embodiment | Single-pass yield of acrylonitrile (%) | Acrylonitrile selectivity (%) | Propylene conversion (%) |
| 1 | 78.5 | 80.0 | 98.1 |
| 2 | 76.8 | 77.2 | 99.5 |
| 3 | 80.4 | 81.6 | 98.5 |
| 4 | 77.1 | 78.0 | 98.8 |
| 5 | 77.8 | 81.2 | 95.8 |
| 6 | 83.2 | 83.8 | 99.4 |
| 7 | 80.6 | 81.8 | 98.5 |
| 8 | 75.6 | 79.9 | 94.6 |
| 9 | 82.2 | 82.4 | 99.8 |
| 10 | 77.3 | 80.1 | 96.5 |
| 11 | 78.2 | 83.4 | 93.8 |
| 12 | 81.3 | 81.6 | 99.6 |
Claims (4)
1. ammoxidation method to manufacturing unsaturated nitrile catalyst is with SiO
2, Al
2O
3Or its mixture is carrier, comprises the composition that has following general formula with atomic ratio measuring:
Mo
12Bi
aFe
bNi
cMg
dNa
eA
fB
gO
x
Wherein: A is selected from least a among K, Rb, Cs or the Li;
B is selected from least a among Co, Ca, Ba, Be, Sr, Cu, Zn, Mn, Te, Ce or the La;
The span of a is 0.1～2.0;
The span of b is 0.5～4.0;
The span of c is 0.1～10;
The span of d is 0.1～5.0;
The span of e is＞0～0.5;
The span of f is＞0～0.5;
The span of e+f sum is 0.01～0.7;
The span of g is＞0～5.0;
X satisfies the required oxygen atom sum of other element valence, and the consumption of carrier is 30～70% of a catalyst weight.
2. ammoxidation method to manufacturing unsaturated nitrile catalyst according to claim 1, the span that it is characterized in that a is 0.2～1.0; The span of b is 1.0～2.0; The span of c is 2.0～7.0; The span of d is 0.5～3.5; The span of e is 0.01～0.5; The span of f is 0.01～0.2; The span of e+f sum is 0.01～0.4; The span of g is 0.05～2.0.
3. ammoxidation method to manufacturing unsaturated nitrile catalyst according to claim 2, the span that it is characterized in that g is 0.1～0.8.
4. ammoxidation method to manufacturing unsaturated nitrile catalyst according to claim 1, the consumption that it is characterized in that carrier is 40～60% of a catalyst weight.
Priority Applications (1)
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101992091B (en) * | 2009-08-31 | 2012-05-23 | 中国石油化工股份有限公司 | Unsaturated nitrile fluid catalyst prepared by ammoxidation and preparation method thereof |
| CN102040543B (en) * | 2009-10-13 | 2012-05-30 | 中国石油化工股份有限公司 | Method for producing unsaturated nitrile through ammoxidation |
| CN101811058B (en) * | 2009-02-19 | 2012-09-05 | 中国石油化工股份有限公司 | Unsaturated nitrile fluid catalyst prepared by ammoxidation |
| CN103769138A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Ammonia oxidation to unsaturated nitrile fluid catalyst, preparation method and application of ammonia oxidation to unsaturated nitrile fluid catalyst |
| CN105498810A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Catalyst for preparation of 3-acetoxy propionaldehyde |
| CN105498786A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Catalyst for synthesis of 3-acetoxy propionaldehyde |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1013079B (en) * | 1987-05-14 | 1991-07-10 | 中国石油化工总公司 | Production method of acrylonitrile catalyst |
| US5093299A (en) * | 1990-01-09 | 1992-03-03 | The Standard Oil Company | Catalyst for process for the manufacture of acrylonitrile and methacrylonitrile |
| CN1055285C (en) * | 1997-12-11 | 2000-08-09 | 中国石油化工总公司 | Catalyst for propylene and isobutylene ammoxidation fluidized bed |
| CN1137881C (en) * | 2001-06-29 | 2004-02-11 | 中国石化上海石油化工股份有限公司 | Process for preparing catalyst used for oxidizing ammonia |
-
2006
- 2006-08-11 CN CN2006100299485A patent/CN101121130B/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811058B (en) * | 2009-02-19 | 2012-09-05 | 中国石油化工股份有限公司 | Unsaturated nitrile fluid catalyst prepared by ammoxidation |
| CN101992091B (en) * | 2009-08-31 | 2012-05-23 | 中国石油化工股份有限公司 | Unsaturated nitrile fluid catalyst prepared by ammoxidation and preparation method thereof |
| CN102040543B (en) * | 2009-10-13 | 2012-05-30 | 中国石油化工股份有限公司 | Method for producing unsaturated nitrile through ammoxidation |
| CN103769138A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Ammonia oxidation to unsaturated nitrile fluid catalyst, preparation method and application of ammonia oxidation to unsaturated nitrile fluid catalyst |
| CN103769138B (en) * | 2012-10-25 | 2015-12-16 | 中国石油化工股份有限公司 | Unsaturated nitrile fluid catalyst prepared by ammoxidation, preparation method and application thereof |
| CN105498810A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Catalyst for preparation of 3-acetoxy propionaldehyde |
| CN105498786A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Catalyst for synthesis of 3-acetoxy propionaldehyde |
| CN105498810B (en) * | 2014-09-25 | 2018-02-13 | 中国石油化工股份有限公司 | Prepare the catalyst used in 3 acetoxyl group propionic aldehyde |
| CN105498786B (en) * | 2014-09-25 | 2018-07-17 | 中国石油化工股份有限公司 | Synthesize the catalyst used in 3- acetoxyl group propionic aldehyde |
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| CN101121130B (en) | 2010-10-27 |
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