CN102371156B - Unsaturated nitrile fluidized bed catalyst prepared by ammoxidation and its preparation method - Google Patents
Unsaturated nitrile fluidized bed catalyst prepared by ammoxidation and its preparation method Download PDFInfo
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- CN102371156B CN102371156B CN2010102614870A CN201010261487A CN102371156B CN 102371156 B CN102371156 B CN 102371156B CN 2010102614870 A CN2010102614870 A CN 2010102614870A CN 201010261487 A CN201010261487 A CN 201010261487A CN 102371156 B CN102371156 B CN 102371156B
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Abstract
The present invention relates to a fluidized bed catalyst of unsaturated nitrile which is produced by an ammoxidation and a preparation method. The present invention mainly solves the problems in the prior art that the specific surface of an acrylonitrile catalyst is low, the specific surface is decreased with prolongation of the reaction time, the decreased pore volume and the decreased acrylonitrile selectivity reduce the yield of acrylonitrile. According to the invention, silica sol is taken as a carrier, and the catalyst contains active components, the general formula of which is as follows: in the formula of Mo12BiaFebNicXdYeZfQgKhOx, the Q is selected from at least one of Zr, Ti or Th, and is reacted with silica sol and embedded in silica sol micelle to produce the catalyst, the aperture distribution is narrow, and the sintering process is effectively prevented. The technical scheme better solves the problems, and can be used for the industrial production of acrylonitrile which is produced by a propylene ammoxidation.
Description
Technical field
The present invention relates to fluid catalyst of a kind of prepared by ammoxidation unsaturated nitrile and preparation method thereof, particularly about fluid catalyst of propylene, butylene preparing acrylonitrile by ammoxidation, butene nitrile and preparation method thereof.
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 up to now, the acrylonitrile catalyst specific surface is low, and, along with the prolongation in reaction time, specific surface descends, and pore volume reduces, and acrylonitrile selectively descends, the problem that causes acrylonitrile yield to reduce.
Summary of the invention
One of technical problem to be solved by this invention is in prior art, to exist the acrylonitrile catalyst specific surface low, and the prolongation along with the reaction time, specific surface descends, pore volume reduces, acrylonitrile selectively descends, the problem that causes acrylonitrile yield to reduce, provide a kind of new unsaturated nitrile fluid catalyst prepared by ammoxidation.This catalyst has for the reaction of prepared by ammoxidation unsaturated nitrile that catalyst specific surface is high, pore volume is large, pore structure is stable, and acrylonitrile is selectively stablized, the advantage of acrylonitrile yield good stability.Two of technical problem to be solved by this invention is to provide a kind of preparation method corresponding with the catalyst of one of technical solution problem.
For one of 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
fQ
gK
hO
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;
Q is at least one being selected from Zr, Ti or Th;
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 f is>0~0.5;
The span of e+f sum is 0.15~10.0;
The span of g is>0~0.2;
The span of h is>0~0.6;
X meets the required oxygen atom sum of other element valence, and the consumption of carrier is catalyst weight 30~70%; Wherein high-valency metal element Q first with the Ludox effect, embed the Ludox micelle and introduce catalyst.
In technique scheme, the consumption preferable range of carrier is catalyst weight 40~60%; The value preferable range of g is 0.01~0.1.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the preparation method of described unsaturated nitrile fluid catalyst prepared by ammoxidation comprises the following steps:
A) by the water-soluble solution I that obtains in the Q source of the solubility of aequum;
B) by the water-soluble solution II that obtains of the salt that is selected from Bi, Fe, Ni, X, Y, Z and K of aequum;
C) by the water-soluble solution III that obtains of the ammonium molybdate of aequum;
D), by solution I and the effect of Ludox Ludox, embed the Ludox micelle and obtain IV;
E) after IV is added to solution III mixes, then add solution II to obtain required catalyst pulp;
F) catalyst pulp, after mist projection granulating, obtains required catalyst in 0.2~4 hour in 520~660 ℃ of lower calcination activations.
In technique scheme, 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, high-valency metal element Q elder generation and Ludox effect, embed the Ludox micelle, with the oxygen element bridging of silicon oxygen bond in Ludox, combine closely, other metallic element starting materials are made mixed salt solution after dissolving, and make slurry with the Ludox carrier after the Q element interaction 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: 0.084MPa (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, be valid data during at (95~105) %.
Propylene conversion, acrylonitrile yield and optionally be defined as:
The present invention by introducing high valence elements Q in the Ludox carrier, make after catalyst because of the electrical charge rejection effect between high valence elements, the sintering process that has effectively stoped catalyst, the specific surface of catalyst is high, pore volume is large, pore structure is stable, suppressed well the generation of side reaction in the ammoxidation reaction, the principal product acrylonitrile selectively significantly improves, thereby improved acrylonitrile yield, as shown in table 2 result: 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%, obtained technique effect preferably, and what is more important catalyst pores Stability Analysis of Structures, its activity stability excellence, embodiment 10 catalyst through 2000 hours the reaction after, acrylonitrile selectively by 86.4%, become 85.8%, acrylonitrile yield becomes 84.5% by 85.1%, and specific surface is by 46.3m
2/ g becomes 43.7m
2/ g, pore volume becomes 0.236ml/g by 0.240ml/g, almost there is no much variations, the catalyst of result embodiment 1 as shown in table 3 through 2000 hours the reaction after, acrylonitrile selectively by 80.3%, become 76.1%, acrylonitrile yield becomes 70.8% by 78.5%, and specific surface is by 41.2m
2/ g becomes 36.4m
2/ g, pore volume becomes 0.186ml/g by 0.202ml/g, descends significantly, and result is as shown in table 4.
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 preparation according to table 1 catalyst, and its only difference is 1.1 gram KNO
3the Ludox that adds 1400 grams 40% (weight), stir 0.5 hour, makes part K stabilized silica sol, obtains the material A finished product; But not by 1.1 gram KNO
3with 0.9 gram NaNO
3with 2.0 gram CsNO
3dissolve together.Catalyst is investigated by above-mentioned investigation appreciation condition, and initial activity and stability result are respectively in Table 2,3.
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 0.7Sm 0.2Zr 0.01K 0.07+46%SiO 2 |
Embodiment 2 | Mo 12Bi 0.5Fe 1.9Ni 5.8Mg 2.3La 0.8Ti 0.2K 0.1Rb 0.08+46%SiO 2 |
Embodiment 3 | Mo 12Bi 0.2Fe 2.0Ni 6.8Mg 0.9Sm 0.6K 0.1Cs 0.05Zr 0.06+50%SiO 2 |
Embodiment 4 | Mo 12Bi 2.0Fe 1.5Ni 4.5Co 4.0Ti 0.04La 1.5Cu 0.6K 0.02Cs 0.09+52%SiO 2 |
Embodiment 5 | Mo 12Bi 0.8Fe 1.2Ni 3.0Mg 1.8La 0.8Sm 0.2K 0.05Cs 0.05Ti 0.02Al 0.8+50%SiO 2 |
Embodiment 6 | Mo 12Bi 1.2Fe 2.8Ni 5.3Mn 0.7Ce 0.8Ca 0.2K 0.11Cs 0.054Zr 0.09Ti 0.35+50%SiO 2 |
Embodiment 7 | Mo 12Bi 0.9Fe 4.9Ni 4.5Mg 2.8Pb 0.2Ce 1.3Ti 0.03K 0.12Cs 0.13+52%SiO 2 |
Embodiment 8 | Mo 12Bi 0.7Fe 2.5Ni 5.5Ti 0.3Ce 0.3K 0.15Cs 0.1Li 0.05Zr 0.01+47%SiO 2 |
Embodiment 9 | Mo 12Bi 2.0Fe 3.0Ni 4.5Mg 2.3La 0.8K 0.05Cs 0.1Zr 0.03+48%SiO 2 |
Embodiment 10 | Mo 12Bi 2.0Fe 2.5Ni 4.5Mg 1.8Ce 1.2K 0.08Rb 0.05Cs 0.05Zr 0.04Ti 0.05+50%SiO 2 |
Embodiment 11 | Mo 12Bi 1.3Fe 2.1Ni 4.3Mg 2.2Ce 0.4Al 0.6Zr 0.02Ti 0.04K 0.12Cs 0.07Li 0.03+51%SiO 2 |
Embodiment 12 | Mo 12Bi 0.4Fe 1.6Ni 3.8Mg 1.8La 0.6Sm 0.4K 0.15Cs 0.05Ti 0.1Zr 0.02+50%SiO 2 |
Embodiment 13 | Mo 12Bi 1.4Fe 1.8Ni 6.3Mn 0.5Ce 0.3Ca 0.2K 0.11Cs 0.09Zr 0.02Ti 0.08+50%SiO 2 |
Embodiment 14 | Mo 12Bi 2.4Fe 2.0Ni 4.8Mg 1.8Ce 1.2K 0.06Rb 0.07Cs 0.08Zr 0.08Ti 0.05+50%SiO 2 |
Embodiment 15 | Mo 12Bi 0.7Fe 1.7Ni 5.9Mg 2.4Ce 0.9Zr 0.04Ti 0.01K 0.14Cs 0.12+51%SiO 2 |
Table 2 catalyst is investigated result
Single-pass yield of acrylonitrile (%) | Acrylonitrile selective (%) | Propylene conversion (%) | |
Comparative example 1 | 78.5 | 80.3 | 97.8 |
Embodiment 1 | 82.8 | 85.9 | 96.4 |
Embodiment 2 | 83.9 | 86.1 | 97.4 |
Embodiment 3 | 81.7 | 86.5 | 94.5 |
Embodiment 4 | 84.7 | 87.2 | 97.1 |
Embodiment 5 | 82.3 | 87.5 | 94.1 |
Embodiment 6 | 81.6 | 85.2 | 95.8 |
Embodiment 7 | 83.6 | 85.3 | 98.0 |
Embodiment 8 | 84.0 | 85.4 | 98.4 |
Embodiment 9 | 81.4 | 82.5 | 98.7 |
Embodiment 10 | 84.3 | 86.1 | 97.9 |
Embodiment 11 | 85.1 | 86.4 | 98.5 |
Embodiment 12 | 83.5 | 85.7 | 97.4 |
Embodiment 13 | 82.1 | 83.9 | 97.9 |
Embodiment 14 | 82.8 | 84.0 | 98.6 |
Embodiment 15 | 83.7 | 85.1 | 98.3 |
Table 3 embodiment 10 catalyst stabilities are investigated result
Table 4 comparative example 1 catalyst stability is investigated result
Claims (6)
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
fQ
gK
hO
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;
Q is at least one being selected from Zr, Ti or Th;
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 f is>0 and is below 0.5;
The span of e+f sum is 0.15~10.0;
The span of g is>0 and is below 0.2;
The span of h is>0 and is below 0.6;
X meets the required oxygen atom sum of other element valence, and the consumption of carrier is catalyst weight 30~70%; Wherein high-valency metal element Q first with the Ludox effect, embed the Ludox micelle and introduce catalyst.
2. 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%.
3. unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 1, the span that it is characterized in that h is 0.05~0.4.
4. the preparation method of unsaturated nitrile fluid catalyst prepared by ammoxidation claimed in claim 1 comprises the following steps:
A) by the water-soluble solution I that obtains in the Q source of the solubility of aequum;
B) by the water-soluble solution II that obtains of the salt that is selected from Bi, Fe, Ni, X, Y, Z and K of aequum;
C) by the water-soluble solution III that obtains of the ammonium molybdate of aequum;
D), by solution I and Ludox effect, embed the Ludox micelle and obtain IV;
E) after IV is added to solution III mixes, then add solution II to obtain required catalyst pulp;
F) catalyst pulp, after mist projection granulating, obtains required catalyst in 0.2~4 hour in 520~660 ℃ of lower calcination activations.
5. the preparation method of unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 4, the calcination activation temperature range that it is characterized in that catalyst is 550~640 ℃.
6. the preparation method of unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 4, the calcination activation time range that it is characterized in that catalyst is 0.5~2 hour.
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CN103657669A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing unsaturation nitrile through ammoxidation and method thereof |
CN103736496B (en) * | 2012-10-17 | 2015-10-21 | 中国石油化工股份有限公司 | Unsaturated nitrile fluid catalyst prepared by ammoxidation preparation method |
CN103769127B (en) * | 2012-10-17 | 2015-11-18 | 中国石油化工股份有限公司 | Ammoxidation method to manufacturing unsaturated nitrile fluid-bed catalyst |
CN103769129B (en) * | 2012-10-17 | 2015-12-16 | 中国石油化工股份有限公司 | Fluid catalyst of prepared by ammoxidation unsaturated nitrile and preparation method thereof |
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 |
CN105195165B (en) * | 2015-10-23 | 2017-09-29 | 中海油天津化工研究设计院有限公司 | A kind of fluid catalyst of olefin ammoxidation unsaturated nitrile and preparation method thereof |
KR20220008669A (en) * | 2020-07-14 | 2022-01-21 | 주식회사 엘지화학 | Ammoxidation catalyst for propylene, manufacturing method of the same catalyst, ammoxidation methode using the same catalyst |
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CN1129408A (en) * | 1993-08-17 | 1996-08-21 | 旭化成工业株式会社 | Ammoxidation catalyst composition |
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