CN103769138B - Unsaturated nitrile fluid catalyst prepared by ammoxidation, preparation method and application thereof - Google Patents
Unsaturated nitrile fluid catalyst prepared by ammoxidation, preparation method and application thereof Download PDFInfo
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- CN103769138B CN103769138B CN201210412584.4A CN201210412584A CN103769138B CN 103769138 B CN103769138 B CN 103769138B CN 201210412584 A CN201210412584 A CN 201210412584A CN 103769138 B CN103769138 B CN 103769138B
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Abstract
The present invention relates to a kind of unsaturated nitrile fluid catalyst prepared by ammoxidation, preparation method and application thereof, mainly solve acrylonitrile catalyst Lattice Oxygen content in prior art low, easily and gas phase oxygen generation deep oxidation, acrylonitrile selectivity is not high, causes the problem that acrylonitrile yield is low for propylene.The present invention is carrier by adopting with Ludox, the active constituent containing following general formula represents: Mo
12bi
afe
bni
cx
dy
ez
fq
gk
ho
x, wherein Q is at least one be selected from Sb, Nb or Ta, and first and Ludox effect by it, embed Ludox micelle, the technical scheme making catalyst solves this problem preferably, can be used in the industrial production of ammoxidating propylene to produce acrylonitrile.
Description
Technical field
The present invention relates to a kind of fluid catalyst of prepared by ammoxidation unsaturated nitrile, preparation method and application thereof.
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 up to now, acrylonitrile catalyst because of Lattice Oxygen content low, easily and gas phase oxygen generation deep oxidation, all there is acrylonitrile selectivity not high, cause the problem that acrylonitrile yield is low in propylene.
Summary of the invention
One of technical problem to be solved by this invention be exist in prior art acrylonitrile catalyst because of Lattice Oxygen content low, propylene easily and gas phase oxygen generation deep oxidation, acrylonitrile selectivity is not high, cause the problem that acrylonitrile yield is low, a kind of new unsaturated nitrile fluid catalyst prepared by ammoxidation is provided.This catalyst is used for the reaction of prepared by ammoxidation unsaturated nitrile, and to have catalyst crystal lattice oxygen content high, and propylene and Lattice Oxygen are reacted, and acrylonitrile selectivity is high, the advantage that acrylonitrile yield significantly improves.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.Three of technical problem to be solved by this invention is to provide a kind of application of described catalyst.
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, the active component containing following general formula represents:
Mo
12Bi
aFe
bNi
cX
dY
eZ
fQ
gK
hO
x
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 La, Ce or Sm;
Z is at least one be selected from Rb, Li or Cs;
Q is at least one be selected from Sb, Nb or Ta;
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 is for meeting the oxygen atom sum needed for other element valence, and the consumption of carrier is 30 ~ 70% of catalyst weight; Wherein high-valency metal element Q elder generation and Ludox effect, embed Ludox micelle and introduce catalyst.
In technique scheme, the consumption preferable range of carrier is 40 ~ 60% of catalyst weight.The value preferable range of a is 0.5 ~ 4.0; The value preferable range of b is 0.5 ~ 5.0; The value preferable range of c is 0.5 ~ 5.0; The value preferable range of d is 0.5 ~ 5.0; The value preferable range of e is 0.5 ~ 5.5; The value preferable range of f is 0.01 ~ 0.3; The value preferable range of e+f sum is 0.2 ~ 8.0; The value preferable range of g is 0.01 ~ 0.16; The value preferable range of h is 0.05 ~ 0.4.X preferred version is at least one be selected from Mg, Co, Ca or Cu.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method of unsaturated nitrile fluid catalyst prepared by ammoxidation, comprises the following steps:
A) solution I is obtained by water-soluble for the Q source of the solubility of aequum;
B) solution II is obtained by water-soluble for the salt being selected from Bi, Fe, Ni, X, Y, Z and K of aequum;
C) solution III is obtained by water-soluble for the ammonium molybdate of aequum;
D) by solution I and the effect of Ludox Ludox, embed Ludox micelle and obtain IV;
E) be added to after solution III mixes by IV, then add solution II required catalyst pulp;
F) catalyst pulp is after mist projection granulating, and at 520 ~ 660 DEG C, calcination activation obtains required catalyst in 0.2 ~ 4 hour.
In technique scheme, the calcination activation temperature preferable range of catalyst is 550 ~ 640 DEG C.Calcination activation time preferable range is 0.5 ~ 2 hour.
The coprecipitation preparation that catalyst can be familiar with those skilled in the art.The starting material of required metallic element is corresponding water soluble salt, high-valency metal element Q elder generation and Ludox effect, embed Ludox micelle, combine closely with the oxygen element bridging of silicon oxygen bond in Ludox, other metallic element starting materials make mixed salt solution after dissolving, and make slurry with the Ludox carrier coprecipitation after Q element interaction, the aging rear spray drying granulation of slurry, then high-temperature roasting obtains finished catalyst, calcination activation temperature preferable range is 550 ~ 640 DEG C, and calcination activation time preferable range is 0.5 ~ 2 hour.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: a kind of method of ammoxidating propylene to produce acrylonitrile, and catalyst wherein used is above-mentioned unsaturated nitrile fluid catalyst prepared by ammoxidation.
In technique scheme, with propylene, ammonia and air for raw material, material molar ratio propylene/ammonia/air=1/ (1.05 ~ 1.30)/(9.2 ~ 9.8), reaction condition is: reaction temperature 420 ~ 440 DEG C, reaction pressure 0.06 ~ 0.14MPa, propylene load WWH=0.06 ~ 0.10 hour of catalyst
-1.
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, and with gas-chromatography and chemical analysis binding analysis product, and calculates Carbon balance, is 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 by introducing high valence elements Q in Ludox carrier; make catalyst because of Lattice Oxygen enrich; propylene and Lattice Oxygen are reacted; inhibit the generation of side reaction in ammoxidation reaction well; principal product acrylonitrile selectivity significantly improves; thus improve acrylonitrile yield, as shown in table 2 result: the Lattice Oxygen of catalyst is increased to about 200 μm of ol/g of embodiment, rising scale 1 ~ 3 times by 65 μm of ol/g of comparative example 1; Acrylonitrile selectivity is increased to about 86% of embodiment by 80.3% of comparative example 1, and single-pass yield of acrylonitrile is then increased to about 84% by 78.5%, 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 the preparation of table 1 catalyst composition, its only difference is 1.1 grams of KNO
3add the Ludox of 1400 gram 40% (weight), stir 0.5 hour, make part K stabilized silica sol, obtain material A finished product; But not by 1.1 grams of KNO
3with 0.9 gram of NaNO
3with 2.0 grams of 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 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 2.2Ni 6.6Co 1.0Ce 0.7Sm 0.2Sb 0.01K 0.07+46%SiO 2 |
| Embodiment 2 | Mo 12Bi 0.5Fe 1.6Ni 4.5Mg 2.5La 0.8Nb 0.2K 0.1Rb 0.08+46%SiO 2 |
| Embodiment 3 | Mo 12Bi 0.4Fe 2.0Ni 5.8Mg 1.2Sm 0.6K 0.1Cs 0.05Ta 0.06+50%SiO 2 |
| Embodiment 4 | Mo 12Bi 1.0Fe 1.2Ni 4.5Co 3.5Sb 0.04Nb 0.1La 1.5Cu 0.6K 0.02Cs 0.09+52%SiO 2 |
| Embodiment 5 | Mo 12Bi 0.8Fe 1.5Ni 5.4Mg 1.8La 0.3Sm 0.2K 0.05Cs 0.05Ta 0.02Sb 0.08+50%SiO 2 |
| Embodiment 6 | Mo 12Bi 1.2Fe 2.6Ni 5.9Mn 0.2Ce 0.8Ca 0.1K 0.11Cs 0.05Sb 0.09Nb 0.09+50%SiO 2 |
| Embodiment 7 | Mo 12Bi 0.8Fe 2.6Ni 5.5Mg 1.8Ce 1.3Nb 0.09Ta 0.02K 0.12Cs 0.13+52% SiO 2 |
| Embodiment 8 | Mo 12Bi 1.5Fe 2.5Ni 7.0Nb 0.3Ce 0.3K 0.15Cs 0.1Li 0.05 +47%SiO 2 |
| Embodiment 9 | Mo 12Bi 2.0Fe 3.5Ni 2.5Mg 4.0La 0.8K 0.05Cs 0.1Nb 0.09Ta 0.11+48%SiO 2 |
| Embodiment 10 | Mo 12Bi 2.0Fe 2.1Ni 5.8Mg 1.5Ce 1.2K 0.08Rb 0.05Cs 0.05Sb 0.1Nb 0.05+50%SiO 2 |
| Embodiment 11 | Mo 12Bi 1.3Fe 1.8Ni 2.8Mg 4.2Ce 0.6Nb 0.02Ta 0.08K 0.12Cs 0.07Li 0.03 +51%SiO 2 |
| Embodiment 12 | Mo 12Bi 0.4Fe 2.6Ni 3.4Mg 2.5La 0.3Sm 0.5K 0.15Cs 0.05Nb 0.02Ta 0.12+50%SiO 2 |
| Embodiment 13 | Mo 12Bi 1.4Fe 1.4Ni 6.0Mn 0.2Ce 0.5Ca 0.2K 0.11Cs 0.09Sb 0.06Nb 0.05+50%SiO 2 |
| Embodiment 14 | Mo 12Bi 2.1Fe 2.0Ni 4.8Mg 1.5Ce 1.2K 0.06Rb 0.07Cs 0.08Nb 0.08Ta 0.02+50%SiO 2 |
| Embodiment 15 | Mo 12Bi 0.6Fe 2.2Ni 6.4Mg 2.2Ce 0.5Sb 0.08Nb 0.03K 0.14Cs 0.12+51%SiO 2 |
Table 2
Claims (9)
1. a unsaturated nitrile fluid catalyst prepared by ammoxidation take Ludox as carrier, the active component containing following general formula represents:
Mo
12Bi
aFe
bNi
cX
dY
eZ
fQ
gK
hO
x
Wherein:
X is selected from least one in Mg, Co, Ca, Be, Cu, Zn, Pb, Mn or Te;
Y is selected from least one in La, Ce or Sm;
Z is selected from least one in Rb, Li or Cs;
Q is selected from least one in Sb, Nb or Ta;
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, and non-vanishing;
The span of e+f sum is 0.15 ~ 10.0;
The span of g is 0 ~ 0.2, and non-vanishing;
The span of h is 0 ~ 0.6, and non-vanishing;
X is for meeting the oxygen atom sum needed for other element valence, and the consumption of carrier is 30 ~ 70% of catalyst weight; Wherein high-valency metal element Q elder generation and Ludox effect, embed Ludox micelle and introduce catalyst.
2. unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 1, is characterized in that the consumption of carrier is catalyst weight 40 ~ 60%.
3. unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 1, is characterized in that the span of a is 0.5 ~ 4.0; The span of b is 0.5 ~ 5.0; The span of c is 0.5 ~ 5.0; The span of d is 0.5 ~ 5.0; The span of e is 0.5 ~ 5.5; The span of f is 0.01 ~ 0.3; The span of e+f sum is 0.2 ~ 8.0; The span of g is 0.01 ~ 0.16; The span of h is 0.05 ~ 0.4.
4. unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 1, is characterized in that X is selected from least one in Mg, Co, Ca or Cu.
5. the preparation method of unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 1, comprises the following steps:
A) solution I is obtained by water-soluble for the Q source of the solubility of aequum;
B) solution II is obtained by water-soluble for the salt being selected from Bi, Fe, Ni, X, Y, Z and K of aequum;
C) solution III is obtained by water-soluble for the ammonium molybdate of aequum;
D) by solution I and Ludox effect, embed Ludox micelle and obtain IV;
E) be added to after solution III mixes by IV, then add solution II required catalyst pulp;
F) catalyst pulp is after mist projection granulating, and at 520 ~ 660 DEG C, calcination activation obtains required catalyst in 0.2 ~ 4 hour.
6. the preparation method of unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 5, is characterized in that the calcination activation temperature of catalyst is 550 ~ 640 DEG C.
7. the preparation method of unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 5, is characterized in that the calcination activation time of catalyst is 0.5 ~ 2 hour.
8. a method for ammoxidating propylene to produce acrylonitrile, is characterized in that catalyst wherein used is unsaturated nitrile fluid catalyst prepared by ammoxidation according to claim 1.
9. the method for ammoxidating propylene to produce acrylonitrile according to claim 8, it is characterized in that with propylene, ammonia and air for raw material, material molar ratio propylene/ammonia/air=1/ (1.05 ~ 1.30)/(9.2 ~ 9.8), reaction condition is: reaction temperature 420 ~ 440 DEG C, reaction pressure 0.06 ~ 0.14MPa, propylene load WWH=0.06 ~ 0.10 hour of catalyst
-1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302796A (en) * | 1999-10-28 | 2001-07-11 | 上海石油化工股份有限公司 | Process for preparing acrylonitrile or methyl acrylonitrile by ammoxidizing propylene or isobutylene |
| CN101121130A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Ammoxidation method to manufacturing unsaturated nitrile catalyst |
| CN102371156A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Unsaturated nitrile fluidized bed catalyst prepared by ammoxidation and its preparation method |
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|---|---|---|---|---|
| JP4187856B2 (en) * | 1999-01-19 | 2008-11-26 | 旭化成ケミカルズ株式会社 | Catalyst and method for producing unsaturated nitrile using the same |
| US20040102318A1 (en) * | 2002-11-27 | 2004-05-27 | Brazdil James F. | Method for enhancing the productivity of vanadium antimony oxide catalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302796A (en) * | 1999-10-28 | 2001-07-11 | 上海石油化工股份有限公司 | Process for preparing acrylonitrile or methyl acrylonitrile by ammoxidizing propylene or isobutylene |
| CN101121130A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Ammoxidation method to manufacturing unsaturated nitrile catalyst |
| CN102371156A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Unsaturated nitrile fluidized bed catalyst prepared by ammoxidation and its preparation method |
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