CN103736496A - Preparation method of fluidized bed catalyst for unsaturated nitril prepared by ammoxidation - Google Patents
Preparation method of fluidized bed catalyst for unsaturated nitril prepared by ammoxidation Download PDFInfo
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- CN103736496A CN103736496A CN201210392986.2A CN201210392986A CN103736496A CN 103736496 A CN103736496 A CN 103736496A CN 201210392986 A CN201210392986 A CN 201210392986A CN 103736496 A CN103736496 A CN 103736496A
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Abstract
The invention relates to a preparation method of a fluidized bed catalyst for unsaturated nitril prepared by ammoxidation. The preparation method mainly solves the problems, namely the low propylene conversion rate, the low and rapidly-reduced acrylonitrile selectivity and the low yield of acrylonitrile, which are caused by low oxygen storing and releasing capability, the small specific surface, and liability to sinter at the reaction temperature of an acrylonitrile catalyst in the prior art. According to the technical scheme adopted by the preparation method, silica sol is adopted as a carrier, the catalyst contains active components shown as the general formula Mo<12>Bi<a>Fe<b>Ni<c>X<d>Y<e>Z<f>K<g>O<x>, and sosoloid is firstly formed under action of a specific precipitator and then is prepared into a catalyst, wherein the Y is at least two rare earth elements. By the technical scheme, the problems are solved well and the preparation method can be used in the industrial production of acrylonitrile prepared by propylene ammoxidation.
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 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 a, b unsaturated nitrile technique, and the core technology of this technique is the catalyst that uses a kind of active component to contain Mo, Bi.Through constantly improving, Mo-Bi series catalysts is very ripe at present, industrial, by preparing acrylonitrile by allylamine oxidation technique, is widely used.The improvement of catalyst is in the past 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 good oxidation-reduction stability and good reaction yield, 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, and in carrier starting material Ludox, adding 2～25% grain diameter is that the solid silica of 5～100 nanometers improves catalyst performance.
The conversion ratio of above patented technology to raising catalyst, the discharge of ammonia ratio and then minimizing amine wastewater of sulphuric acid in reduction course of reaction, there has been certain effect the aspects such as the life-span of extending catalyst; But all there is acrylonitrile catalyst storage oxygen and discharge that the ability of oxygen is low, specific surface is low, and be easy to sintering under reaction temperature in patent up to now report, cause propylene conversion low, acrylonitrile is selectively low, and fast-descending, causes the problem that acrylonitrile yield is low.
Summary of the invention
Technical problem to be solved by this invention is in existing technology of preparing, to have acrylonitrile catalyst storage oxygen and discharge that the ability of oxygen is low, specific surface is low, and be easy to sintering under reaction temperature, cause propylene conversion low, acrylonitrile is selectively low, and fast-descending, cause the problem that acrylonitrile yield is low, a kind of new unsaturated nitrile fluid catalyst prepared by ammoxidation preparation method is provided.Catalyst prepared by the method has effective ability, specific surface and anti-caking power that has improved catalyst storage oxygen and discharged oxygen, 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 unsaturated nitrile fluid catalyst prepared by ammoxidation preparation method, and take Ludox as carrier, described catalyst contains the active component that following general formula represents:
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 two kinds that are selected from La, Ce, Pr, Nd 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 0.1～3;
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 Y is prepared into catalyst after two kinds or above rare earth element first form solid solution again, the span of the ratio of the molal quantity of its molar content greatest member and other element molal quantity sums is 0.2～20, and its rare earth solid solution precipitating reagent is selected from least one in ethamine, methylamine, pyridine, triethanolamine, ethylenediamine, ammonium carbonate, carbonic hydroammonium, urea or ammoniacal liquor.
In technique scheme, Y is prepared into catalyst after two kinds or above rare earth element first form solid solution with precipitating reagent again, the preferred span of the ratio of the molal quantity of its molar content greatest member and other element molal quantity sums is 0.5～10, and optimum valuing range is 1～5.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.The value preferable range of f is 0.01～0.35.The value preferable range of g is 0.001～0.1.
The starting material of required metallic element is corresponding water soluble salt, and Ludox carrier adds rare earth solid-solution powder after making slurry by coprecipitation, aging rear spray drying granulation, and then high-temperature roasting obtains catalyst finished product.
In the embodiment providing below, 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 calculate Carbon balance, when Carbon balance is valid data during 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 selective (%)=
× 100 %
Propylene conversion
The present invention by introducing and make rare earth element solid solution through specific precipitating reagent in acrylonitrile catalyst formula, because the difference of its solid solution cation radius causes distortion of lattice and blemish, promote the oxidation one of body phase oxygen to reduce, cause the ability of high storage and release oxygen, catalyst specific surface increases, thereby enhancing redox property, increase the selective oxidation reaction of propylene and Lattice Oxygen, and then it is selective also to have significantly improved acrylonitrile, acrylonitrile yield obviously improves.As shown in table 2 result: the oxygen storage capacity of catalyst is increased to approximately 200～400 μ mol/g of embodiment by 83 μ mol/g of comparative example 1, approximately 3～5 times of rising ratios, put oxygen amount is increased to embodiment approximately 200 μ mol/g by 45 μ mol/g of comparative example 1, approximately 4 times of rising ratios, specific surface is by the 34m of comparative example 1
2/ g is increased to approximately 40～50m of embodiment
2/ g, effect is remarkable; Acrylonitrile is selectively increased to 86% left and right of embodiment by 80.3% of comparative example 1, propylene adornment rate is increased to 99% left and right of embodiment by 97.8% of comparative example 1, and single-pass yield of acrylonitrile is increased to and is up to 87.2% by 78.5%, has obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
The specific embodiment
[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 ℃, 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 grams of Fe (NO
3)
39H
2o adds in 70 ℃ 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
2after O stirring and dissolving, make material D.
In 20 grams of water, add 1.1 grams of KNO
3, 0.9 gram of NaNO
3with 2.0 grams of CsNO
3after dissolving, added and in material D, formed material E.
Material E is dripped under rapid stirring in material C, form catalyst pulp.Dry in 70 ℃ of sprayings after aging 3 hours, by the roasting 3 hours at 580 ℃ in rotary calciner of the particle of gained, obtain finished catalyst.
[embodiment 1～15]
According to the identical preparation process of comparative example 1, according to table 1 catalyst composition Kaolinite Preparation of Catalyst, difference is only that rare earth element is first by precipitating reagent co-precipitation, oven dry, roasting be ground to 20 microns and add below.Catalyst is investigated by above-mentioned investigation appreciation condition, and activity rating result, catalyst storage oxygen, release oxygen amount and surface analysis the results are shown in Table 2.
Table 1
| ? | Catalyst composition | Precipitating reagent |
| 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 | Nothing |
| Embodiment 1 | Mo 12Bi 2.0Fe 2.5Ni 4.5Mg 1.8La 0.8Sm 0.2K 0.05Cs 0.05Na 0.05+50%Si O 2 | Ammoniacal liquor |
| Embodiment 2 | Mo 12Bi 0.4Fe 2.9Ni 5.2Mg 1.5La 0.3Nd 0.2K 0.1Rb 0.08+46%SiO 2 | Carbonic hydroammonium |
| Embodiment 3 | Mo 12Bi 0.6Fe 1.0Ni 6.8Mg 1.2La 0.3Nd 0.2Sm 0.6K 0.1Cs 0.05+50%SiO 2 | Ethamine/urea=1:1 |
| Embodiment 4 | Mo 12Bi 0.2Fe 1.5Ni 4.2Co 2.6La 0.5Pr 0.1Sm 0.2Nd 0.1K 0.02Cs 0.09+52%SiO 2 | Methylamine/ammoniacal liquor=2:1 |
| Embodiment 5 | Mo 12Bi 1.5Fe 2.2Ni 3.0Mg 2.8La 0.8Sm 0.2K 0.05Cs 0.05+50%SiO 2 | Triethanolamine |
| Embodiment 6 | Mo 12Bi 0.2Fe 2.8Ni 3.3Mn 1.7Ce 0.4La 0.1Pr 0.1Sm 0.2Nd 0.2K 0.11Cs 0.05+50%SiO 2 | Pyridine/ethylenediamine=1:4 |
| Embodiment 7 | Mo 12Bi 1.2Fe 3.5Ni 3.1Mg 2.4Pb 0.2Ce 1Pr 0.1Nd 0.2K 0.12Cs 0.13+52% SiO 2 | Ammonium carbonate |
| Embodiment 8 | Mo 12Bi 0.5Fe 2.5Ni 7.5Ce 0.3Nd 0.2K 0.15Cs 0.1Li 0.05 +47%SiO 2 | Triethanolamine/ammoniacal liquor=1:8 |
| Embodiment 9 | Mo 12Bi 2.2Fe 2.0Ni 4.5Mg 4.3Pr 0.1Nd 0.2K 0.05Cs 0.1Zr 0.03+48%SiO 2 | Methylamine/pyridine=1:5 |
| Embodiment 10 | Mo 12Bi 1.3Fe 2.1Ni 6.5Mg 1.5Ce 0.2Sm 0.2Nd 0.2K 0.08Rb 0.05Cs 0.05+50%SiO 2 | Carbonic hydroammonium |
| Embodiment 11 | Mo 12Bi 0.8Fe 2.7Ni 3.3Mg 4.0La 0.1Pr 0.1Sm 0.2K 0.12Cs 0.07Li 0.03+51%SiO 2 | Ammonium carbonate/carbonic hydroammonium=1:3 |
| Embodiment 12 | Mo 12Bi 0.4Fe 2.6Ni 5.5Mg 2.8La 0.2Sm 0.4K 0.15Cs 0.05+50%SiO 2 | Ethylenediamine/methylamine/pyridine=1:5:2 |
| Embodiment 13 | Mo 12Bi 1.4Fe 3.0Ni 6.7Mn 0.2Ce 0.03Sm 0.02Nd 0.5Ca 0.2K 0.11Cs 0.09+50%SiO 2 | Carbonic hydroammonium/urea=1:1 |
| Embodiment 14 | Mo 12Bi 0.2Fe 1.0Ni 4.8Mg 0.8Ce 0.02La 0.01Pr 0.5Sm 0.02K 0.06Cs 0.08+50%SiO 2 | Urea |
| Embodiment 15 | Mo 12Bi 1.7Fe 2..2Ni 5.0Mg 1.4Ce 0.3La 0.1Pr 0.1Nd 0.2K 0.14Cs 0.12+51%SiO 2 | Ethylenediamine |
Table 2
Claims (9)
1. a unsaturated nitrile fluid catalyst prepared by ammoxidation preparation method, take Ludox as carrier, described catalyst contains the active component that following general formula represents:
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 two kinds that are selected from La, Ce, Pr, Nd 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 0.1～3;
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 Y is prepared into catalyst after two kinds or above rare earth element first form solid solution again, the span of the ratio of the molal quantity of its molar content greatest member and other element molal quantity sums is 0.2～20, and its rare earth solid solution precipitating reagent is selected from least one in ethamine, methylamine, pyridine, triethanolamine, ethylenediamine, ammonium carbonate, carbonic hydroammonium, urea or ammoniacal liquor.
2. unsaturated nitrile fluid catalyst prepared by ammoxidation preparation method according to claim 1, it is characterized in that Y is prepared into catalyst after two kinds or above rare earth element first form solid solution again, the span of the ratio of the molal quantity of its molar content greatest member and other element molal quantity sums is 0.5～10.
3. unsaturated nitrile fluid catalyst prepared by ammoxidation preparation method according to claim 2, is characterized in that the span of the molal quantity of molar content greatest member and the ratio of other element molal quantity sums is 1～5.
4. unsaturated nitrile fluid catalyst prepared by ammoxidation preparation method according to claim 1, the consumption that it is characterized in that carrier is catalyst weight 40～60%.
5. unsaturated nitrile fluid catalyst prepared by ammoxidation preparation method according to claim 1, is characterized in that catalyst pulp is after mist projection granulating, and at 520～660 ℃, calcination activation obtains required catalyst for 0.2～4 hour.
6. unsaturated nitrile fluid catalyst prepared by ammoxidation preparation method according to claim 5, the calcination activation temperature range that it is characterized in that catalyst is 550～640 ℃.
7. unsaturated nitrile fluid catalyst prepared by ammoxidation preparation method according to claim 5, is characterized in that calcination activation time range is 0.5～2 hour.
8. unsaturated nitrile fluid catalyst prepared by ammoxidation preparation method according to claim 1, the span that it is characterized in that f is 0.01～0.35.
9. unsaturated nitrile fluid catalyst prepared by ammoxidation preparation method according to claim 1, the span that it is characterized in that g is 0.001～0.1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105195165A (en) * | 2015-10-23 | 2015-12-30 | 中国海洋石油总公司 | Ammoxidation of olefin to unsaturated nitrile fluid catalyst and preparation method thereof |
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| 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 |
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Patent Citations (5)
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| US20040102642A1 (en) * | 2002-11-27 | 2004-05-27 | Brazdil James F | Preparation of vanadium antimony oxide based catalysts using nano-scale iron |
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| CN101306376A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Tellurium containing alkane ammoxidation reaction catalyst |
| 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 |
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| CN105195165A (en) * | 2015-10-23 | 2015-12-30 | 中国海洋石油总公司 | Ammoxidation of olefin to unsaturated nitrile fluid catalyst and preparation method thereof |
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