CN1092539C - Fluidized bed catalyst for ammoxidation of propylene to produce acrylonitrile - Google Patents
Fluidized bed catalyst for ammoxidation of propylene to produce acrylonitrile Download PDFInfo
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- CN1092539C CN1092539C CN99113806A CN99113806A CN1092539C CN 1092539 C CN1092539 C CN 1092539C CN 99113806 A CN99113806 A CN 99113806A CN 99113806 A CN99113806 A CN 99113806A CN 1092539 C CN1092539 C CN 1092539C
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- propylene
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- acrylonitrile
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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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- 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
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Abstract
The present invention relates to a fluidized-bed catalyst for preparing acrylonitrile from ammoxidated propene. The catalyst contains silicon dioxide carriers and a composition with the following chemical formula: AaBbCcNa<d>Tl<e>Mg<f>Ni<g>Fe<h>Bi<j>Mo12Ox, wherein A represents at least one element selected from kalium, rubidium and cesium, B represents at least one element selected from cobalt, manganese and zinc, and C represents one or multiple elements selected from chromium, calcium, phosphorus, arsenic, antimony, tungsten, vanadium and boron. The catalyst has the characteristics of operational adaption under the conditions of high pressure and high load, low CO and CO2 generation and capability of maintaining high acrylonitrile yield, and can be used in industrial production.
Description
The present invention relates to fluidized bed catalyst for ammoxidation of propylene to produce acrylonitrile.
Acrylonitrile is important Organic Chemicals, and it is produced by the ammoxidation of propylene reaction.For obtaining the fluid catalyst of high activity, high selectivity, people have carried out a series of improvement through constantly exploring.These improve and mostly relate to catalyst activity partly, pay attention to the collocation between the catalyst activity component, and improve activity of such catalysts and selectivity, thereby reach the raising of acrylonitrile once through yield, and the raising of producing load.
In process units, acrylonitrile catalyst can use under high propylene load, high-response pressure condition, and reaches high-caliber reactivity worth, and this is the target of pursuing in the acrylonitrile industrial production always.High load capacity, reaction under high pressure condition can improve the disposal ability of acrylonitrile output and reactor.The catalyst of anti-the high load capacity can reduce loaded catalyst to the process units of certain scale, and can make reactor expand energy, and production capacity can suitably improve according to the market demand in factory like this; High pressure resistant catalyst can satisfy day by day the environmental requirement that improves, and emptying waste gas in absorption tower can rely on tower top pressure directly to send in the stove to burn, reduce the air pollution that not treated direct emptying brings.
High load capacity, high pressure mean that the concentration of reactant propylene, ammonia and oxygen in the reaction atmosphere increases, it requires catalyst must possess the ability of handling more reactants in the unit interval, so the reactivity worth of acrylonitrile catalyst under high load capacity, condition of high voltage, its essence is reflected catalyst activity and optionally the height, the combination property of catalyst itself is had higher requirement.Because the activity of acrylonitrile is to reduce gradually along with the rising of reaction pressure, confirms general every rising 0.01MPa reaction pressure through test, catalyst activity also reduces about about 1%.The height of same reaction load also can impact catalyst activity, though the increase of reaction load can help the raising of selectivity of product, but the reaction load improves the decline influence of the thing conversion ratio that induces reaction and improves the positive influences that bring greater than selectivity, and therefore the raising of reaction load can cause that product yield descends.
Introduced a kind of ammoxidating propylene to produce acrylonitrile technology in the document US 4228098, catalyst system therefor is to be main active constituent with molybdenum-bismuth-iron-sodium-phosphorus in its technology, its catalyst does not contain the chromium element in forming, when emphasizing that bismuth and iron keep certain proportionate relationship in catalyst, catalyst can have been given play to better comprehensive performance.Disclosed catalyst examination condition is that catalyst propylene load (WWH) is 0.050 hour in the fluidized-bed reactor in this technology
-1, reaction pressure is 0.05MPa, this moment, single-pass yield of acrylonitrile was up to 80.9%, be not disclosed in the examination data of catalyst under high propylene load, the high-response pressure condition, but from disclosed data as can be seen, under the constant situation of other reaction condition, the single-pass yield of acrylonitrile during reaction pressure 0.05MPa is than the examination data under the normal pressure low nearly 5%.There is following shortcoming in above-mentioned document: lack the data under high propylene load, the high-response pressure condition on the one hand, the production capacity of this sampling device is lower; The once through yield of acrylonitrile is not high yet on the other hand.Introduced the technology and the catalyst of ammoxidating propylene to produce acrylonitrile among document US 5175334, the US5212137, catalyst is to be main active constituent with molybdenum-bismuth-iron-nickel-magnesium one caesium-potassium, and cerium and chromium were optional elements during its catalyst was formed.Disclosed catalyst examination condition is for to check and rate catalyst in the document in φ 2.54cm fixed-bed micro-reactor, 430 ℃ of reaction temperatures, and 6.0 seconds times of contact, catalyst propylene load (WWH) is about 0.043 hour by calculating as can be known
-1, this moment, single-pass yield of acrylonitrile was up to 84.2%, did not disclose other reaction conditions.Because in the document, be the data that in fixed bed, obtain on the one hand, be difficult to represent the response situation of catalyst in fluid bed, the document does not reflect the condition of pressure on the other hand, the reaction load is also lower, so can this catalyst fail to reflect the situation that adapt to high pressure, high load capacity reaction condition.All contain alkali metal potassium in above-mentioned in addition two documents, the inventor thinks can increase the existence of potassium in the catalyst growing amount of carbon dioxide, thereby cause the reactant deep oxidation, reduces the yield of purpose product acrylonitrile.
A kind of propylene, isobutene ammonia oxidizing catalyst are disclosed among the document Chinese patent CN1194180.This catalyst is main active constituent with molybdenum-bismuth-iron-cobalt-magnesium-thallium, pressure is 0.082MPa in the investigation condition in the document, load WWH is 0.06, for middle pressure, middle air speed are investigated condition, can not illustrate under high pressure, high-speed condition, the performance condition of catalyst does not disclose by-product CO and CO in addition in the document
2Generation situation data.
The objective of the invention is in order to overcome the shortcoming that above-mentioned document does not all relate to high pressure, high load operation and brings the reactant deep oxidation owing to the high potassium content of use, a kind of new fluidized bed catalyst for ammoxidation of propylene to produce acrylonitrile is provided, it is few that this catalyst has the amount of carbon dioxide of generation, be fit to high pressure, high load operation, and keep high activity and characteristics optionally.
Technical purpose of the present invention is to realize by following technical scheme: a kind of fluidized bed catalyst for ammoxidation of propylene to produce acrylonitrile, contain the following composition of silica supports and chemical formula:
A
aB
bC
cNa
dTl
eMg
fNi
gFe
hBi
iMo
12O
x
In the formula: A is at least a element that is selected from potassium, rubidium, the caesium;
B is at least a element that is selected from cobalt, manganese, the zinc;
C is one or more elements that are selected from chromium, calcium, phosphorus, arsenic, antimony, tungsten, vanadium, the boron;
A, b, c, d, e, f, g, h, i be respectively A, B, C, sodium, thallium, magnesium, nickel, iron, bismuth and
12 molybdenum atom ratios;
Wherein: a value is 0.001～0.7;
The b value is 0～5;
The c value is 0.1～3;
The d value is 0.01～0.7;
The e value is 0.001～0.7, and condition is that the value of a+d+e sum is 0.1～1.5;
The f value is 0.5～4;
The g value is 0.5～10;
The h value is 0.5～4;
The i value is 0.5～2;
The x value is for satisfying the summation of other element valence requisite oxygen atomicity;
The carrier dioxide-containing silica is 30～70% by weight percentage in the catalyst.
In the technique scheme, the preferable range of the value of a+d+e sum is 0.2～1.0; The preferable range of e value is 0.01～0.5; The preferable range of f value, g value and i value is respectively 1～3,2～8,1～3; In the catalyst carrier dioxide-containing silica by weight percentage preferable range be 40～60%.
Main points of the present invention are to replace all or part of expensive cobalt with nickel and alkaline-earth metal magnesium in the acrylonitrile fluidized-bed catalyst component, and replace a part of alkali metal with thallium, especially potassium, so both avoided in the catalyst because a large amount of potassium produce too much carbon dioxide when existing, thereby the problem that causes the product acrylonitrile yield to descend, after being used with thallium and other component simultaneously, given the performance that catalyst adaptation high pressure, high load capacity reaction condition are operated, making catalyst is 0.085 hour at propylene load (WWH)
-1, reaction pressure is under the operating condition of 0.14MPa, its CO and CO
2Total growing amount only be about 10%, and the high energy of acrylonitrile once through yield reaches 79.5%, obtained good effect.
Catalyst manufacture method of the present invention can be undertaken by well-established law.At first catalyst each component and carrier and water are mixed into slurry, the spray-dried microspheroidal that is shaped to, catalyst is made in last roasting.The preparation of slurry is that the aqueous solution of catalyst each component and carrier are undertaken by the described method of Chinese patent 87103455.7 (CN1005248B).
The employed raw material of each component is in the catalyst of the present invention:
The most handy its nitrate of component category-A element, hydroxide maybe can be decomposed into the salt of oxide.
The most handy its nitrate of component category-B element, hydroxide maybe can be decomposed into the salt of oxide.
Phosphorus in the component C dvielement, the most handy its corresponding acids of tungsten or its ammonium salt; Antimony can use antimony oxide, antimony pentoxide, hydrolysis to generate the halide and the antimony colloidal sol of antimony oxide; Other available its oxide or be decomposed into the salt of oxide, the preferably water miscible nitrate of used salt.
The most handy chromium trioxide of component chromium (Cr VI), chromic nitrate or the mixture of the two.
Component sodium can be with sodium nitrate, NaOH, sodium metasilicate or any sodium compound that can decompose.
Component iron, bismuth, nickel, magnesium, thallium can or be decomposed into the salt of oxide, the preferably water miscible nitrate of used salt with its oxide.
The component molybdenum can be with molybdenum oxide or ammonium molybdate.
Activity of such catalysts of the present invention examination is to carry out in internal diameter is 38 millimeters fluidized-bed reactor.Loaded catalyst 400g, 440 ℃ of reaction temperatures, reaction pressure 0.14MPa, raw material proportioning mol ratio is a propylene: ammonia: air=1: 1.2: 9.8, the propylene load (WWH) of catalyst is 0.085 hour
-1
Propylene conversion, acrylonitrile selectivity and once through yield are defined as follows in the present invention:
The invention will be further elaborated below by embodiment.[embodiment 1]
With 3.2 gram cesium nitrates, 1.1 gram sodium nitrate and 3.44 gram thallium nitrates mixing, add water 30 grams, the dissolving of heating back gets material (A); 8.3 gram chromium trioxides are dissolved in the 8.3 gram water, get material (B); It is in 5% the ammoniacal liquor that 19.2 gram ammonium tungstates are dissolved in 100 milliliters of weight concentrations, 391.1 gram ammonium molybdates are dissolved in 50～90 ℃ of hot water of 320 grams, with two solution mix material (C); With 80.6 gram bismuth nitrates, 94.7 gram magnesium nitrates, 268.5 gram nickel nitrates and 134.3 gram ferric nitrates mixing, add water 65 grams, the dissolving of heating back gets material (D).
With material (A) and 1250 gram weight concentration is that 40% Ludox mixes, under agitation add material (B) and (C) and (D), fully stir slurry, by well-established law the slurry of making is shaped to framboid in spray dryer, it is 89 millimeters at internal diameter at last, length is 1700 millimeters, and (in 610 ℃ of roastings 1 hour, the catalyst of making consisted of: 50%CS in the rotary roasting furnace of φ 89 * 1700mm)
0.09Cr
0.45W
0.45Na
0.15Tl
0.07Mg
2.0Ni
5.0Fe
1.8Bi
0.9Mo
12O
x+ 50%SiO
2[embodiment 2～9 and comparative example 1～4]
Adopt method preparation substantially the same manner as Example 1 to have the different catalyst of forming in the following table, and, the results are shown in Table 1 with carrying out the reaction that ammoxidation of propylene generates acrylonitrile under the prepared catalyst reaction condition below.
The reaction condition of the foregoing description and comparative example is:
φ 38mm fluidized-bed reactor
440 ℃ of reaction temperatures
Reaction pressure 0.14MPa loaded catalyst 400g catalyst propylene load (WWH) 0.085 hour
-1Raw material proportioning (mole) C
3 =/ NH
3/ air=1/1.2/9.8
Table 1
| Embodiment | Catalyst is formed | Once through yield % | AN selectivity % | C 3 ＝Conversion ratio % | ||
| AN | CO | CO 2 | ||||
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 comparative examples 1 comparative example 2 comparative examples 3 comparative examples 4 | 50％Cs 0.09Cr 0.45W 0.45Na 0.15Tl 0.07Mg 2.0Ni 5.0Fe 1.8Bi 0.9Mo 12O x+50％SiO 2 50％Cs 0.09Cr 0.45W 0.45Na 0.15Tl 0.07Mg 2.0Ni 5.0Fe 1.8Bi 0.9Mo 12O x+50％SiO 2 50％Cs 0.09Cr 0.45Mn 0.45Na 0.15Tl 0.09Mg 2.0Ni 5.0Fe 1.8Bi 0.9Mo 12O x+50％SiO 2 50％Cs 0.07Cr 0.45P 0.45Na 0.15Tl 0.15Mg 2.2Ni 5.1Fe 1.8Bi 1.0Mo 12O x+50％SiO 2 50％Cs 0.13Cr 0.45Sb 0.45P 0.25Na 0.15Tl 0.05Mg 2.2Ni 5.1Fe 1.8Bi 1.0Mo 12O x+50％SiO 2 50％Cs 0.09Cr 0.45P 0.25W 0.25Na 0.15Tl 0.13Mg 2.2Ni 5.1Fe 1.8Bi 1.0Mo 12O x+50％SiO 2 50％Cs 0.07K 0.09Cr 0.45W 0.25Na 0.15Tl 0.13Mg 2.2Ni 5.1Fe 1.8Bi 1.0Mo 12O x+50％SiO 2 50％Rb 0.09Cs 0.05Cr 0.45V 0.25W 0.25Na 0.15Tl 0.09Mg 2.0Ni 5.1Fe 1.8Bi 1.0Mo 12O x+50％SiO 2 50％K 0.15Cs 0.04Cr 0.45P 0.15W 0.25Na 0.15Tl 0.1Mg 2.0Ni 5.1Fe 1.8Bi 1.0Mo 12O x+50％SiO 2 50％Cs 0.05K 0.17Cr 0.45Mn 0.45Na 0.15Co 5.0Ni 2.0Fe 1.8Bi 0.9Mo 12O x+50％SiO 2 50％K 0.21Cr 0.45Mn 0.45Na 0.15Co 5.0Ni 2.0Fe 1.8Bi 0.9Mo 12O x+50％SiO 2 50％Cs 0.07K 0.15Cr 0.45W 0.45Na 0.15Co 4.3Ni 2.4Fe 1.8Bi 0.9Mo 12O x+50％SiO 2 50％Cs 0.09Cr 0.45W 0.45Na 0.15Mg 2.0Ni 5.0Fe 1.8Bi 0.9Mo 12O x+509SiO 2 | 79.5 79.0 78.3 78.2 79.1 78.1 79.5 78.2 77.8 76.9 76.3 77.2 77.5 | 3.8 4.0 4.1 4.2 4.1 4.2 4.1 3.9 4.1 3.7 4.0 3.7 4.5 | 6.0 6.2 6.5 6.4 6.1 6.7 6.0 7.0 6.6 8.9 9.4 8.5 8.6 | 80.7 80.0 80.2 79.6 81.5 80.0 80.9 80.3 80.0 78.6 77.8 79.2 79.3 | 98.5 98.7 97.6 98.2 97.1 97.6 98.3 97.4 97.3 97.8 98.1 97.5 97.7 |
Claims (5)
1, a kind of fluidized bed catalyst for ammoxidation of propylene to produce acrylonitrile, contain the following composition of silica supports and chemical formula:
A
aB
bC
cNa
dTl
eMg
fNi
gFe
hBi
iMo
12O
x
In the formula: A is at least a element that is selected from potassium, rubidium, the caesium;
B is at least a element that is selected from cobalt, manganese, the zinc;
C is one or more elements that are selected from chromium, calcium, phosphorus, arsenic, antimony, tungsten, vanadium, the boron;
A, b, c, d, e, f, g, h, i be respectively A, B, C, sodium, thallium, magnesium, nickel, iron, bismuth and
12 molybdenum atom ratios;
Wherein: a value is 0.001～0.7;
The b value is 0～5;
The c value is 0.1～3;
The d value is 0.01～0.7;
The e value is 0.001～0.7, and condition is that the value of a+d+e sum is 0.1～1.5;
The f value is 0.5～4;
The g value is 0.5～10;
The h value is 0.5～4;
The i value is 0.5～2;
The x value is for satisfying the summation of other element valence requisite oxygen atomicity;
The carrier dioxide-containing silica is 30～70% by weight percentage in the catalyst.
2, according to the described fluidized bed catalyst for ammoxidation of propylene to produce acrylonitrile of claim 1, the value that it is characterized in that the a+d+e sum is 0.2～1.0.
3,, it is characterized in that the e value is 0.01～0.5 according to the described fluidized bed catalyst for ammoxidation of propylene to produce acrylonitrile of claim 1.
4,, it is characterized in that f value, g value and h value are respectively 1～3,2～8,1～3 according to the described fluidized bed catalyst for ammoxidation of propylene to produce acrylonitrile of claim 1.
5,, it is characterized in that the carrier dioxide-containing silica is 40～60% by weight percentage in the catalyst according to the described fluidized bed catalyst for ammoxidation of propylene to produce acrylonitrile of claim 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113806A CN1092539C (en) | 1999-06-24 | 1999-06-24 | Fluidized bed catalyst for ammoxidation of propylene to produce acrylonitrile |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113806A CN1092539C (en) | 1999-06-24 | 1999-06-24 | Fluidized bed catalyst for ammoxidation of propylene to produce acrylonitrile |
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| Publication Number | Publication Date |
|---|---|
| CN1287883A CN1287883A (en) | 2001-03-21 |
| CN1092539C true CN1092539C (en) | 2002-10-16 |
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|---|---|---|---|
| CN99113806A Expired - Fee Related CN1092539C (en) | 1999-06-24 | 1999-06-24 | Fluidized bed catalyst for ammoxidation of propylene to produce acrylonitrile |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4159759B2 (en) * | 2001-04-13 | 2008-10-01 | ダイヤニトリックス株式会社 | Method for producing molybdenum-bismuth-iron-containing composite oxide fluidized bed catalyst |
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1999
- 1999-06-24 CN CN99113806A patent/CN1092539C/en not_active Expired - Fee Related
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| CN1287883A (en) | 2001-03-21 |
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