CN1230460A - Catalyst for ammonoxidating propylene to produce acrylonitrile - Google Patents
Catalyst for ammonoxidating propylene to produce acrylonitrile Download PDFInfo
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- CN1230460A CN1230460A CN 98110738 CN98110738A CN1230460A CN 1230460 A CN1230460 A CN 1230460A CN 98110738 CN98110738 CN 98110738 CN 98110738 A CN98110738 A CN 98110738A CN 1230460 A CN1230460 A CN 1230460A
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- value
- catalyst
- propylene
- acrylonitrile
- produce acrylonitrile
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Abstract
The catalyst consists of SiO2 as carrier and the composite with the chemical formula of AaBbNacSrdNifFekBihMo12Ox, where A is one or more elements selected from Li, Rb and Cs; B is one or more elements selected from Mn, Cr, Sb, P, W Sm, T1 and Ce. The catalyst is adaptable to high pressure, high load operation and has the feature of high acrylonitrile yield, and is used for fluid bed in industrial production.
Description
The present invention relates to catalyst for ammonoxidating 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-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.
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 use potassium, a kind of new catalyst for ammonoxidating 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 catalyst for ammonoxidating propylene to produce acrylonitrile, form by silica supports and the following composition of chemical formula: A
aB
bNa
cSr
dMg
eNi
fFe
gBi
hMo
12O
x
A is one or more elements that are selected from lithium, rubidium, the caesium in the formula;
B is one or more elements that are selected from manganese, chromium, antimony, phosphorus, tungsten, samarium, thallium, the cerium;
A, b, c, d, e, f, g, h be respectively A, B, sodium, strontium, magnesium, nickel, iron, bismuth and
12 molybdenum atom ratios;
Wherein: a value is 0.01～0.7;
The b value is 0.01～4;
The c value is 0.1～0.7, and condition is that a value and c value sum are 0.1～1.0:
The d value is 0.01～2;
E value, f value and g value are 0.5～8;
The h value is 0.1～2;
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.
A value and c value sum preferable range are 0.2～0.7 in the technique scheme; The preferable range of d value is 0.01～1.0; The preferable range of e value, f value and g value is respectively 0.5～3,0.5～6 and 0.5～3; The preferable range of h value is 0.1～1.5; In the catalyst carrier dioxide-containing silica by weight percentage preferable range be 40～60%.
Main points of the present invention are with nickel and alkaline-earth metal magnesium in the acrylonitrile fluidized-bed catalyst component, strontium replaces the cobalt of covering price costliness, and replace a part of alkali metal with alkaline alkaline-earth metal strontium, especially whole potassium, so both avoided in the catalyst because potassium produces too much carbon dioxide when existing, thereby the problem that causes the product acrylonitrile yield to descend, after being used with strong basicity alkaline-earth metal strontium and other component simultaneously, give catalyst and adapted to high pressure, the performance of high load capacity reaction condition operation, making catalyst is 0.085 hour at propylene load (WWH)
-1, reaction pressure is under the operating condition of 0.14MPa, the acrylonitrile once through yield is the highest still to reach 79.4%, has 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 corresponding acids of phosphorus, tungsten or its ammonium salt in the component category-B element; 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, cerium 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 aluminate.
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 6.6 gram strontium nitrates mixing, add water 30 grams, the dissolving of heating back gets thing
Material (A); 8.3 gram chromium trioxides are dissolved in the 8.3 gram water, get material (B); 19.2 gram ammonium tungstates are dissolved in 100 milliliters of weight
Concentration is in 5% the ammoniacal liquor, 391.1 gram ammonium molybdates are dissolved in 50～90 ℃ of hot water of 320 grams, with two solution mix thing
Material (C); 80.6 gram bismuth nitrates, 94.7 gram magnesium nitrates, 268.5 gram nickel nitrates and 134.3 gram ferric nitrates are mixed, add water 65
Gram, the dissolving of heating back gets material (D).
With material (A) and 1250 gram weight concentration is that 40% Ludox mixes, and under agitation adds material (B) and (C) and (D),
Fully stir slurry, by well-established law the slurry of making is shaped to framboid in spray dryer, be 89 at internal diameter at last
Millimeter, length is 1700 millimeters, and (in 610 ℃ of roastings 1 hour, that makes urged in the rotary roasting furnace of φ 89 * 1700mm)
Changing agent consists of: 50%Cs
0.09Cr
0.45W
0.45Na
0.15Sr
0.17Mg
2.0Ni
5.0Fe
1.8Bi
0.9Mo
12O
x+ 50%SiO
2
[embodiment 2～9 and comparative example 1～3]
Adopt method preparation substantially the same manner as Example 1 to have the different catalyst of forming in the following table, and urge with prepared
Change and carry out the reaction that ammoxidation of propylene generates acrylonitrile under the agent reaction condition below, the results are shown in Table 1.
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
-1
Raw 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 | ?50％Cs 0.09Cr 0.45W 0.45Na 0.15Sr 0.17Mg 2.0Ni 5.0Fe 1.8Bi 0.9Mo 12O x+50％Si0 2?50％Rb 0.09Cr 0.45Mn 0.45Na 0.15Sr 0.17Mg 2.0Ni 5.0Fe 1.8Bi 0.9Mo 12O x+50％SiO 2?50％Cs 0.09Cr 0.45Mn 0.45Na 0.15Sr 0.17Mg 2.0Ni 5.0Fe 1.8Bi 0.9Mo 12O x+50％SiO 2?50％Cs 0.07Cr 0.45P 0.45Na 0.15Sr 0.15Mg 2.2Ni 5.1Fe 1.8Bi 1.0Mo 12O x+50％SiO 2?50％Cs 0.13Cr 0.45Mn 0.45P 0.25Na 0.15Sr 0.15Mg 2.2Ni 5.1Fe 1.8Bi 1.0Mo 12O x+50％SiO 2?50％Cs 0.09Cr 0.45P 0.25W 1.25Na 0.15Sr 0.15Mg 2.2Ni 5.1Fe 1.8Bi 1.0Mo 12O x+50％SiO 2?50％Cs 0.07Cr 0.45Mn 0.45W 0.25Na 0.15Sr 0.15Mg 2.2Ni 5.1Fe 1.8Bi 1.0Mo 12O x+50％SiO 2?50％Rb 0.09Cr 0.45Mn 0.45W 0.25N 0.15Sr 0.15Mg 2.0Ni 5.1Fe 1.8Bi 1.0Mo 12O x+50％SiO 2?50％Li 0.15Cs 0.04Cr 0.45Mn 0.45W 0.25Na 0.15Sr 0.15Mg 2.0Ni 5.1Fe 1.8Bi 1.0Mo 12O x+50％SiO 2?50％Cs 0.05K 0.17Cr 0.45Mn 0.15Na 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 | ????79.4 ????79.0 ????78.8 ????78.5 ????78.8 ????77.5 ????79.5 ????78.9 ????79.1 ????76.9 ????76.3 ????77.2 | ????3.8 ????3.8 ????3.7 ????4.1 ????3.5 ????4.1 ????4.1 ????3.9 ????3.9 ????3.7 ????4.0 ????3.7 | ????7.0 ????7.5 ????7.5 ????6.7 ????6.7 ????7.3 ????6.8 ????7.2 ????7.0 ????8.9 ????9.4 ????8.5 | ????80.6 ????80.0 ????80.0 ????80.5 ????80.9 ????79.7 ????80.9 ????80.3 ????80.6 ????78.6 ????77.8 ????79.2 | ????98.5 ????98.7 ????98.5 ????97.5 ????97.4 ????97.3 ????98.3 ????98.3 ????98.1 ????97.8 ????98.1 ????97.5 |
Claims (6)
1, a kind of catalyst for ammonoxidating propylene to produce acrylonitrile, form by silica supports and the following composition of chemical formula:
A
aB
bNa
cSr
dMg
eNi
fFe
gBi
hMo
12O
x
A is one or more elements that are selected from lithium, rubidium, the caesium in the formula;
B is one or more elements that are selected from manganese, chromium, antimony, phosphorus, tungsten, samarium, thallium, the cerium;
A, b, c, d, e, f, g, h be respectively A, B, sodium, strontium, magnesium, nickel, iron, bismuth and
12 molybdenum atom ratios;
Wherein: a value is 0.01～0.7;
The b value is 0.01～4;
The c value is 0.1～0.7, and condition is that a value and c value sum are 0.1～1.0;
The d value is 0.01～2;
E value, f value and g value are 0.5～8;
The h value is 0.1～2;
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,, it is characterized in that a value and c value sum are 0.2～0.7 according to the described catalyst for ammonoxidating propylene to produce acrylonitrile of claim 1.
3,, it is characterized in that the d value is 0.01～1.0 according to the described catalyst for ammonoxidating propylene to produce acrylonitrile of claim 1.
4,, it is characterized in that e value, f value and g value are respectively 0.5～3,0.5～6 and 0.5～3 according to the described catalyst for ammonoxidating propylene to produce acrylonitrile of claim 1.
5,, it is characterized in that the h value is 0.1～1.5 according to the described catalyst for ammonoxidating propylene to produce acrylonitrile of claim 1.
6,, it is characterized in that the carrier dioxide-containing silica is 40～60% by weight percentage in the catalyst according to the described catalyst for ammonoxidating propylene to produce acrylonitrile of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110738A CN1081488C (en) | 1998-03-30 | 1998-03-30 | Catalyst for ammonoxidating propylene to produce acrylonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110738A CN1081488C (en) | 1998-03-30 | 1998-03-30 | Catalyst for ammonoxidating propylene to produce acrylonitrile |
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| Publication Number | Publication Date |
|---|---|
| CN1230460A true CN1230460A (en) | 1999-10-06 |
| CN1081488C CN1081488C (en) | 2002-03-27 |
Family
ID=5220761
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98110738A Expired - Fee Related CN1081488C (en) | 1998-03-30 | 1998-03-30 | Catalyst for ammonoxidating propylene to produce acrylonitrile |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101147867B (en) * | 2006-09-20 | 2010-08-11 | 中国石油化工股份有限公司 | Fluidized bed catalyst for oxidation of propene ammonia |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS582232B2 (en) * | 1977-12-31 | 1983-01-14 | 旭化成株式会社 | Method for producing acrylonitrile |
| CN1005248B (en) * | 1987-05-14 | 1989-09-27 | 中国石油化工总公司上海石油化工研究所 | Acrylonitrile fluidized bed sodium-containing catalyst |
| US4994247A (en) * | 1989-09-08 | 1991-02-19 | Phillips Petroleum Company | Preparation of catalyst for oxidation of carbon monoxide |
| US5175334A (en) * | 1990-01-09 | 1992-12-29 | The Standard Oil Company | Process for the manufacture of acrylonitrile and methacrylonitrile |
| CN1036051C (en) * | 1991-12-13 | 1997-10-08 | 中国科学院兰州化学物理研究所 | Optical catalyst for air purification |
| DE4431634C1 (en) * | 1994-09-06 | 1996-01-18 | Hawema Werkzeugschleifmaschine | Machine tool grinding machine |
| CN1127689A (en) * | 1995-01-26 | 1996-07-31 | 大昭和精机株式会社 | Tapper mechanism |
| JPH08231487A (en) * | 1995-02-28 | 1996-09-10 | Asahi Chem Ind Co Ltd | Production of acrylonitrile |
| CN1127691A (en) * | 1995-06-05 | 1996-07-31 | 青岛市建材一厂 | Sand blower |
| CN1063101C (en) * | 1996-08-06 | 2001-03-14 | 中国石油化工总公司 | Fluidized bed catalyst for preparing acrylonitrile |
-
1998
- 1998-03-30 CN CN98110738A patent/CN1081488C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101147867B (en) * | 2006-09-20 | 2010-08-11 | 中国石油化工股份有限公司 | Fluidized bed catalyst for oxidation of propene ammonia |
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| CN1081488C (en) | 2002-03-27 |
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Granted publication date: 20020327 Termination date: 20100330 |