CN1130261C - Propylene ammonoxidizing fluid bed catalyst - Google Patents
Propylene ammonoxidizing fluid bed catalyst Download PDFInfo
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- CN1130261C CN1130261C CN99119953A CN99119953A CN1130261C CN 1130261 C CN1130261 C CN 1130261C CN 99119953 A CN99119953 A CN 99119953A CN 99119953 A CN99119953 A CN 99119953A CN 1130261 C CN1130261 C CN 1130261C
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- propylene
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 propylene ammon-oxidizing fluid bed catalyst which comprises a silicon dioxide carrier and a composition with a chemical formula as follows by an atomic ratio: AaBbCcCedMgeGefFegBihMoiOx, wherein in the formula, A is at least two selected from Li, Na, K, Rb and Cs; B is at least one selected from Co, Ni, Mn, Ca, Cu, W, Cr and V; C is at least one selected from B, P and As. The catalyst of the present invention is particularly suitable for being used under the conditions of low reaction temperature, high reaction pressure and high propylene load. Moreover, the present invention can keep high output rate of acrylonitrile and can be used in industrial production.
Description
The present invention relates to fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation.
Vinyl cyanide is important Organic Chemicals, and it is produced by the ammoxidation of propylene reaction.For obtaining the fluid catalyst of high reactivity, highly selective, people have carried out a series of improvement through constantly exploring.These improve and mostly relate to the catalyst activity composition, pay attention to the collocation between the catalyst activity component, and improve activity of such catalysts and selectivity, thereby reach the raising of vinyl cyanide once through yield, and the raising of producing load.
Oxidation proceses of ammonia is produced vinyl cyanide through 30 years of development, and the throughput of factory and the market requirement are near balance.The main development trend of acrylonitrile process has been turned to the transformation of original factory, further to cut down the consumption of raw materials and to increase throughput by the construction new device at present.By transformation to original factory, change the bottleneck in effective catalyst and the elimination production technique, the throughput of vinyl cyanide might improve 50～80%, and required investment only is 20～30% of a new device, economic benefit is very huge.
Can produce two problems during factory transforms: 1. the reaction pressure of fluidized-bed reactor will rise; 2. the loading capacity of catalyzer can not be too many.The catalyzer that for this reason requires to use instead should have higher propylene load and can bear higher reaction pressure.
The reaction pressure of fluidized-bed reactor is to be determined to the resistance drop that absorbs a series of interchanger, tower and pipe arrangement the cat head by reactor outlet.Because the increase of throughput obviously increases the inventory of reactor outlet, above-mentioned resistance drop is increased.In addition, each heat exchanger heat transfer area also need increase heat-exchange equipment inadequately, and resistance drop is further increased.Because environmental requirement, the reactor off-gas that absorbs cat head is forbidden directly to be discharged in the atmosphere, deliver to stove and burn.If like this without induced draft fan, then must improve the absorption tower top pressure.For all the foregoing reasons, the working pressure of reactor will increase by 0.5～1.0 times than design load at present, promptly reaches more than the 0.08MPa.
Above-mentioned second load that problem is a catalyzer, i.e. WWH.Its definition is a catalyzer per ton, per hour manageable tonnage.Because the increase of reactor feed amount, if the load of catalyzer is constant, then the catalyzer loading capacity is also wanted corresponding increase.But water-cooled tube insufficient height in the intrinsic fluidized-bed reactor, so the fluid height of catalyst reactor might surpass the height of water-cooled tube.In addition, because the increase of reactor feed amount, so operating linear velocity also significantly improves.The combined influence of these two variations might make reactor dilute phase temperature rise, and causes carbon dioxide production to increase, and the vinyl cyanide selectivity descends.Therefore the WWH of catalyzer is higher can prevent the problems referred to above.If can effectively reduce temperature of reaction, can cut down the consumption of energy on the one hand in addition, also can improve reaction condition on the other hand, reach the purpose that improves acrylonitrile yield.
The WWH that improves catalyzer in theory should increase the adsorption activation ability of catalyzer to propylene, but at present still in the catalyst-free certain element can improve report to propylene adsorption activation ability.The catalyzer of following composition has been proposed in document CN1021638C:
A
aB
bC
cNi
dCo
eNa
fFe
gBi
hM
iMo
jO
x
Wherein A is potassium, rubidium, caesium, samarium, thallium; B is manganese, magnesium, strontium, calcium, barium, lanthanum, rare earth element; C is phosphorus, arsenic, boron, antimony, chromium; M is tungsten, vanadium.
Above-mentioned catalyzer can obtain higher single-pass yield of acrylonitrile, but the propylene of catalyzer load is lower, and single-pass yield of acrylonitrile descends bigger under higher reaction pressure.Studies show that further the B component in the above-mentioned catalyzer is relevant with performance under high pressure to the load of catalyzer with M.Though some element in the B component has effect to improving single-pass yield of acrylonitrile, and the raising of catalyst loading and the performance of high-response pressure are had negative impact, be unfavorable for that catalyzer adapts to elevated pressures, operates under the higher load condition.Once in stipulating in CN1021638C in addition that above-mentioned catalyzer was formed, the summation of i and j is 12, promptly is a constant.Cancel this regulation in the present invention,, will influence single-pass yield of acrylonitrile because molybdenum component will reduce when increasing by this regulation M component.
Introduced a kind of germanic ammoxidation catalyst that obtains the high acrylonitrile yield among document U55688739 and the US5770757.Adopt molybdenum, bismuth, germanium system in the document, alkali metal containing in the optional elements, but the unexposed example that contains sodium among the embodiment, only disclosing reaction pressure in addition in the document is non-pressurized reaction conditions, not the concrete investigation data under high pressure, high-load condition.
The objective of the invention is to overcome the catalyzer that exists in the above-mentioned document do not relate to adaptation than high-response pressure, high operational load and under the low reaction temperatures condition problem of reactivity worth, a kind of new fluidized bed catalyst for preparing acrylonitrile by propene ammonia oxidation is provided.This catalyzer can adapt at higher reaction pressure, higher load, operate than under the condition than low reaction temperatures and lower air/propylene, and keeps high vinyl cyanide once through yield.
The objective of the invention is to realize by following technical scheme: a kind of fluidized bed catalyst for ammoxidation of propylene, contain with the following composition of atomic ratio measuring chemical formula:
A
aB
bC
cCe
dMg
eGe
fFe
gBi
hMo
iO
x
A is selected among Li, Na, K, Rb or the Cs at least two kinds in the formula;
B is selected from least a among Co, Ni, Mn, Cu, W, Cr or the V;
C is selected from least a among B, P or the As;
The span of a is 0.01～1.5;
The span of b is 0.1～12.0;
The span of c is 0.01～0.45;
The span of d is 0.2～3.0;
The span of e is 0.8～7.5;
The span of f is 0.01～2.0;
The span of g is 0.1～4.0;
The span of h is 0.2～2.5;
The span of i is 12.0～14.5;
X satisfies the required Sauerstoffatom sum of each element valence in the catalyzer;
Wherein support of the catalyst is selected from silicon-dioxide, aluminum oxide or its mixture, and its consumption is 30～70% by weight percentage.
The value preferable range of a is 0.01～0.7 in the technique scheme, the value preferable range of c is 0.01～0.45, and the value preferable range of d is 0.3～2.0, and the value preferable range of e is 1.0～4.0, the value preferable range of f is 0.01～1.0, and the value preferable range of g is 1.0～3.0.The preferred silicon-dioxide of support of the catalyst, its consumption are 40～60% by weight percentage.
The manufacture method of catalyzer of the present invention there is no particular requirement, can be undertaken by well-established law.At first the catalyzer each component is made solution, be mixed and made into slurry with carrier again, the spray-dried microspheroidal that is shaped to, catalyzer is made in last roasting.The preparation of slurry is preferably undertaken by the CN1005248C method.
The raw material of making catalyzer of the present invention is:
The aluminium component is with aluminum oxide or ammonium molybdate in the catalyzer.
The most handy corresponding acids of phosphorus, arsenic and boron or its ammonium salt in the catalyzer; Tungsten can be with ammonium tungstate or its oxide compound; Vanadium can be used ammonium meta-vanadate; Its oxide compound of germanium; The most handy chromium trioxide of chromium, chromium nitrate or the mixture of the two; Other component can maybe can be decomposed into the salt of oxide compound with its nitrate, oxide compound, but preferably uses water miscible nitrate.
Raw material available silicon colloidal sol, silicon gel or both mixtures as carrier silicon-dioxide.If use silicon sol, its quality will meet the requirement of CN1005248C.
It is 47～55% back spraying dryings that the prepared slurry heating is concentrated to solid content.Spray-dryer available pressure formula, two streamings or centrifugal turntable formula, but, can guarantee that the catalyzer of making has good size-grade distribution with centrifugal better.
The roasting of catalyzer can be divided into two stages and carry out: each element decomposition of salts and high-temperature roasting in the catalyzer.The catabolic phase temperature is preferably 200～300 ℃, and the time is 0.5～2 hour.Maturing temperature is 500～800 ℃, is preferably 550～700 ℃; Roasting time is 20 minutes to 2 hours.Above-mentioned decomposition and roasting are carried out respectively in two stoving ovens, also can be divided into two zones in a stove, also can finish simultaneously in the continous way rotary roasting furnace and decompose and roasting.In catalyst decomposes and roasting process, to feed an amount of air, prevent that catalyzer is by over reduction.
Adopt the specification of catalyzer manufacturing vinyl cyanide of the present invention required propylene, ammonia and molecular oxygen identical with other ammoxidation catalyst of use.Though the low molecule saturated hydrocarbon content in the raw material propylene to the reaction did not influence, considers that from economic point of view density of propylene is more preferably greater than 85% (mole).Ammonia can be used fertilizer grade liquefied ammonia.Reaction desired molecule oxygen can be used pure oxygen from technical standpoint, oxygen enrichment and air, but from economy and the most handy air of security consideration.
Entering the ammonia of fluidized-bed reactor and the mol ratio of propylene is between 0.8～1.5, is preferably 1.0～1.3.The mol ratio of air and propylene is 8～10.5, is preferably 9.0～9.8.If owing to some operational reason must with higher air than the time, can increase to 11, reaction is not had great effect.But from security consideration, the excess of oxygen in the reactant gases can not preferably be not more than 4% greater than 7% (volume).
When catalyzer of the present invention was used for fluidized-bed reactor, temperature of reaction was 420～470 ℃, was preferably 425～450 ℃.Therefore catalyzer of the present invention is a kind of low reaction temperatures, high pressure, high loading catalyzer of being applicable to, reaction pressure can be more than 0.08MPa in production equipment, for example, and 0.08～0.15MPa.Also do not have any disadvantageous effect if reaction pressure is lower than 0.08MPa, single-pass yield of acrylonitrile can further improve.
The propylene load (WWH) of catalyzer of the present invention is 0.06～0.15 hour
-1, be preferably 0.07～0.10 hour
-1Loading to hang down not only wastes catalyzer, and carbon dioxide production is increased, and selectivity descends, and is disadvantageous.Loading does not too highly have practical significance, because the catalyzer add-on is very few, the heat transfer area that can make catalyst layer internal cooling water pipe causes temperature of reaction uncontrollable less than removing the required area of reaction heat.
The product of making vinyl cyanide with catalyzer of the present invention reclaims process for refining, and available existing production technique need not done any transformation.The eluting gas that is fluidized-bed reactor is removed unreacted ammonia through neutralizing tower, with water at low temperature whole organic products is absorbed again.Absorption liquid gets high-purity propylene nitrile product through extractive distillation after dehydrogenation cyanic acid and the processed.
The present invention is by adding component germanium in molybdenum, bismuth, iron catalyst system, find that this catalyst system has than high-response pressure (0.14MPa), and (WWH is 0.085 hour to higher load
-1) operational capability under the condition, in catalyst system, add component magnesium and cerium again, find that this catalyst system under 430 ℃ of conditions of temperature of reaction, has advantages of high catalytic activity and selectivity; Suitably add other effective active components in addition, make this catalyzer 430 ℃ of temperature of reaction, elevated pressures 0.14MPa, higher load 0.085 hour
-1With low air/propylene ratio is (mole) condition under to operate at 9.5: 1, and its vinyl cyanide once through yield reaches as high as 80.5%, has obtained effect preferably.
Activity of such catalysts of the present invention examination is to carry out in internal diameter is 38 millimeters fluidized-bed reactor.Loaded catalyst 400 grams, 430 ℃ of temperature of reaction, reaction pressure 0.14MPa, proportioning raw materials (mole) is a propylene: ammonia: air=1: 1.2: 9.5, the propylene load (WWH) of catalyzer is 0.085 hour
-1
Propylene conversion, vinyl cyanide selectivity and once through yield are defined as follows in the present invention:
The invention will be further elaborated below by embodiment.[embodiment 1]
2.1 gram cesium nitrates, 4.35 gram SODIUMNITRATE and 1.91 gram saltpetre are mixed, add water 30 gram and heating for dissolving, obtain material (A); 8.37 gram chromium trioxides are dissolved in the 9 gram water, get material (B); 421.3 gram ammonium molybdates are dissolved in 60～90 ℃ of hot water of 350 grams, get material (C); 87.2 gram Bismuth trinitrates, 292 gram nickelous nitrates, 50.4 gram cerous nitrates, 102 gram magnesium nitrates, 1.27 gram germanium oxides and 168 gram iron nitrates are mixed, add water 120 grams, after the heating for dissolving as material (D); Take by weighing phosphoric acid solution 4.01 grams as material (E).
With material (A) and 1285 gram weight concentration is that 40% silicon sol mixes, under agitation add material (B), (C), (D) and (E) successively, after fully stirring, get slurry, according to well-established law the slurry of making is carried out the framboid moulding in spray-dryer, it is 89 millimeters at internal diameter at last, length be in the rotary roasting furnace of 1700 millimeters (89 * 1700 millimeters of φ) in 605 ℃ of roastings 1.5 hours, make and consist of 50%K
0.1Na
0.28Cs
0.07P
0.025Ni
5.6Cr
0.35Ce
0.35Mg
1.2Ge
0.05Fe
2.0Bi
0.75Mo
12.5O
x+ 50%SiO
2[embodiment 2～8 and comparative example 1～4]
Adopt method preparation substantially the same manner as Example 1 to have the different catalyzer of forming in the following table, and under following reaction conditions, carry out the reaction that ammoxidation of propylene generates vinyl cyanide, the results are shown in Table 1 with prepared catalyzer.
The reaction conditions of the foregoing description and comparative example is:
38 millimeters fluidized-bed reactors of φ
430 ℃ of temperature of reaction
Reaction pressure 0.14MPa
Loaded catalyst 400 grams
Catalyzer propylene load (WWH) 0.085 hour
-1
Unstripped gas proportioning (mole) C
3 =/ NH
3/ air=1/1.2/9.5
Table 1
| Embodiment | Catalyzer is formed | Acrylonitrile yield % | Vinyl cyanide selectivity % | Propylene conversion % |
| Embodiment 1 | K 0.1Na 0.28Cs 0.07P 0.025Ni 5.6Cr 0.35Ce 0.35Mg 1.2Ge 0.05Fe 2.0Bi 0.75Mo 12.5O x | 80.5 | 81.9 | 98.3 |
| Embodiment 2 | K 0.1Na 0.28Cs 0.07P 0.03Co 4.5Cr 0.35W 0.12Ce 0.35Mg 1.2Ge 0.075Fe 2.0Bi 0.75Mo 12.5O x | 79.9 | 81.5 | 98.0 |
| Embodiment 3 | K 0.1Na 0.28Cs 0.07P 0.03Ni 5.6Mn 0.1W 0.12Ce 0.45Mg 1.2Ge 0.05Fe 2.0Bi 0.75Mo 12.5O x | 80.0 | 81.8 | 97.8 |
| Embodiment 4 | K 0.1Na 0.28Cs 0.07As 0.05Ni 5.6Cr 0.45Ce 0.50Mg 1.5Ge 0.05Fe 2.0Bi 0.75Mo 12.5O x | 79.7 | 81.7 | 97.6 |
| Embodiment 5 | K 0.1Na 0.28Cs 0.07As 0.05Ni 5.6W 0.12Ce 0.30Mg 1.2Ge 0.075Fe 2.0Bi 0.75Mo 12.5O x | 79.6 | 81.1 | 98.2 |
| Embodiment 6 | K 0.14Cs 0.07As 0.05V 2.0Cr 0.4Mn 0.1W 0.12Ce 0.25Mg 1.2Ge 0.075Fe 2.5Bi 0.75Mo 12.5O x | 80.1 | 81.2 | 98.6 |
| Embodiment 7 | K 0.14Cs 0.07P 0.025V 2.0Cr 0.45W 0.14Ce 0.35Mg 1.2Ge 0.035Fe 2.0Bi 1.0Mo 12.5O x | 79.7 | 81.0 | 98.4 |
| Embodiment 8 | K 0.1Na 0.28Cs 0.07P 0.025V 2.0Cr 0.4Cu 0.15Ce 0.35Mg 1.2Ge 0.05Fe 2.0Bi 0.75Mo 12.5O x | 79.5 | 81.1 | 98.0 |
| Comparative example 1 | Mo 12Bi 0.9Fe 1.8Ni 2.0Co 5.0Na 0.15Mn 0.45Cr 0.45K 0.17Cs 0.05O x | 76.3 | ||
| Comparative example 2 | Mo 12Bi 0.9Fe 1.8Ni 2.4Co 4.3Na 0.15W 0.45Cr 0.45K 0.15Cs 0.07O x | 76.5 | ||
| Comparative example 3 | Mo 12Bi 0.9Fe 1.8Ni 2.0Co 5.0Na 0.15Mn 0.45Cr 0.45K 0.21O x | 75.7 | ||
| Comparative example 4 | Mo 12Bi 0.9Fe 1.8Ni 5.0Mg 2.0Na 0.15W 0.45Cr 0.45Cs 0.09O x | 76.9 |
Claims (7)
1, a kind of fluidized bed catalyst for ammoxidation of propylene, contain with the following composition of atomic ratio measuring chemical formula:
A
aB
bC
cCe
dMg
eGe
fFe
gBi
hMo
iO
x
A is selected among Li, Na, K, Rb or the Cs at least two kinds in the formula;
B is selected from least a among Co, Ni, Mn, Cu, W, Cr or the V;
C is selected from least a among B, P or the As;
The span of a is 0.01～1.5;
The span of b is 0.1～12.0;
The span of c is 0.01～0.45;
The span of d is 0.2～3.0;
The span of e is 0.8～7.5;
The span of f is 0.01～2.0;
The span of g is 0.1～4.0;
The span of h is 0.2～2.5;
The span of i is 12.0～14.5;
X satisfies the required Sauerstoffatom sum of each element valence in the catalyzer;
Wherein support of the catalyst is selected from silicon-dioxide, aluminum oxide or its mixture, and its consumption is 30～70% by weight percentage.
2, according to the described fluidized bed catalyst for ammoxidation of propylene of claim 1, the span that it is characterized in that a is 0.01～0.7.
3, according to the described fluidized bed catalyst for ammoxidation of propylene of claim 1, the span that it is characterized in that d is 0.3～2.0.
4, according to the described fluidized bed catalyst for ammoxidation of propylene of claim 1, the span that it is characterized in that e is 1.0～4.0.
5, according to the described fluidized bed catalyst for ammoxidation of propylene of claim 1, the span that it is characterized in that f is 0.01～1.0.
6, according to the described fluidized bed catalyst for ammoxidation of propylene of claim 1, the span that it is characterized in that g is 1.0～3.0.
7, according to the described fluidized bed catalyst for ammoxidation of propylene of claim 1, it is characterized in that support of the catalyst is a silicon-dioxide, its consumption is 40～60% by weight percentage.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99119953A CN1130261C (en) | 1999-11-03 | 1999-11-03 | Propylene ammonoxidizing fluid bed catalyst |
| JP2001518186A JP4095302B2 (en) | 1999-08-19 | 2000-06-21 | Fluidized bed catalyst for the ammoxidation of propylene to acrylonitrile. |
| PCT/CN2000/000167 WO2001014057A1 (en) | 1999-08-19 | 2000-06-21 | Fluid bed catalyst for ammoxidation of propylene to acrylonitrile |
| BRPI0013338-8A BR0013338B1 (en) | 1999-08-19 | 2000-06-21 | fluidized bed catalyst for propylene amoxidation to acrylonitrile. |
| AU53871/00A AU5387100A (en) | 1999-08-19 | 2000-06-21 | Fluid bed catalyst for ammoxidation of propylene to acrylonitrile |
| MXPA02001574A MXPA02001574A (en) | 1999-08-19 | 2000-06-21 | Fluid bed catalyst for ammoxidation of propylene to acrylonitrile. |
| DE10084931.8T DE10084931B3 (en) | 1999-08-19 | 2000-06-21 | Fluid bed catalyst for the ammoxidation of propylene to acrylonitrile |
| ROA200200166A RO120244B1 (en) | 1999-08-19 | 2000-06-21 | Fluidized bed catalyst for ammoxidation of propylene into acrylonitrile |
| US09/642,289 US6420307B1 (en) | 1999-08-19 | 2000-08-18 | Fluidized-bed catalyst for propylene ammoxidation to acrylonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99119953A CN1130261C (en) | 1999-11-03 | 1999-11-03 | Propylene ammonoxidizing fluid bed catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN1295063A CN1295063A (en) | 2001-05-16 |
| CN1130261C true CN1130261C (en) | 2003-12-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99119953A Expired - Fee Related CN1130261C (en) | 1999-08-19 | 1999-11-03 | Propylene ammonoxidizing fluid bed catalyst |
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| CN (1) | CN1130261C (en) |
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|---|---|---|---|---|
| CN100368082C (en) * | 2004-09-24 | 2008-02-13 | 中国石油化工股份有限公司 | Fluidized bed catalyst for prodn. of acrylonitrile |
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| Publication number | Publication date |
|---|---|
| CN1295063A (en) | 2001-05-16 |
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