CN1169783C - Fluidized bed catalyst for preparing acrylonitrile by ammoxidation - Google Patents

Fluidized bed catalyst for preparing acrylonitrile by ammoxidation Download PDF

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CN1169783C
CN1169783C CNB011321938A CN01132193A CN1169783C CN 1169783 C CN1169783 C CN 1169783C CN B011321938 A CNB011321938 A CN B011321938A CN 01132193 A CN01132193 A CN 01132193A CN 1169783 C CN1169783 C CN 1169783C
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catalyzer
span
propylene
ammoxidation
catalyst
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CN1418867A (en
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炜 安
安炜
吴粮华
陈欣
戴毅敏
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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Sinopec Shanghai Research Institute of Petrochemical Technology
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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 by propylene ammoxidation, and the catalyst contains a silicon dioxide carrier and a composition, wherein the composition has the chemical formula of Mo12BiaFebNicRedNaeXfYgOm measured by an atomic ratio, and in the chemical formula, X is at least one selected from Li, K, Rb, Cs, Sm and Tl; Y is at least one selected from Co, Mg, Mn, Ca, Ce, La, B, P and Cr. The catalyst of the present invention is especially suitable for being used under the conditions of a temperature slightly lower than the temperature of usual reaction, low ratio of air to propylene, high reaction pressure and high propylene load, a high acrylonitrile single-pass yield can be maintained, and the fluidized bed catalyst can be used in industrial production.

Description

The fluid catalyst of preparing acrylonitrile by ammoxidation
Technical field
The present invention relates to a kind of fluid catalyst of ammoxidating propylene to prepare acrylonitrile.
Background technology
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 40 years of development, and the throughput of factory and the market requirement are near balance.The main development trend of acrylonitrile process is built the technological transformation that new device turns to original factory by emphasis, further to cut down the consumption of raw materials and to increase throughput 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 be able to move under higher propylene load and higher reaction pressure, and keeps higher acrylonitrile yield.
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 handles the tonnage of propylene.Under the constant situation of catalyst loading, the reactor feed amount increases, and then the catalyzer loading capacity is also wanted corresponding increase; In addition, the reactor feed amount increases, and causes operating linear velocity also to significantly improve, and bed height increases.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 loading capacity of catalyzer reduces, and WWH is higher can to prevent the problems referred to above, and WWH improves in addition, can obtain higher purpose product output by the unit's of making device in the same time.
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 the catalyzer that a kind of catalyzer that uses molybdenum, bismuth, iron, nickel, magnesium, potassium and caesium system carries out preparing acrylonitrile by allylamine oxidation among document US 5093299 and the US5212137.Find out that from embodiment its catalyst system is not contain sodium, though mention thulium cerium and chromium in the optional elements, only use as optional elements.There is not to disclose the collocation service condition of other rare earth element and chromium and magnesium elements among the embodiment.The investigation condition of embodiment is a fixed bed, and 430 ℃ of temperature of reaction are not mentioned reaction pressure concrete in the experimental implementation and operational load situation data.This fixed bed investigation condition is difficult to reflect the truth of fluidized bed process.Introduce in this patent, its catalyzer can be operated under lower slightly usually temperature of reaction, and it has advantages of high catalytic activity and advantages of excellent oxidation-reduction stability, thereby compares conditional operation applicable to lower air/propylene.
Introduced a kind of manufacture method of vinyl cyanide among the flat 8-27089 of document.It adopts the catalyzer of molybdenum, bismuth, iron, magnesium and tungsten system to carry out the ammoxidation of propylene reaction, and the investigation condition among the document embodiment is a normal pressure, does not mention the situation data under high pressure, high operational load condition.
Summary of the invention
Technical problem to be solved by this invention is to overcome the catalyzer that exists in the above-mentioned document not relate to problem than high-response pressure and operational load, and a kind of fluid catalyst of new preparing acrylonitrile by ammoxidation is provided.This catalyzer can adapt under usually lower slightly temperature of reaction, lower air/propylene mol ratio, higher reaction pressure and higher loading condiction to be operated, and keeps high vinyl cyanide once through yield.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparing acrylonitrile by ammoxidation fluid catalyst, contain silica supports and with the following composition of atomic ratio measuring chemical formula:
Mo 12Bi aFe bNi cRe dNa eX fY gO m
X is selected from least a among Li, K, Rb, Cs, Sm or the T1 in the formula;
Y is selected from least a among Co, Mg, Mn, Ca, Ce, La, B, P or the Cr;
The span of a is 0.1～2.0;
The span of b is 0.1～3.0;
The span of c is 2.0～8.0;
The span of d is 0.001～1.0;
The span of e is 0.01～1.0;
The span of f is 0.01～1.5;
The span of g is 0.1～6.0;
M satisfies the required Sauerstoffatom sum of each element valence in the catalyzer;
Wherein the consumption of carrier silicon-dioxide is 30～70% by weight percentage in the catalyzer.
The value preferable range of d is 0.001～0.1 in the technique scheme, and more preferably scope is 0.001～0.05.The value preferable range of g is 1.0～4.5, and the consumption preferable range of carrier silicon-dioxide is 40～60% by weight percentage in the catalyzer.
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:
Molybdenum component in the catalyzer is with molybdenum oxide or ammonium molybdate.
The most handy corresponding acids of phosphorus in the catalyzer and boron or its ammonium salt; Germanium can be used germanium oxide; The most handy chromium trioxide of chromium, chromium nitrate or the mixture of the two; The most handy its nitrate of all the other components, oxyhydroxide maybe can be decomposed into the salt of oxide compound.
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,, and prevent that catalyzer is by over reduction with generation catalyst activity phase.
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 420～450 ℃, was preferably 425～435 ℃.Catalyzer of the present invention is a kind of lower slightly temperature of reaction usually that is applicable to, low air/propylene mol ratio, high pressure, high loading catalyzer, and therefore reaction pressure can be operated under the 0.14MPa condition in production equipment.Also do not have any disadvantageous effect if reaction pressure is lower than 0.14MPa, 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 0.08～0.12 hour -1Loading to hang down not only wastes catalyzer, and carbon dioxide production is increased, and selectivity descends, and is disadvantageous.
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.
Because the rhenium in the component is to improving load, reduce temperature of reaction and reducing air/propylene than favourable, and cooperation is formed with the catalyst formulation of optimizing, show that by test catalyzer of the present invention can adapt in 425 ℃ lower slightly usually of temperature of reaction, (WWH is 0.11 hour than high-response pressure (0.14MPa), higher load -1), lower air/propylene mol ratio is condition under to operate at 9.5: 1, and the vinyl cyanide once through yield has been up to 80.5% level, 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, 425 ℃ 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 0.11 hour -1
Propylene conversion, vinyl cyanide selectivity and once through yield are defined as follows in the present invention:
Figure C0113219300071
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
2.05 gram cesium nitrates, 3.88 gram SODIUMNITRATE are mixed with 1.75 gram saltpetre, add water 30 grams and the dissolving of heating back, obtain material (A); 12.5 gram chromium trioxides are dissolved in the 15 gram water, get material (B); 402.2 gram ammonium molybdates are dissolved in 60～90 ℃ of hot water of 350 grams, get material (C); 65.0 gram Bismuth trinitrates, 15.25 gram manganous nitrates, 290.5 gram nickelous nitrates, 46.8 gram cerous nitrates, 98.5 gram magnesium nitrates and 175.25 gram iron nitrates and 2.83 gram nitric acid rheniums are mixed, add water 250 grams, after the heating for dissolving as material (D); Take by weighing phosphoric acid solution 4.35 grams as material (E).
With material (A) and 1280 gram weight concentration is that 40% silicon sol mixes, under agitation add material (C), (B), (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 600 ℃ of roastings 2.0 hours, make and consist of: 50%K 0.1Na 0.20Cs 0.065P 0.025Cr 0.35Ce 0.35Ni 6.0Mg 1.25Mn 0.15Re 0.05Fe 2.0Bi 0.75Mo 12.0O m+ 50%SiO 2
[embodiment 2～5 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
425 ℃ of temperature of reaction
Reaction pressure 0.14MPa
Loaded catalyst 400 grams
Catalyzer propylene load (WWH) 0.11 hour -1
Proportioning raw materials (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 0.20Cs 0.065P 0.025Cr 0.35Ce 0.35Ni 6.0Mg 1.25Mn 0.15Re 0.05Fe 2.0Bi 0.75Mo 12.0O m 80.5 81.7 98.5
Embodiment 2 K 0.1Na 0.20Cs 0.065B 0.02Cr 0.30Ce 0.35Ni 6.0Mg 1.25Mn 0.15Re 0.1Fe 2.0Bi 0.75Mo 12.0O m 79.8 81.4 98.0
Embodiment 3 K 0.10Na 0.20Cs 0.05B 0.02Cr 0.30La 0.25Ni 6.0Mg 1.25Mn 0.15Re 0.001Fe 2.0Bi 0.75Mo 12.0O m 79.6 81.1 98.2
Embodiment 4 Li 0.1Na 0.20Cs 0.065P 0.025Cr 0.35Ce 0.40Co 2.5Ni 3.0Mg 1.25Mn 0.15Re 0.010Fe 2.0Bi 0.75Mo 12.0O m 80.0 81.2 98.5
Embodiment 5 K 0.15Na 0.20Rb 0.05P 0.025Cr 0.35Ce 0.35Ni 5.5Mg 1.25Mn 0.20Re 0.025Fe 2.0Bi 0.75Mo 12.0O m 80.3 81.3 98.8
Comparative example 1 Mo 12Bi 0.9Fe 1.8Ni 2.0Co 5.0Na 0.15Mn 0.45Cr 0.45K 0.17Cs 0.05O x 76.0
Comparative example 2 Mo 12Bi 0.9Fe 1.8Ni 2.4Co 4.3Na 0.15W 0.45Cr 0.45K 0.15Cs 0.07O x 76.3
Comparative example 3 Mo 12Bi 0.9Fe 1.8Ni 2.0Co 5.0Na 0.15Mn 0.45Cr 0.45K 0.21O x 75.4
Comparative example 4 Mo 12Bi 0.9Fe 1.8Ni 5.0Mg 20Na 0.15W 0.45Cr 0.45Cs 0.09O x 76.7

Claims (5)

1, a kind of fluid catalyst of preparing acrylonitrile by ammoxidation, contain silica supports and with the following composition of atomic ratio measuring chemical formula:
Mo 12Bi aFe bNi cRe dNa eX fY gO m
X is selected from least a among Li, K, Rb, Cs, Sm or the Tl in the formula;
Y is selected from least a among Co, Mg, Mn, Ca, Ce, La, B, P or the Cr;
The span of a is 0.1～2.0;
The span of b is 0.1～3.0;
The span of c is 2.0～8.0;
The span of d is 0.001～1.0;
The span of e is 0.01～1.0;
The span of f is 0.01～1.5;
The span of g is 0.1～6.0;
M satisfies the required Sauerstoffatom sum of each element valence in the catalyzer;
Wherein the consumption of carrier silicon-dioxide is 30～70% by weight percentage in the catalyzer.
2, according to the fluid catalyst of the described preparing acrylonitrile by ammoxidation of claim 1, the span that it is characterized in that d is 0.001～0.1.
3, according to the fluid catalyst of the described preparing acrylonitrile by ammoxidation of claim 2, the span that it is characterized in that d is 0.001～0.05.
4, according to the fluid catalyst of the described preparing acrylonitrile by ammoxidation of claim 1, the span that it is characterized in that g is 1.0～4.5.
5, according to the fluid catalyst of the described preparing acrylonitrile by ammoxidation of claim 1, the consumption that it is characterized in that carrier silicon-dioxide in the catalyzer is 40～60% by weight percentage.
CNB011321938A 2001-11-14 2001-11-14 Fluidized bed catalyst for preparing acrylonitrile by ammoxidation Expired - Lifetime CN1169783C (en)

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