CN1413978A - Fluidized-bed catalyst for preparing acrylonitrile - Google Patents

Fluidized-bed catalyst for preparing acrylonitrile Download PDF

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CN1413978A
CN1413978A CN01131944A CN01131944A CN1413978A CN 1413978 A CN1413978 A CN 1413978A CN 01131944 A CN01131944 A CN 01131944A CN 01131944 A CN01131944 A CN 01131944A CN 1413978 A CN1413978 A CN 1413978A
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catalyzer
span
vinyl cyanide
propylene
reaction
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CN1160315C (en
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谢国煌
陈欣
吴粮华
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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

A fluidized-bed catalyst for preparing acrylonitrile contains SiO2 as carrier and the composition: Mo12BiaFebNicNadCueCefXgYhOx, where X is chosen from (at least one of) LI, K, Rb, Cs and Sm, and Y is chosen from Co, Mg, Zn, Ca, Sn, Zn, La, B, P and Cr. Its advantage is high output rate of acrylonitrile.

Description

The fluid catalyst of preparation vinyl cyanide
Technical field
The present invention relates to a kind of fluid catalyst for preparing vinyl cyanide.
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.Therefore the catalyzer that requires to use instead should be able to be operated under higher propylene load and higher reaction pressure, and can keep 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.Because the increase of reactor feed amount, if the load of catalyzer is constant, then the catalyzer loading capacity is wanted corresponding increase.In addition, because the reactor feed amount increases, operating linear velocity is significantly improved.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, and the increase of the load of catalyzer can make same reactor obtain more purpose product in the unit time in addition.
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 i 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 evaluating 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 preparation vinyl cyanide is provided.This catalyzer can adapt in usually lower slightly temperature of reaction, lower air/propylene to be operated under than, higher reaction pressure and higher loading condiction, 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 fluid catalyst for preparing vinyl cyanide, contain silica supports and with the following composition of atomic ratio measuring chemical formula:
Mo 12Bi aFe bNi cNa dCu eCe fX gY hO x
X is selected from least a among Li, K, Rb, Cs or the Sm in the formula;
Y is selected from least a among Co, Mg, Mn, Ca, Sn, Zn, La, B, P or the Cr;
The span of a is 0.1～2.5;
The span of b is 0.1～7.0;
The span of c is 0.1～9.0;
The span of d is 0.01～1.0;
The span of e is 0.01～2.5;
The span of f is 0.01～3.0;
The span of g is 0.01～1.0;
The span of h is 0.1～5.0;
X satisfies the required Sauerstoffatom sum of each element valence in the catalyzer;
Wherein the amount of carrier silicon-dioxide is 30～70% by weight percentage in the catalyzer.
The value preferable range of e is 0.1～1.5 in the technique scheme, and the value preferable range of f is 0.1～2.0.In the catalyzer amount of carrier silicon-dioxide by weight percentage preferable range be 40～60%.
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; 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 can be carried out respectively in two stoving ovens, also can carry out in 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 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 425～450 ℃, was preferably 425～435 ℃.Catalyzer of the present invention is a kind of lower slightly temperature of reaction usually that is applicable to, lower 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 0.06～0.10 hour -1, be preferably 0.08～0.10 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.
Owing to introduced the element of copper and cerium in the component simultaneously, shown by test: catalyzer of the present invention can adapt at lower slightly usually 430 ℃ of temperature of reaction, air/propylene mol ratio 9.3: 1, (WWH is 0.085 hour than high-response pressure (0.14MPa), higher load -1) operate under the condition, and the vinyl cyanide once through yield has been up to 80.7% 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, 430 ℃ of temperature of reaction, reaction pressure 0.14MPa, proportioning raw materials (mole) is a propylene: ammonia: air=1: 1.2: 9.3, 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:
Figure A0113194400061
Figure A0113194400071
Figure A0113194400072
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, cupric nitrates, 42.8 grams, 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 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 0.35Cu 1.0Ni 6.0Mg 1.25Mn 0.15Fe 2.0Bi 0.75Mo 12.0O x+50％SiO 2。[embodiment 2～4 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
Proportioning raw materials (mole) C 3 =/ NH 3/ air=1/1.2/9.3
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 0.35Cu 1.0Ni 6.0Mg 1.25Mn 0.15Fe 2.0Bi 0.75Mo 12.0O x ????80.9 ????82.6 ????97.9
Embodiment 2 ?K 0.1Na 0.20Cs 0.065B 0.02Cr 0.30Ce 0.35Cu 0.5Ni 6.0Mg 1.25Mn 0.15Fe 2.0Bi 0.75Mo 12.0O x ????80.0 ????82.O ????97.6
Embodiment 3 ?Li 0.1Na 0.20Cs 0.065P 0.025Cr 0.35Ce 0.40Co 2.5Cu 0.1Ni 3.0Mg 1.25Mn 0.15Fe 2.0Bi 0.75Mo 12.0O x ????80.5 ????82.1 ????98.0
Embodiment 4 ?K 0.15Na 0.20Rb 0.05P 0.025Cr 0.35Ce 0.35Cu 0.15Ni 5.5Mg 1.25Mn 0.20Fe 2.0Bi 0.75Mo 12.0O x ????81.0 ????82.5 ????98.2
Comparative example 1 ?Mo 12Bi 0.9Fe 1.8Ni 2.0Co 5.0Na 0.15Mn 0.45Cr 0.45K 0.17Cs 0.05O x ????76.6
Comparative example 2 ?Mo 12Bi 0.9Fe 1.8Ni 2.4Co 4.3Na 0.15W 0.45Cr 0.45K 0.15Cs 0.07O x ????76.9
Comparative example 3 ?Mo 12Bi 0.9Fe 1.8Ni 2.0Co 5.0Na 0.15Mn 0.45Cr 0.45K 0.21O x ????75.9
Comparative example 4 ?Mo 12Bi 0.9Fe 1.8Ni 5.0Mg 2.0Na 0.15W 0.45Cr 0.45Cs 0.09O x ????77.1

Claims (4)

1, a kind of fluid catalyst for preparing vinyl cyanide, contain silica supports and with the following composition of atomic ratio measuring chemical formula:
Mo 12Bi aFe bNi cNa dCu eCe fX gY hO x
X is selected from least a among Li, K, Rb, Cs or the Sm in the formula;
Y is selected from least a among Co, Mg, Mn, Ca, Sn, Zn, La, B, P or the Cr;
The span of a is 0.1～2.5;
The span of b is 0.1～7.0;
The span of c is 0.1～9.0;
The span of d is 0.01～1.0;
The span of e is 0.01～2.5;
The span of f is 0.01～3.0;
The span of g is 0.01～1.0;
The span of h is 0.1～5.0;
X satisfies the required Sauerstoffatom sum of each element valence in the catalyzer;
Wherein the amount of silicon-dioxide is 30～70% by weight percentage in the catalyzer.
2, according to the fluid catalyst of the described preparation vinyl cyanide of claim 1, the span that it is characterized in that e is 0.1～1.5.
3, according to the fluid catalyst of the described preparation vinyl cyanide of claim 1, the span that it is characterized in that f is 0.1～2.0.
4, according to the fluid catalyst of the described preparation vinyl cyanide of claim 1, the amount that it is characterized in that carrier silicon-dioxide in the catalyzer is 40～60% by weight percentage.
CNB011319445A 2001-10-22 2001-10-22 Fluidized-bed catalyst for preparing acrylonitrile Expired - Lifetime CN1160315C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN109772351A (en) * 2017-11-14 2019-05-21 中国石油化工股份有限公司 A kind of catalyst and its preparation method and application producing 1,4- butynediols coproduction propilolic alcohol

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN109772351A (en) * 2017-11-14 2019-05-21 中国石油化工股份有限公司 A kind of catalyst and its preparation method and application producing 1,4- butynediols coproduction propilolic alcohol
CN109772351B (en) * 2017-11-14 2021-10-08 中国石油化工股份有限公司 Catalyst for producing 1, 4-butynediol and co-producing propiolic alcohol and preparation method and application thereof

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