CN101733117B - High-stability fluid catalyst for producing acrylonitrile - Google Patents

High-stability fluid catalyst for producing acrylonitrile Download PDF

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CN101733117B
CN101733117B CN2008100439653A CN200810043965A CN101733117B CN 101733117 B CN101733117 B CN 101733117B CN 2008100439653 A CN2008100439653 A CN 2008100439653A CN 200810043965 A CN200810043965 A CN 200810043965A CN 101733117 B CN101733117 B CN 101733117B
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acrylonitrile
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fluid catalyst
propylene
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CN101733117A (en
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汪国军
吴粮华
陈卫军
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • Y02P20/00—Technologies relating to chemical industry
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Abstract

The invention relates to a high-stability fluid catalyst for producing acrylonitrile by propylene ammoxidation, which mainly solves the problem of poor stability of catalysts in the prior art. The high-stability fluid catalyst adopts silicon dioxide, aluminum oxide or a mixture thereof as a carrier and comprises a composition with the following chemical formula in atomic ratio: AaBbGecBafPrdBieMo12Ox, wherein A is at least one of Li, Na, K, Rb or Cs; and B is at least one of Ca, Mn, Fe, Co or Ni. The technical scheme solves the problem better, and can be used for industrial production of the acrylonitrile under the high propylene loading condition.

Description

Produce the high-stability fluid catalyst of acrylonitrile
Technical field
The present invention relates to a kind of high-stability fluid catalyst of producing acrylonitrile.
Background technology
Acrylonitrile is important Organic Chemicals, and it is through the ammoxidation of propylene reacted.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 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 acrylonitrile once through yield, and the raising of producing load.
Ammonia oxidation is produced acrylonitrile through 40 years of development, and the production capacity of factory and the market demand are near balance.The main development trend of acrylonitrile process is built the technological transformation that new equipment turns to original factory by emphasis, further to cut down the consumption of raw materials and to increase production capacity at present.Through transformation to original factory, change effective catalyst and the bottleneck of eliminating in the production technology, the production capacity of acrylonitrile might improve 50～80%, and required investment is merely 20～30% of new device, economic benefit is very huge.
The useful load of requirement catalyst can not be too many when original acrylonitrile installation expanded ability, and the catalyst that for this reason requires to use instead keeps high acrylonitrile yield under higher propylene load.After reactor size and production capacity are confirmed, the reactor charge catalyst what with catalyst can bear load relevant, i.e. WWH.Its definition is a catalyst per ton, per hour can handle the tonnage of propylene.When the reactor feed amount increases, if the load of catalyst is constant, then the catalyst useful load is also wanted corresponding increase.But cooling water pipe insufficient height in the intrinsic fluidized-bed reactor, so the fluid height of catalyst reactor might surpass the height of cooling water pipe.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 acrylonitrile selectivity descends, and therefore the catalyst of higher WWH can prevent the problems referred to above.
The WWH that improves catalyst in theory should increase the adsorption activation ability of catalyst to propylene, but certain element can improve the report to propylene adsorption activation ability in the present catalyst-free still.Introduced the catalyst that a kind of catalyst 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.Introduce in this patent, its catalyst can be operated under lower slightly usually reaction temperature, and it has advantages of high catalytic activity and advantages of excellent oxidation-reduction stability, thereby compares conditional operation applicable to lower air/propylene.But it should be noted; The investigation condition of above-mentioned patent working example is a fixed bed; 430 ℃ of reaction temperatures are not mentioned reaction pressure concrete in the experimental implementation and operational load situation data, more do not relate to the reactivity worth and the stability problem of catalyst under the high load capacity.
Introduced a kind of manufacturing approach of acrylonitrile among the flat 8-27089 of document, it adopts the catalyst 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.With regard to the acrylonitrile yield of initial reaction stage, disclosed catalyst has had bigger improvement in the above-mentioned patent document.
With regard to the acrylonitrile yield of initial reaction stage, disclosed catalyst has had bigger improvement in the above-mentioned patent document.But not only do not relate to catalyst acrylonitrile yield data under higher propylene load and higher reaction pressure in above-mentioned all patents; More do not relate to catalyst under higher propylene load and higher reaction pressure, acrylonitrile yield data after the long-time running.
A kind of catalyst that contains preparing acrylonitrile by allylamine oxidation at least a at least a in molybdenum, bismuth, cerium, iron, nickel, magnesium or the zinc, potassium or caesium or the rubidium is disclosed among document JP 9401312 and the CN1121321A.Introduce in this patent, its catalyst can prevent effectively under the situation in reaction time that acrylonitrile yield from reducing prolonging, but its evaluating catalyst is under quite low reaction pressure and low operational load condition, to carry out.
A kind of fluid catalyst of preparing acrylonitrile by propene ammonia oxidation is disclosed among the document CN1285237A.Catalyst is formed available A aB bC cGe dNa eFe fBi gMo 12O xFormula representes that A is selected from least two kinds among Li, K, Rb, Cs, Sm, In or the T1 in the formula; B is selected from least a among P, Sb, Cr, W, Pr, Ce, As, B, Te, Cd or the V; C is selected from Ni, Co or its mixture.
A kind of fluid catalyst of producing acrylonitrile is disclosed among the document CN1285238A.Catalyst is formed available Mo 12Bi aFe bW cPr dNa eX fY gZ hO iFormula representes that X is selected among P, As, B, Ge, Ga, Al, Sn, Pb, Cr, V, Nb or the Tb at least a in the formula; Y is selected among Co, Ni, Mn, Mg, Ca, Sr, Zn or the Cd at least a; Z is selected among K, Rb, Cs, In, T1, Sm or the Te at least a.This invention catalyst can be used for the acrylonitrile commercial production, but in this catalyst, tungsten is indispensable element during catalyst is formed.
Disclose a kind of oxide component that contains molybdenum-bismuth-iron-sodium system among the document CN1172689A and added the acrylonitrile fluidized-bed catalyst of thulium praseodymium, neodymium or their mixtures, but in this catalyst, contained at least a element in phosphorus, arsenic, boron, antimony, chromium, tungsten, the vanadium.
Summary of the invention
Technical problem to be solved by this invention is to have in the past that not relating to finishes drilling at higher propylene load with than high-response pressure does and stability problem in the technology, and a kind of high-stability fluid catalyst of new production acrylonitrile is provided.This catalyst not only can have higher acrylonitrile yield under higher propylene load and higher reaction pressure, and operation has the advantage of good stability under these conditions.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of high-stability fluid catalyst of producing acrylonitrile, contain with the following composition of atomic ratio measuring chemical formula:
A aB bGe cBa fPr dBi eMo 12O x
A is selected from least a among Li, Na, K, Rb and the Cs in the formula;
B is selected from least a among Ca, Mn, Fe, Co or the Ni;
The span of a is 0.01～2.5;
The span of b is 1～15;
The span of c is>0～5;
The span of d is 0.01～3;
The span of e is 0.01～3;
The span of f is 0.1～4;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
Wherein catalyst carrier is selected from silica, aluminium oxide or its mixture, and its consumption is 30～70% by weight percentage.
The value preferable range of a is 0.05～1.5 in the technique scheme; The value preferable range of b is 2.5～12, and the value preferable range of c is 0～3.0, and the value preferable range of d is 0.1～2.5; The value preferable range of e is 0.1～2.5, and the span of f is 0.5～2.5.The catalyst carrier preferred version is a silica, and its consumption preferable range is 40～60% by weight percentage.
The manufacturing approach of catalyst of the present invention does not have specific (special) requirements, can be undertaken by well-established law.At first the catalyst each component is processed solution, be mixed and made into slurry with carrier again, the spray-dried microspheroidal that is shaped to, catalyst is processed in last roasting.The preparation of slurry is preferably undertaken by the CN1005248C method.
The raw material of making catalyst of the present invention is:
Molybdenum component in the catalyst is with molybdenum oxide or ammonium molybdate.
The most handy its nitrate of all the other each components, oxalates, hydroxide, oxide maybe can be decomposed into the salt of oxide.
Raw material available silicon colloidal sol, silicon gel or both mixtures as carrier silica.If use Ludox, its quality will meet the requirement of CN1005248C.
It is 47～55% back spray-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 catalyst of processing has good size distribution with centrifugal better.
The roasting of catalyst can be divided into two stages and carry out: each element decomposition of salts and high-temperature roasting in the catalyst.The catabolic phase temperature is preferably 200～300 ℃, and the time is 0.5～2 hour.Sintering 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 roasters, also can in a stove, be divided into two zones, also can in the continous way rotary roasting furnace, accomplish simultaneously and decompose and roasting.In catalyst decomposes and roasting process, to feed an amount of air,, and prevent that catalyst is by over reduction with generation catalytic activity phase.
Adopt the specification of catalyst manufacturing acrylonitrile 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.
Getting into 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 8.8～9.8.If owing to some operational reason must with higher air than the time, can increase to 11, reaction is not had significant impact.But from security consideration, the excess of oxygen in the reacting gas can not preferably be not more than 4% greater than 7% (volume).
When catalyst of the present invention was used for fluidized-bed reactor, reaction temperature was 410～470 ℃, was preferably 420～450 ℃.Therefore catalyst of the present invention is a kind of catalyst that is applicable to elevated pressures, high load capacity, and reaction pressure can be more than 0.08MPa in process units, for example, and 0.08～0.18MPa.Also do not have any adverse effect if reaction pressure is lower than 0.08MPa, acrylonitrile yield can further improve.
The propylene load (WWH) of catalyst of the present invention is 0.045～0.15 hour -1, be preferably 0.06～0.13 hour -1Loading to hang down not only wastes catalyst, and carbon dioxide production is increased, and selectivity descends, and is disadvantageous.Loading does not too highly have practical significance, because the catalyst addition is very few, the heat transfer area that can make cooling water pipe in the catalyst layer causes reaction temperature uncontrollable less than removing the required area of reaction heat.
The product of making acrylonitrile with catalyst of the present invention reclaims process for refining, and available existing production technology 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.
Isolate and alternate cooperative effect according to the selective oxidation reaction active site; Introduce the suitable activity position during catalyst of the present invention is formed and isolated element and the mutually synergistic element of activity; Make to make the alternate existing mutual cooperative effect of each thing in the catalyst, promote propylene to transform, have thing relative activity position to play suitable buffer action again; Propylene is transformed to generating the acrylonitrile direction, thereby greatly reduce the deep oxidation accessory substance.Use the catalyst among the present invention to carry out the ammoxidation of propylene reaction, can under higher propylene load and higher reaction pressure, obtain higher acrylonitrile yield.Using catalyst of the present invention, is 0.14MPa in reaction pressure, and the propylene load is 0.085 hour -1Operate under the condition, its acrylonitrile yield can reach 80%, and through running in 1200 hours, keeps acrylonitrile yield constant basically, has obtained better technical effect.
Activity of such catalysts of the present invention examination is in internal diameter is 38 millimeters fluidized-bed reactor, to carry out.Loaded catalyst 400 grams, 440 ℃ of reaction temperatures, reaction pressure 0.14MPa, proportioning raw materials (mole) is a propylene: ammonia: air=1: 1.2: 9.8, the propylene load (WWH) of catalyst is 0.085 hour -1
The definition of propylene conversion, acrylonitrile selectivity and once through yield is following in the present invention:
Figure G2008100439653D00051
Figure G2008100439653D00052
Figure G2008100439653D00053
Through embodiment the present invention is done further elaboration below.
The specific embodiment
[embodiment 1]
Dissolve with adding water 11 grams and heating the back 1.6 gram NaOH and 4.1 restrains potassium hydroxide, obtain material (A); 850.0 gram ammonium molybdates are dissolved in 60～90 ℃ of hot water of 800 grams, get material (B); 157.5 gram bismuth nitrates, 286.8 gram manganese nitrates, 418.6 gram barium nitrates, 594.5 gram nickel nitrates, 330.4 gram ferric nitrates are mixed; Add water 340 grams, as material (C), take by weighing 26.6 gram praseodymium nitrates and 23.9 gram germanium oxides after the heating for dissolving; Add water 15 grams, get material (D).
With material (A) and 2475 gram weight concentration is that 40% Ludox mixes; Under agitation add material (B), (C) and (D) successively; After fully stirring, get slurry; According to well-established law the slurry of processing is carried out the framboid moulding in spray dryer; Be 89 millimeters at internal diameter at last, length be in the rotary roasting furnace of 1700 millimeters (
Figure G2008100439653D0005182745QIETU
89 * 1700 millimeters) in 600 ℃ of roastings 2.0 hours, process and consist of:
50％K 0.15Na 0.1Fe 2.0Ni 5.0Mn 2.0Ba 2.0Ge 0.6Pr 0.4Bi 0.85Mo 12.0O x+50％SiO 2。
[embodiment 2～6 and comparative example 1～4]
Adopt the catalyst that has different compositions in the following table with embodiment 1 essentially identical method preparation, and under following reaction condition, carry out the reaction that ammoxidation of propylene generates acrylonitrile with prepared catalyst, the result sees table 1.
The reaction condition of the foregoing description and comparative example is:
millimeter fluidized-bed reactor
440 ℃ of reaction temperatures
Reaction pressure 0.14MPa
Loaded catalyst 400 grams
Catalyst propylene load (WWH) 0.085 hour -1
Proportioning raw materials (mole) C 3 =/ NH 3/ air=1/1.2/9.8
Reaction result was calculated in the reaction beginning in back 4 hours, 400 hours, 800 hours and 1200 hours respectively.
Table 1
Figure G2008100439653D00061

Claims (7)

1. high-stability fluid catalyst of producing acrylonitrile, by forming with the following composition of atomic ratio measuring chemical formula:
A aB bGe cBa fPr dBi eMo 12O x
A is selected from least a among Li, K, Rb and the Cs in the formula;
B is selected from least a among Ca, Mn, Fe, Co or the Ni;
The span of a is 0.01～2.5;
The span of b is 1～15;
The span of c is greater than 0 and smaller or equal to 5;
The span of d is 0.01～3;
The span of e is 0.01～3;
The span of f is 0.1～4;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
Wherein catalyst carrier is selected from silica, aluminium oxide or its mixture, and its consumption is 30～70% by weight percentage.
2. according to the high-stability fluid catalyst of the said production acrylonitrile of claim 1, the span that it is characterized in that a is 0.05～1.5.
3. according to the high-stability fluid catalyst of the said production acrylonitrile of claim 1, the span that it is characterized in that b is 2.5～12.
4. according to the high-stability fluid catalyst of the said production acrylonitrile of claim 1, the span that it is characterized in that c is greater than 0 and smaller or equal to 3.
5. according to the high-stability fluid catalyst of the said production acrylonitrile of claim 1, the span that it is characterized in that d is 0.1～2.5.
6. according to the high-stability fluid catalyst of the said production acrylonitrile of claim 1, the span that it is characterized in that e is 0.1～2.5; The span of f is 0.5～2.5.
7. according to the high-stability fluid catalyst of the said production acrylonitrile of claim 1, it is characterized in that catalyst carrier is a silica, its consumption is 40～60% by weight percentage.
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CN103657669A (en) * 2012-09-05 2014-03-26 中国石油化工股份有限公司 Fluidized bed catalyst for preparing unsaturation nitrile through ammoxidation and method thereof
CN103769140B (en) * 2012-10-25 2016-05-18 中国石油化工股份有限公司 Acrylonitrile fluidized-bed catalyst and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5688739A (en) * 1995-05-01 1997-11-18 The Standard Oil Company Ammoxidation catalysts containing germanium to produce high yields of acrylonitrile
US5770757A (en) * 1995-06-05 1998-06-23 The Standard Oil Company Ammoxidation catalysts containing germanium to produce high yields of acrylonitrile
EP1075871A1 (en) * 1998-04-23 2001-02-14 Mitsubishi Rayon Co., Ltd. Catalyst for producing unsaturated nitrile
CN1507948A (en) * 2002-12-17 2004-06-30 中国石油化工股份有限公司 Fluidized bed catalyst for preparing acrylonitrile
CN1810358A (en) * 2005-01-26 2006-08-02 中国石油化工股份有限公司 Acrylonitrile fluid bed catalyst

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5688739A (en) * 1995-05-01 1997-11-18 The Standard Oil Company Ammoxidation catalysts containing germanium to produce high yields of acrylonitrile
US5770757A (en) * 1995-06-05 1998-06-23 The Standard Oil Company Ammoxidation catalysts containing germanium to produce high yields of acrylonitrile
EP1075871A1 (en) * 1998-04-23 2001-02-14 Mitsubishi Rayon Co., Ltd. Catalyst for producing unsaturated nitrile
CN1507948A (en) * 2002-12-17 2004-06-30 中国石油化工股份有限公司 Fluidized bed catalyst for preparing acrylonitrile
CN1810358A (en) * 2005-01-26 2006-08-02 中国石油化工股份有限公司 Acrylonitrile fluid bed catalyst

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