CN100393406C - Method for the thermal treatment of an active catalytic mass - Google Patents
Method for the thermal treatment of an active catalytic mass Download PDFInfo
- Publication number
- CN100393406C CN100393406C CNB200480015576XA CN200480015576A CN100393406C CN 100393406 C CN100393406 C CN 100393406C CN B200480015576X A CNB200480015576X A CN B200480015576XA CN 200480015576 A CN200480015576 A CN 200480015576A CN 100393406 C CN100393406 C CN 100393406C
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- China
- Prior art keywords
- swivelling pipe
- air
- catalyst
- multielement oxide
- rotary tube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011850 water-based material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
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- C07C57/03—Monocarboxylic acids
- C07C57/04—Acrylic acid; Methacrylic acid
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/20—Details, accessories, or equipment peculiar to rotary-drum furnaces
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- F27—FURNACES; KILNS; OVENS; RETORTS
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- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/20—Details, accessories, or equipment peculiar to rotary-drum furnaces
- F27B7/36—Arrangements of air or gas supply devices
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Abstract
The invention relates to a method for the thermal treatment of the precursor mass to an active catalytic mass in a rotating tube oven (2) with a through gas flow, wherein, at least a partial amount of the gas flowing through the rotating tube oven is run in a loop (19). The invention further relates to the corresponding rotating tube oven device and tube bundle reactors, for the partial gas phase oxidation of acrolein to give acrylic acid, reactors are loaded with the catalyst, the catalytic active mass of which may be obtained after the method for thermal treatment.
Description
The present invention relates to flow through therein the method for in the rotary tube furnace of air-flow the precursor material of catalytic active material being heat-treated.
In this article, the term catalytic active material is construed as the solid except that reactant of (for example in the gas-phase chemical reaction) in the chemical reaction, carries out temperature and/or the raising generation expectation product selectivity that this chemical reaction needs with reduction.Chemical reaction generally occurs in the surface (interface) of catalytic active material.
This heterogeneous catalytic reaction both can be carried out in liquid phase in principle, can carry out in gas phase again, and its example has heterogeneous catalyzed hydration effect, dehydrogenation and oxidative dehydrogenation effect, and incomplete oxidation and incomplete amine oxidation.Wherein, active material can powder type and after the mechanograph that produces certain geometrical shape through shaping and the form that obtains is used.The latter can for example followingly carry out: introduce (absorption) inner surface to pre-molded carrier, at this moment use the term supported catalyst; Be applied to the outer surface of pre-molded carrier, at this moment use the term coated catalysts; Or suppress, use the term unsupported catalyst this moment.Precursor material itself can be shaped, or only catalytic active material be shaped.
The complete oxidation of organic compound (for example, saturated or unsaturated hydrocarbons, alcohol or aldehyde) is interpreted as that in this article all carbon that are contained in the organic compound all change oxide (CO, the CO of carbon into
2).
Other reaction of all of organic compound and oxygen (comprising the oxidative dehydrogenation effect) is considered as incomplete oxidation in this article.Not exclusively the amine oxidation is in there being ammonia in addition with the different of incomplete oxidation effect.
Now substantially known molded or not molded catalytic active material can followingly obtain usually: make be generally do not have catalytic activity maybe can have reduction activity and can be through molded or without molded precursor material, and this precursor material is exposed in the specific atmosphere at elevated temperatures.
For example, DE-A 10211275 dehydrogenation described in embodiment precursor material in the air-flow (hydrogen, air, nitrogen) that changes the activation under the temperature (500 ℃) that raises and in gas phase the purposes in the catalyst in the heterogeneous catalysis dehydrogenation of hydrocarbon.
Similarly, EP-A 529853, EP-A 318295, EP-A 608838, WO 01/96270, EP-A 731077, EP-A 1260495, EP-A 1254709, EP-A 1192987, EP-A 962253, EP-A 1262235, EP-A 1090684, DE-A 19835247, EP-A 895809, DE-A10261186, EP-A 774297, WO 02/24620, EP-A 668104, DE-A 2161450, EP-A 724481, EP-A 714700, DE-A 10046928 and DE-A 19815281 have described the heat treatment of precursor material in the atmosphere of suitable wide region of multielement oxide active material.In these were open, suggestion was used as the quite catalytic active material in the catalyst of the incomplete gaseous oxidation of heterogeneous catalysis of broad organic compound and the oxidation of gas phase amine of scope with obtaining multielement oxide active material.
By and large, these heat treatments can be carried out in the quite wide type of furnace of scope, for example, and rotating table furnace, revolving burner, belt calcining furnace, fluid bed furnace or shaft (tower) furnace.
More and more important (referring to WO 02/24620) is that all precursor materials to be heated are handling under the condition quite uniformly, with the active material of all being measured with suitable uniform properties.
For example, the active material that has suitable uniform properties in a large number more is applicable in the higher heterogeneous gas phase catalysis of the reactant load of active material, because at this moment can adopt on reactor cross section thermal rection condition especially uniformly.
Based on this background, WO 02/24620 suggestion utilizes special belt calciner plant to carry out the heat treatment of this precursor material.Yet the defective of belt calcining is that it carries out on the fixed bed of precursor material.Yet, in this fixed bed, can form obstruction usually heat treated whole precursor material is carried out even heat treated thermograde.
By contrast, in moving bed, be preferred to the heat treatment of precursor material (as the heat treatment representative in rotary tube furnace).Because the continuously active of precursor material in rotary tube furnace, this material has formed continuously from the homogenize bed, wherein can not form, for example, focus or cold spot.Most of heat treatments of precursor material comprise heat release or endothermic process, and this can form focus (position of the maximum temperature in the heat treatment precursor material) or emerge cold spot (position of the minimum temperature in the heat treatment precursor material).Yet too high and low excessively temperature all can influence the catalytic property of active material unfriendly.
Another viewpoint is the thermal decomposition process that most of heat treatments of precursor material are attended by chemical composition in the precursor material, has generated gaseous decomposition product, and they may have favourable or adverse influence to the gained quality of active material.In both cases, all be favourable from homogenize in the moving bed.
The heat treatment of precursor material in rotary tube furnace of active material has been proposed among DE-A 19815281 (for example, embodiment 1), DE-A 10046928 (for example, preparation example 1) and the EP-A 714700 (embodiment) especially.
Astoundingly, the heat treatment in this rotary tube furnace industrial be to carry out in the mode that the inclination angle with swivelling pipe and level is adjusted to non-vanishing value.The peak of swivelling pipe is the introducing point of precursor material, the position that the minimum point based material is discharged.The continued operation of rotation piping, precursor material system promptly to be heated is continuously supplied to a side of swivelling pipe, is delivered to minimum point continuously from peak in swivelling pipe, and discharges continuously in minimum point.Precursor material is usually along the path experience heat treatment by swivelling pipe.
Defective is that this continuous process only can make material to be heated be detained the quite short time in swivelling pipe.
For setting up the atmosphere of expectation, make the precursor material of relevant air-flow and conveying pass through swivelling pipe inversely usually.Under the simplest situation, this air-flow can be made up of air, but in other cases, also can be especially (reducibility gas for example is as hydrogen or ammonia by available gas; Or inert gas, as nitrogen) form.
The shortcoming of described method is the quite high requirement of these gases, and they further do not utilize after leaving swivelling pipe.Another shortcoming is to discharge with air-flow by the gas with advantageous effects that thermal decomposition forms in material, and can not show its advantageous effects again (for example, by NH
4 +The NH that forms
3, by NO
3 -The NO that forms
2, or by CO
3 2-The CO that forms
2Or CO).This favourable effect can be a reduction for example.
The desirable temperature that is present in the material in the swivelling pipe normally produces indirectly by make the specified temp that the rotation tube wall reaches from the outside.
For avoiding radially reaching axial-temperature gradient significantly in the swivelling pipe, suitable is with air-flow will be supplied in the swivelling pipe by this air-flow of swivelling pipe after being preheated to material in the swivelling pipe temperature required again.
The thermal content of this air-flow can not further be utilized usually when leaving swivelling pipe, and this is a shortcoming.
In view of prior art, the purpose of this invention is to provide the method for in a kind of rotary tube furnace that flows through air-flow therein the precursor material of catalytic active material being heat-treated, the method has overcome the shortcoming in the art methods basically.
The inventor finds, this purpose can realize by a kind of method of in the rotary tube furnace of air-flow the precursor material of catalytic active material being heat-treated that flows through therein, wherein makes the flow through air-flow circulation of rotary tube furnace of at least a portion.
Under the simplest situation, the air-flow of the rotary tube furnace of flowing through can be made up of air, but also can include the gas of usefulness, as CO, CO
2, NH
3, N
2, NO
x, SO
2, or acetonitrile, or by these gas compositions.But the mixture that also can comprise these gases, or form by this mixture.
In this novel method, the air-flow of the rotary tube furnace of flowing through can be 〉=0 to 500 cubic metre (S.T.P.)/hour, or be under the situation of powder type at precursor material, be up to 300 cubic metres (S.T.P.)/hour.The air-flow of rotary tube furnace of flowing through often can be 〉=50 to 500 (or 300), be generally 100 to 300 cubic metres (S.T.P.)/hour.
Need suitable rotary tube type furnace apparatus to implement this novel method.This Design of device below is described, but therefore it does not limit the rotary tube type furnace apparatus that this novel method maybe can supply this purposes to use by any way.
Fig. 1 shows and to be suitable for for example schematic diagram of the rotary tube type furnace apparatus of this novel method (and being used among the embodiment), below used Reference numeral also relate to this figure.Adjustment process is preferably carried out under the control of computer.
The center element that is suitable for carrying out the rotary tube type furnace apparatus of this novel method is a swivelling pipe 1.
It can be for example 4000 millimeters long, and has 700 millimeters internal diameter.It can be made by stainless steel 1.4893, and has 10 millimeters wall thickness and (be up to 15 meters, be up to 12 meters swivelling pipe length usually and also be applicable to this novel method certainly; Swivelling pipe length in this novel method usually 〉=1 meter, often 〉=4 meters; Internal diameter is generally 20 centimetres to 2 meters, often is 20 centimetres to 1 meter).
Can by rights reciprocating type lance shape thing be installed on the inner surface of rotary tube furnace.It is mainly used in heat treated precursor material in rotary tube furnace (material to be heated) is promoted, and therefore promote in moving bed from homogenize.For example, based on described described other size of giving an example of swivelling pipe device of the present invention that is suitable for of giving an example, the height of reciprocating type lance shape thing can be 5 centimetres (all size systems are relative to each other, and are used among the embodiment).In principle, each reciprocating type lance shape thing can extend on the whole length of swivelling pipe.But reciprocating type lance shape thing should only extend on a part of length of swivelling pipe.In exemplary specific embodiments, it can have for example 23.5 centimetres length.In these cases, according to the present invention, if install on one of rotary tube furnace identical height a plurality of (a plurality of) reciprocating type lance shape thing (for example, four=quadruple body) is equidistant on circumference (for example, every 90 °), this will be favourable.With regard to application technology, will be favourable if having a plurality of polyads along swivelling pipe.In the exemplary specific embodiment, there are eight this quadruple bodies (interval is 23.5 centimetres under each situation) along swivelling pipe.The reciprocating type lance shape thing of two adjacent polyads (quadruple body) preferably is present on the circumference of swivelling pipe interlaced with each otherly.Rotary tube furnace begin the place and preferably there is not reciprocating type lance shape thing in terminal (in the exemplary specific embodiment the most preceding and last 23.5 centimetres).
The peripheral speed of swivelling pipe preferably can change.Typical speed is that per minute＞0 is to 5 or 3 commentaries on classics.But advantageously swivelling pipe inverse clock or clockwise rotation.For example, under the situation of clockwise rotation, material remains in the swivelling pipe; For example, under the situation of inverse clock rotation, precursor material to be heated is delivered to outlet 4 by the inclination of swivelling pipe from charging aperture 3, and shifts out by discharging servicing unit (for example, oar) spin tube.
The inclination angle of swivelling pipe and level preferably can change.Typical scope is 0 to 4 ° or 2 °.In batch operation, it in fact is 0 °.In continued operation, the minimum point of swivelling pipe is positioned at the material outlet.
Material feeding is preferably controlled volume through the rotating vane feeder, or utilizes balance to carry out quality control.As previously mentioned, material discharge system controls by the direction of rotation of swivelling pipe.
In size as above in the batch operation of the swivelling pipe of (and size also can be bigger or less, to carry out foregoing novel method), but the material of heat treatment 200 to 600 kilogram quantities.This amount exists only in the heating part of swivelling pipe usually.
As wanting,, reach the essential circulation volume of this purpose (under the simplest situation, being pipeline system) according to rotary tube type furnace apparatus needs used in the present invention in order to make the flow through air-flow circulation of rotary tube furnace of at least a portion according to required for the present invention.Though it is with the static mode setting, swivelling pipe movably (rotation) is installed.
Under each situation,, can use by the ball bearing or the gap of graphite or teflon (Teflon) ring sealing (graphite or teflon are pressed into fitted seal) for making fixing and rotary components is connected with each other in the swivelling pipe inlet and in the swivelling pipe outlet.Because graphite is pressed into the stability of fitted seal to high temperature, thereby it is preferred.
Swivelling pipe is suitable for it to begin the place and end is tapered, and stretches into respectively in the pipe of the pipeloop that imports and derive.
These connect the most handy sealing gas and wash away.Two wash away air-flow 11 enters the inlet of swivelling pipe and the additional air-flow by swivelling pipe of outlet that air-flow comes out from swivelling pipe at air-flow.But it is temperature required and decide in the swivelling pipe that the chemical composition apparent heat treatment of washing away air-flow is used.For example, available air is as sealing gas.Yet, especially under the situation of under higher temperature, heat-treating, preferably use inert gas (for example, nitrogen) as sealing gas, because like this except producing sealing effectiveness, in fact also can be protected from oxidation simultaneously.The amount of sealing gas preferably keeps lowlyer.Therefore, this type of respectively washes away air-flow and is preferably＞and 0 to 50, preferred 1 to 50 cubic metre (S.T.P.)/hour.
Sealing effectiveness is for prevent any incomplete safe composition (for example, the CO on the toxicology that occupies the majority and often also be included in swivelling pipe
2, NO
x, NH
3, CO, SO
2, acetonitrile) atmosphere by static/being rotatably connected to enter in the ambient atmosphere is even more important.
Circulating current (gas circulation) is carried by recycle gas compressor 13 (fan for example, comes from the KXE 160-004030-00 type fan of KonradReitz GmbH), and it is air-breathing on the direction of air-flow outflow swivelling pipe, and exerts pressure on other direction.Be in close proximity to the recycle gas compressor downstream, gas pressure is usually above atmospheric pressure (promptly being higher than an atmospheric pressure).The circulating air outlet is positioned at the downstream of recycle gas compressor, and circulating air can be discharged by control valve 14, and by discharging air compressor 17 (fans; For example, come from the T100/315-R3/500 type of Meidinger) suck.According to the present invention, it will be favourable having pressure reducer 15 (for example orifice plate, for example about 3 times of cross-sectional constriction) as the downstream at the circulating air exit point.Use this pressure reducer, simply mode makes the gas that sucks in the suction side of recycle gas compressor more than the gas of on the pressure side emitting at recycle gas compressor.
In this way, can set up the pressure that reduces a little in swivelling pipe, the air-flow of the swivelling pipe of promptly flowing through pressure when leaving swivelling pipe can be lower than the environmental pressure of swivelling pipe.This measure helps also to guarantee that the atmosphere in the swivelling pipe do not escape to the outside.Yet, also can in swivelling pipe, set up with respect to environmental pressure just over atmospheric pressure.Be in close proximity to from the pressure in the outlet downstream of the air-flow of swivelling pipe often for being higher than 1.0 millibars of external pressures to the value that is lower than 1.2 millibars of external pressures, the pressure of the air-flow of the swivelling pipe of promptly flowing through can be lower than the environmental pressure of swivelling pipe when leaving swivelling pipe.This is preferred according to the present invention.
Pressure in the swivelling pipe should be determined according to the pressure of measuring with pressure sensor.Suitable pressure sensor has, and for example, comes from Hartmann ﹠amp; The AMD 220 type sensors of Braun, it is according to pressure converter (film measuring unit) operate.As pressure sensor 16 being arranged at the downstream of next-door neighbour, then be favourable with regard to application technology from the outlet of the air-flow of swivelling pipe.Can there be other pressure sensor in the upstream that enters the inlet of swivelling pipe at air-flow.This also can be single pressure sensor.Can determine pressure by pressure sensor 16, the operate together of discharging air compressor 17 (on the direction of control valve air-breathing fan), recycle gas compressor and virgin gas charging then.With steady state operation (if or use non-controlled compressor), then control valve 14 is unique pressure regulation devices as two compressors and virgin gas charging.
The speed of the air-flow by swivelling pipe is generally 〉=0.1 meter per second and≤2 meter per seconds.
According to the present invention, should be by heat the material the swivelling pipe from the external heat swivelling pipe.By and large, this heating can realize by directly firing, and its hot burning gas is carried (for example carrying by fan) around the swivelling pipe that is surrounded by shell burner promptly is installed below swivelling pipe.
But swivelling pipe is preferably had shell (for example, the positive parallelepiped) encirclement of electric heating assembly (resistance heated) by the inboard.In order to make temperature even, shell should have this heating component to being less than on the two opposite sides.But preferred heating component surrounds all sides of swivelling pipe.It is usually apart from 10 to 20 centimetres of the outer surfaces of swivelling pipe.In the specific embodiments that (Fig. 1) illustrates for example, swivelling pipe rotates freely in positive parallelepiped 2, this positive parallelepiped 2 has four isometric electrical heating (resistance heated) thermals treatment zone continuous on swivelling pipe length, each thermal treatment zone surround rotary tube furnace around.Each thermal treatment zone can be heated to temperature from room temperature to 850 ℃ with rotating pipeline section accordingly.The maximum heating power of each thermal treatment zone is 30kW.Distance between electrical heating district and the swivelling pipe outer surface is about 10 centimetres.In beginning place and terminal, swivelling pipe stretches out about 30 centimetres from positive parallelepiped.
In addition, heater 10 provide the air-flow that will enter in the swivelling pipe to be heated to preferred temperature before in entering swivelling pipe (for example, the preferred temperature of the material to the swivelling pipe therefore) possibility can keep the constant temperature that is present in the material in the rotary tube furnace.If the heat-producing chemical reaction in the precursor material is followed in the heat treatment of precursor material, then according to the present invention, entering air-flow in the swivelling pipe is preferably in and is lower than under the temperature of the desired temperature of material in (for example, 50 ℃ at the most, often at the most 20 ℃) rotary tube furnace and add in the swivelling pipe.On the other hand, follow endothermic chemical reaction in the precursor material as the heat treatment of precursor material,, enter air-flow in the swivelling pipe and be preferably in and (for example be higher than then according to the present invention, 50 ℃ at the most, often at the most 20 ℃) add in the swivelling pipe under the temperature of the desired temperature of material in the rotary tube furnace.
By and large, heater 10 can be the heater of any kind of.For example, it can be indirect heat exchanger.This heater also can be used as condenser (by changing the temperature of heat medium, for example, using refrigerated brine) in principle.Heater also can heat by direct or indirect burning in principle.Directly or indirectly the steam heating also is suitable.Under the situation of open steam heating, circulating gas pipe should be followed the tracks of heating at least in part, do not condense with the desirable of steam that suppresses to be contained in the air-flow, or if desired, by condensation steam is isolated especially.Often make air communication cross electric heater on electrical heating (resistance heated) metal wire.In illustrational specific embodiments, the use peak power is 1 * 50 kilowatt+1 * 30 kilowatt the 97D that comes from Schniewindt KG (58805 Neuerade, Germany) 80 type CSN continuous flow heaters.
The heating of rotary tube furnace and the heating that enters the air-flow in the swivelling pipe are preferably all controlled by the temperature of material in the swivelling pipe.This is usually by the thermocouple measurement that stretches in the material.For this reason, in illustrational specific embodiments, with lance shape thing 8 (having three thermocouples 9 on it) with in the vertical transfer material in 800 millimeters interval) be installed on the central shaft of swivelling pipe.The arithmetic mean of instantaneous value of three electric thermo-couple temperatures is regarded as the temperature of material.In the material in being present in swivelling pipe, according to the present invention, two maximum deviations of measuring temperature should be lower than 30 ℃, preferably are lower than 20 ℃, especially preferably are lower than 10 ℃, very particularly preferably are lower than 5 or 3 ℃.
In this novel method, heat treatment is carried out under 100 to 1100 ℃ or 200 to 800 ℃ through being everlasting.When catalytic active material is the multielement oxide material, for example, during polymetal oxide materials, this is a particularly suitable.
Under with the situation of multielement oxide material as catalytic active material, this novel method preferably carries out (aforementioned temperature is the based material temperature all the time) under 600 to 800 ℃ or 300 to 600 ℃.
Catalytic active material usually thus novel method make.
In novel method, be present in the temperature speed that the precursor material in the swivelling pipe heats for the heat treatment purpose to be generally≤10 ℃/minute.Temperature speed is≤8 ℃/minute often, be generally≤5 ℃/minute or≤3 ℃/minute, and it typically is≤2 ℃/minute or≤1 ℃/minute.Yet this temperature speed is generally 〉=0.1 ℃/minute, is generally 〉=0.2 ℃/minute, often be 〉=0.3 ℃/minute or 〉=0.4 ℃/minute.
As previously mentioned, heat-producing chemical reaction is often followed in the heat treatment of the precursor material of catalytic active material, and the component of the air-flow by swivelling pipe also often participates in this reaction.
To this novel method, because uncontrolled process can cause excessive heat to produce and the uncontrolled temperature of heat treatment material rises, the character deterioration that causes active material the most at last, thereby, importantly this chemical reaction does not carry out in uncontrolled mode, and will be removed apace by the heat that chemical reaction discharges.
If desired, in order in time to resist this uncontrolled process of material heat treatment, be applicable to that the swivelling pipe device of this novel method preferably has the device of quick cooling usefulness.This can for example carry out with following special effective and efficient manner: the shell (the positive parallelepiped in particular exemplary embodiments) around swivelling pipe has mouthful (longest dimension is generally 60 centimetres) or a hole in a side (for example in the bottom), surrounding air or before can be (for example by fan 5 through the air of cooling, come from the E 315/40-63 type of VentappGmbH) from described mouthful or hole suction, and can discharge by another (relatively) side (for example on top) that is present in shell and the flap 7 with adjustable mouth.Often the swivelling pipe heating is turned off simultaneously.This quick cooling can also stop heat treatment in the very correct time, therefore prevents excessive heat treatment.Another kind of measure is can be with its cooling (in heater 10) before air-flow is conducted to swivelling pipe.
Fast cooling can, for example when the heat treatment of precursor material finishes, in≤5 hours, be generally≤4 hours, often for≤2 hours during in, make the temperature that is present in the material in the swivelling pipe reduce at least 300 ℃.Yet this cooling period was not less than 0.5 hour usually.
As virgin gas is metered in the circulating air part 19 of recirculation, then is favourable with regard to application technology between pressure reducer 15 and heater 10 in fact.As particular exemplary embodiments shown in Figure 1, usually virgin gas basic load (for example, nitrogen 20) is metered into.Utilize at least one current divider, just can respond the measured value of used various component sensors, and the careful component content that is conducted to the air-flow in the swivelling pipe of adjusting.In particular exemplary embodiments, this is the nitrogen/air diverter 21 of response lambda sensor measured value.
Utilize these sensors, can measure the reducibility gas composition every now and then, such as NH
3, CO, NO, N
2O, acetate or aerosol (for example, ammonium acetate), and oxidizing component are such as NO
2And O
2, their content usually must be in narrow especially limit.
In particular exemplary embodiments, two sensors 18 have been installed, promptly one is used to measure ammonia content, and one is used to measure oxygen content.Ammoniacal sensor is general preferred to be operated according to optical measurement principle (absorption of special wavelength light and the ammonia content of gas are proportional).In particular exemplary embodiments, it is to come from Perkin ﹠amp; The MCS 100 type devices of Elmer.On the other hand, lambda sensor is generally based on paramagnetic property of oxygen matter.In particular exemplary embodiments, should use the Oxymat MAT SF 7MB 1010-2CA01-1AA1-Z type Oximat that comes from Siemens as lambda sensor.
Under the situation that is catalytic poly-metal deoxide active material, in this novel heat treated process, by precursor material be converted into catalytic active material during often from swivelling pipe, absorb oxygen in the atmosphere commonly used.By being installed on the upstream that enters the air flow inlet in the swivelling pipe and coming from the lambda sensor in downstream of the air stream outlet of swivelling pipe, but real-time quantitative detects oxygen to be absorbed, and can correspondingly change the oxygen supply (as not changing oxygen supply, the oxygen that then will be conducted to usually in the air-flow that adds swivelling pipe keeps constant in fact) in the air-flow of the swivelling pipe of flowing through.Therefore can avoid the peroxidating or oxygen debtization of active material, therefore improve catalyst performance.It also can carry out with like the reducibility gas composition complete class.
Change into oxidisability when (or on the contrary) from reproducibility when the character of atmosphere commonly used in the swivelling pipe in heat treatment process, this novel circulating air program also proves particularly advantageous in this article.This program in fact really simply mode carry out this and change, thereby the atmosphere in the swivelling pipe is in outside the explosive range all the time.
In the test of novel method, often find that gas composition sensor indicates incorrect value.
This situation has been carried out very careful research, find that this is because the air-flow of the swivelling pipe of flowing through is generally also emitted the very thin dust that is derived from heat treated precursor material, and it is deposited on sensor surface (sensor is generally operated in the mode that sucks a part from air-flow), makes mistakes thereby make to measure.It only use the filter that is installed in the sensor upstream can't overcome this problem, because through blocking after a while, also can make measurement result make mistakes.
The suitable way of head it off is that the upstream of sensor (but) installs cyclone cluster 12 in the downstream of the air stream outlet by swivelling pipe, being gone out by air-flow entrained solid particle separation.Whizzer is by the solid particle of acting in conjunction separate out suspended in gas phase of centrifugal force and gravity; Centrifugal force with the air-flow of eddy current form rotation has quickened the sedimentation of suspended particulate.
Use this cyclone cluster can prevent that also very thin dirt powder is deposited on the wall of circulating gas pipe simultaneously.The deposition of this very thin dirt powder will have significant detrimental effect, for example under the situation that product changes; If promptly heat treated precursor material changes, when previous treated precursor material dirt powder was deposited on the wall, in the process that circulating air passes through, material afterwards can be contaminated; Moreover very thin dirt powder can damage (changing the heat conduction) or block heater 10.
The solid that is deposited in the cyclone cluster is thrown aside.
Because of pressure drop that cyclone cluster produced is compensated by recycle gas compressor.
Also can use any other to be applicable to that the device that separates trickle solid from the gaseous state decentralized photo replaces cyclone cluster in principle.
The circulating air part 22 (discharge gas) of discharging often comprises such as NO
x, CO, acetate, NH
3Or the like gas, therefore it is overall safety not, in discharging gas purification devices 23 these gases is separated usually.
For this reason, generally make discharge gas by scrubbing tower (it comes down to not contain the tower of internals, and comprises the filler with centrifugation in the outlet front) earlier; Discharge the spraying of gas and water-based in the same way or inversely by (having two opposite nozzles of sprinkling direction).
After leaving scrubbing tower, discharge gas and should be conducted in the device (it is generally a branch of tubular filter) that comprises thin dirt powder filter, discharge gas and pass from its inside.Being preferably in muffle furnace at last burns.
In this novel method, be Based Quality flow measurement principle, be particularly suitable for adjusting the total amount of the air-flow that passes through swivelling pipe except that sealing gas based on the principle of the orifice plate measuring principle of pressure reduction and thermal convection current with Coriolis (Coriolis) power.
In particular exemplary embodiments, the Department of Survey of the throughput that is conducted to swivelling pipe except that sealing gas utilizes and comes from KURZ Instruments, Inc., the 455Jr type sensor 28 of Montery (USA) carries out (measuring principle: based on thermal convection current and use the mass flow measurement of isothermal airspeedometer).
But described rotary tube type furnace apparatus continued operation and batch operation.According to the present invention, preferred batch operation.In continued operation, material and gas phase be the reverse rotary tube furnace that passes through preferably.For example, the polymetal oxide materials of DE-A19855913 or WO 02/24620 and prepare required preformed phase (for example, bismuth tungstate and bismuth molybdate) can be by in rotary tube furnace, precursor material being carried out continuous heat and make in the mode of excellence.
Therefore, the rotary tube type furnace apparatus that comprises following assembly is particularly useful for carrying out this novel method:
A) at least one recycle gas compressor 13;
B) at least one discharges air compressor 17;
C) at least one pressure reducer 15;
D) at least one virgin gas charging (20,21);
E) at least one heatable swivelling pipe 1; And
F) at least one circulating gas pipe.
As use nonadjustable compressor 13 and 17, then rotary tube type furnace apparatus also comprises at least one control valve 14.
In addition, favourable specific embodiments also comprises at least one heater 10 according to the present invention.
The specific embodiment very particularly preferably comprises that also at least one is integrated cyclone cluster.
In addition, will be favourable if rotary tube type furnace apparatus comprises the device that cools off fast.
If wish that also the air-flow that rotary tube type furnace apparatus is used for material is carried out wherein by swivelling pipe also can not be the heat treatment that circulates at least pro rata, then advantageously cyclone cluster 12 can be connected with recycle gas compressor 13, and air-flow directly can be conducted to and discharge gas purification devices 23 according to triple valve principle 26.In the case, also can be connected to according to the triple valve principle and discharge the gas purification devices, this connection is positioned at the downstream of recycle gas compressor.Mainly comprise air as air-flow, then it is to suck (27) by recycle gas compressor 13 in the case.Also can be connected to cyclone cluster according to the triple valve principle.In this way, air-flow preferably sucks through swivelling pipe, thereby makes the internal pressure of swivelling pipe be lower than environmental pressure.
More than handle and preferably under the situation of material and air-flow reverse flow, carry out continuously, be about to heat treated material and introduce in the rotary tube furnace, and from rotary tube furnace, discharge in the opposite end of air-flow in the opposite end of air-flow (at the peak of swivelling pipe).
In the particular exemplary embodiments of swivelling pipe device, in continued operation, preferably will be made as at the pressure in the downstream that (air-flow) swivelling pipe exports than low 0.8 millibar of external pressure.In batch operation, identical pressure is set at low 0.2 millibar.
As previously mentioned, this novel method is suitable for the precursor material of all types of catalytic active materials is heat-treated.Precursor material can powder type or is carried out this novel heat treatment with the form of special (catalyst) mechanograph.
For example, it is applicable to preparation containing element Nb and at least a and elements Mo of W and the catalytic activity multielement oxide material of V, total amount in the outer all elements of the deoxygenation in the catalytic activity multielement oxide material, the molar ratio of elements Mo is 20 to 80 moles of %, be contained in Mo and the mol ratio that is contained in the V in the catalytic activity multielement oxide material in the catalytic activity multielement oxide material, Mo/V, be 15: 1 to 1: 1, and corresponding mol ratio Mo/ (total amount of W and Nb) it is 80: 1 to 1: 4.This multielement oxide material often also comprises Cu, and the corresponding mol ratio of Mo/Cu is 30: 1 to 1: 3.The heat treated temperature range of precursor material is generally 300 to 600 ℃.The example of this multielement oxide material of reference is illustrated in down the various advantages of this novel method once more.It can for example followingly make: also comprise the tight dried blend (precursor material) of ammonium ion by comprising the initial compounds preparation of the outer elemental composition of multielement oxide material deoxygenation as component, and make this dried blend in containing O
2And NH
3Atmosphere under 300 to 450 ℃ (material temperature), heat-treat.According to EP-B 72448, the atmosphere system in wherein heat-treating for example, comprises the atmosphere of following ingredients:
-in heat treatment process in the O of each time point from 0.5 to 4 volume %
2,
-at the heat treated whole period average of the reproducibility NH that is 1 to 8 volume %
3,
The steam of-its surplus and/or inert gas,
The NH of atmosphere in heat treatment process
3Content is through being lower than the maximum of 20 volume %.
Aforementioned multielement oxide material except element nb and/or W, and Mo, V and the Cu when needing, also can comprise, for example, element T a, Cr, Ce, Ni, Co, Fe, Mn, Zn, Sb, Bi, alkali metal (Li, Na, K, Rb, Cs), H, alkaline-earth metal (Mg, Ca, Sr, Ba), Si, Al, Ti and Zr.But the multielement oxide material certainly also can be only by element nb and/or W and Mo, V and the Cu when needing form.It especially is suitable as the activity of such catalysts material of methacrylaldehyde to the incomplete gaseous oxidation of acrylic acid heterogeneous catalysis.
Be particularly suitable as methacrylaldehyde to the catalytic activity multielement oxide material of the used active material of the incomplete gas-phase oxidation catalyst of acrylic acid heterogeneous catalysis and meet following stoichiometry general formula I:
Mo
12V
aX
1 bX
2 cX
3 dX
4 eX
5 fX
6 gO
n (I)，
Wherein
X
1Be W, Nb, Ta, Cr and/or Ce,
X
2Be Cu, Ni, Co, Fe, Mn and/or Zn,
X
3Be Sb and/or Bi,
X
4Be one or more alkali metal (Li, Na, K, Rb, Cs) and/or H,
X
5Be one or more alkaline-earth metal (Mg, Ca, Sr, Ba),
X
6Be Si, Al, Ti and/or Zr,
A is 1 to 6,
B is 0.2 to 4,
C is 0 to 18, and is preferred 0.5 to 18,
D is 0 to 40,
E is 0 to 2,
F is 0 to 4,
G be 0 to 40 and
N is by the valence state of the outer element of the deoxygenation among the I and the number that frequency (frequency) is determined, and
Wherein variable is selected in particular range, condition is the total amount in the outer all elements of deoxygenation in the multielement oxide material (I), the molar ratio of elements Mo is 20 to 80 moles of %, be contained in Mo and the mol ratio that is contained in the V in the catalytic activity multielement oxide material (I) in the catalytic activity multielement oxide material (I), Mo/V, it is 15: 1 to 1: 1, and corresponding mol ratio Mo/ (total amount of W and Nb) be 80: 1 to 1: 4 (and if the multielement oxide material comprise Cu, then corresponding mol ratio Mo/Cu is 30: 1 to 1: 3).
Preferred person in the activation multielement oxide material (I) is following material:
X
1Be W, Nb and/or Cr,
X
2Be Cu, Ni, Co and/or Fe,
X
3Be Sb,
X
4Be Na and/or K,
X
5Be Ca, Sr and/or Ba,
X
6Be Si, Al and/or Ti,
A is 2.5 to 5,
B is 0.5 to 2,
C is 0.5 to 3,
D is 0 to 2,
E is 0 to 0.2,
F is 0 to 1,
G be 0 to 15 and
N system is by the valence state of the outer element of deoxygenation among the I and the number of frequency decision.
Yet following multielement oxide active material II is the particularly preferred direct product of novel method:
Mo
12V
aX
1 bX
2 cX
5 fX
6 gO
n (II)，
Wherein
X
1Be W and/or Nb,
X
2Be Cu and/or Ni,
X
5Be Co and/or Sr,
X
6Be Si and/or Al,
A is 3 to 4.5,
B is 1 to 1.5,
C is 0.75 to 2.5,
F is 0 to 0.5,
G is 0 to 8 He
N is the number by the valence state of the outer element of deoxygenation among the II and frequency decision, and
Wherein variable is selected in particular range, its condition is the total amount in the outer all elements of deoxygenation in the multielement oxide active material (II), the molar ratio of elements Mo is 20 to 80 moles of %, be contained in Mo and the mol ratio that is contained in the V in the catalytic activity multielement oxide material (II) in the catalytic activity multielement oxide material (II), Mo/V, it is 15: 1 to 1: 1, corresponding mol ratio Mo/Cu is 30: 1 to 1: 3, and corresponding mol ratio Mo/ (total amount of W and Nb) is 80: 1 to 1: 4.
As mentioned above, use the raw material of the known suitable source (initial compounds) of the outer elemental composition (they have each desirable stoichiometric proportion in multielement oxide active material) of the deoxygenation of required multielement oxide active material as this multielement oxide material of preparation, and through heat treatment very closely by the preferred trickle dried blend of this source preparation, and then carry out the heat place, this close thermal is handled and can be carried out before or after (catalyst) mechanograph that is configured as geometry in particular.According to the present invention, this heat treatment is preferably carried out in advance.The source can be an oxide, also can be by heat the compound that changes oxide at least in the presence of oxygen.Therefore, except oxide, suitable especially initial compounds has halide, nitrate, formates, oxalates, acetate, carbonate or hydroxide.
The suitable initial compounds of Mo, V, W and Nb also can be its oxo-compound (molybdate, vanadate, tungstates and niobates) or by its acid of deriving.Oxygen containing source is favourable equally.
In the dried closely blend the desirable content of ammonium ion simply mode add in the tight dried blend by ammonium ion and obtain respective amount.Can be for example advantageously by using relevant oxometallic acid ammonium ammonium ion to be introduced in the dried closely blend as the source of elements Mo, V, W or Nb.Its example has inclined to one side niobic acid ammonium, ammonium metavanadate, four hydration ammonium heptamolybdates and seven hydration ammonium paratungstates.But can certainly be independent of the required initial compounds in source, with the ammonium donor, such as NH as multielement oxide active material component
4NO
3, or NH
4Cl or ammonium acetate or ammonium carbonate or carbonic hydroammonium or NH
4OH or NH
4CHO
2, or ammonium oxalate, add in the tight dried blend to be heated.
Can dry state on the thorough mixed principle of initial compounds or hygrometric state carry out.As carrying out with dry state, then initial compounds should use with the form of fine-powder, and after mixing, for example, and compacting (for example, film-making) and obtain (catalyst) mechanograph with desirable geometry, and then carry out novel heat treatment.
Preferably carry out but thoroughly mix with hygrometric state.Initial compounds is mixed with each other with the form of the aqueous solution and/or suspension.When only using the source that exists with dissolved form and initial compounds, obtain exceptionally close dried blend by described mixed method as raw material.The preferred solvent that uses is water.Then with water-based material (solution or suspension) drying, and if desired, directly the tight dried blend that makes is like this heat-treated.Drying program preferably carries out (outlet temperature is generally 100 to 150 ℃) by spray-drying, and carries out immediately after the preparation aqueous solution or suspension.The gained powder can be directly molded by compacting.Yet it is too trickle usually and can't directly further process, and therefore, for example should add water then and mediates.Adding rudimentary organic carboxyl acid (for example, acetate) in kneading process also is favourable usually, is benchmark with used dusty material, and typical addition is 5 to 10 weight %.
Then can be with the material forming of obtain obtaining desirable geometry through mediating, drying, and then heat-treat (generation unsupported catalyst); Also can only extrudate be made in its shaping, this extrudate is heat-treated, and then grind into powder (usually≤80 microns), this powder is coated on the inert carrier as moist material after adding low amounts of water and optionally further adding conventional adhesive usually.After coating is finished, carry out drying once more, make ready-to-use coated catalysts thus.Thorough mixed stocker as initial compounds carries out with the form of solution (for example aqueous solution), then also inert porous carrier can be heat-treated with this solution impregnation, drying and then according to the present invention, obtains carried catalyst.In the preparation of coated catalysts, the coating of carrier also can for example utilize moist spray-dried powders to carry out before heat treatment.
The carrier material that is applicable to coated catalysts has, and for example, porous or non-porous aluminas, silica, thorium anhydride, zirconium dioxide, carborundum or silicate are such as magnesium silicate or alumina silicate (for example, coming from the steatite of C 220 types of Ceram Tec).
Carrier can have rule or irregular shape, the carrier with regular shape and obvious surface roughness, and for example, spheroid or hollow circular cylinder with fragment coating are preferred.
Using diameter is that 1 to 8 millimeter, the spherical pieces talcum carrier (for example, coming from the steatite of C 220 types of Ceram Tec) of preferred 4 to the 5 millimeters basic atresia with rough surface are suitable.But 2 to 10 millimeters of length of use, external diameter are that 4 to 10 millimeters cylinder also is suitable as carrier.In addition, if annular carrier, then wall thickness is generally 1 to 4 millimeter.The annular carrier that can preferably use has 2 to 6 millimeters length, 4 to 8 millimeters external diameter and 1 to 2 millimeter wall thickness.Ring with size 7 millimeters * 3 millimeters * 4 millimeters (external diameter * length * internal diameter) is also suitable especially as carrier.
As described in for example DE-A 2909671, EP-A 293859 or EP-A 714700, generally in rotatable container, use the trickle multielement oxide active material that can be in this way makes by heat treatment or use its still pending heat treated trickle precursor material (tight dried blend) coating carrier.The program of EP-A 714700 is preferred.
Be the coating carrier, should carrier is wetting with dusty material to be coated.After the coating, utilize hot-air to carry out drying usually.The coating layer thickness that is applied to the dusty material of carrier is preferably 10 to 1000 microns, and preferred 50 to 500 microns, special 150 to 250 microns.
If unsupported catalyst as previously mentioned, is shaped and also can carries out before or after heat treatment.
For example, unsupported catalyst can be by multielement oxide active material or its still pending heat treated precursor material (tight dried blend) preparation of the powder type that can make according to the present invention, (for example obtain desirable catalyst geometry by compacting, by film-making or extrude), if need, can add auxiliary agent, for example, as graphite or stearic acid and/or the shaping assistant and the reinforcing agent of lubricant, such as microfibre, asbestos, carborundum or the potassium titanate of glass.The suitable geometry of unsupported catalyst has, and for example, has from 2 to 10 millimeters the external diameter and the solid cylinder or the hollow circular cylinder of length.If hollow circular cylinder, 1 to 3 millimeter wall thickness is favourable.Certainly, unsupported catalyst also can be spherical, and sphere diameter can be 2 to 10 millimeters.
Certainly, relevant multielement oxide active material also can powder type, and promptly unshaped is the specific catalyst geometry, with acting on the catalyst (for example, also being used for fluid bed) of methacrylaldehyde to acrylic acid heterogeneous catalysis incomplete oxidation.
Methacrylaldehyde to acrylic acid incomplete gaseous oxidation effect for example itself can use EP-A 724481 or DE-A 19910508 described multielement oxide active materials to carry out.
About the heat treatment of the precursor material of aforementioned multielement oxide material, EP-B 724481 points out (the 5th page, the 25th row and following):
" according to calcination atmosphere required for the present invention simply mode obtain, for example, have about O
2, NH
3And calcine in the stove that therefrom passes through of the admixture of gas of the corresponding composition of inert gas/steam.In less preferred specific embodiments, the required average ammonia content of calcination atmosphere also can add in the dry substance to be calcined by the ammonium ion with respective amount and obtains, and this ion decomposes in calcination process, emits NH
3".
Calcining among the EP-B 724481 is carried out in air circulating oven, wherein especially will comprise the NH of designated volume ratio
3The admixture of gas of (volume %) is conducted to this stove.
By the invention as the application basis, the less preferred specific embodiments of EP-B 724481 is ready-made to be preferred specific embodiments.This is particularly because novel method no longer needs to add external NH in calcination atmosphere
3, but because the passing through of circulating air, to be contained in ammonium ion in the precursor material to be heated as the ammonia source.Another advantage is, because the passing through of circulating air, the method for present patent application has further been utilized and has been contained in the energy in the circulating air and reduced heat treated energy requirement.In addition and since in the swivelling pipe continuously from the homogenize bed, thereby this novel method can prepare in a large number be prepared into batch in have narrow especially activity distribution catalytic active material (especially catalytic activity multielement oxide material).If described catalytic activity multielement oxide material at least a and elements Mo, V and Cu is to prepare methacrylaldehyde to the used catalyst of the incomplete gaseous oxidation of acrylic acid heterogeneous catalysis in order to be used among containing element Nb and the W, particularly when this gas phase incomplete oxidation be when as described in for example DE-A10307983, DE-A 19948523 and DE-A 19910508, under high methacrylaldehyde load, carrying out, this is a particular importance.
Generally speaking, the gas phase incomplete oxidation of this methacrylaldehyde in fact is to carry out in having the bundled tube reactor of one or more humidity provinces, described in for example EP-A 700714, EP-A 700893, DE-A19910508, DE-A 19948523, DE-A 19910506, DE-A 19948241, DE-C2830765, DE-C 2513405, US-A 3147084, DE-A 2201528, EP-A 383224 and DE-A 2903218.
Solid catalyst bed is present in the metal tube (catalyst) of bundled tube reactor, and heat medium passes through around metal tube.Surpass one humidity province if having, then the heat medium that separates on the space of respective number passes through around metal tube.Heat medium is generally molten salt bath.Reactant mixture passes through catalyst tube.
Catalyst tube is made by ferritic steel usually, and has 1 to 3 millimeter wall thickness usually.Its internal diameter is generally 20 to 30 millimeters, often is 21 to 26 millimeters.Its length is preferably 2 to 4 meters.
With regard to application technology, the number that is loaded on the catalyst tube in the bundled tube container is preferably at least 5000, and preferably at least 10000.The number that is loaded on the catalyst tube in the reactor vessel often is 15000 to 30000.Usually get rid of and have the bundled tube reactor that surpasses 40000 catalyst tubes.Catalyst tube is distributed in the container (preferably each catalyst tube has 6 equidistant adjacent tubes) usually equably, distribution should suitably be selected, make adjacent catalyst tube in distance (be catalyst tube at interval) between the intracardiac axle be 35 to 45 millimeters (referring to for example EP-B 468290).
The melt that uses salt (as potassium nitrate, potassium nitrite, natrium nitrosum and/or sodium nitrate) or have an alloy of low-melting metal (as sodium, mercury) and different metal is particularly advantageous as heat exchange medium.
Though with regard to reactor region, generally can guarantee that identical salt temperature acts on each catalyst tube, in fact can't avoid on reactor cross section, existing thermograde fully by flox condition suitable in the bundled tube reactor.As be attended by the remarkable activity gradient on each catalyst tube load in addition in the thermograde on the reactor cross section, then can influence the handling safety of bundled tube reactor unfriendly, because in this case will remarkable difference by methacrylaldehyde in each catalyst tube of bundled tube reactor to the heat of acrylic acid heat release heterogeneous catalysis fixed bed incomplete oxidation generation.Because active increase of catalyst tube load meaning higher conversion ratio, and therefore under uniform temp, more how to produce a heat thereby a situation after will taking place in time per unit.
This novel method can make tool load regularly from the bundled tube reactor of 5000 to 40000 catalyst tubes, and (catalyst comprises described catalytic activity multielement oxide material as active material, this multielement oxide material contains at least a and elements Mo, the V of element nb and W and the C when needing), when randomly drawing 12 catalyst tube rule samples, difference between active arithmetic mean of instantaneous value and the highest or the lowest activity is not more than 8 ℃, often be not more than 6 ℃, usually be not more than 4 ℃, and under favourable situation, be not more than 2 ℃.
About novel method, it should be noted that if being contained in all active materials in the bundled tube reactor is to be lower than 100 or be lower than 75 or be lower than preparation in 50 batches in that precursor material is heat treated, then also can obtain above result.The number of these batches often is 5 to 40.
Use temperature that the salt bath (mixture of the sodium nitrate of the natrium nitrosum of the potassium nitrate of 53 weight %, 40 weight % and 11 weight %) that flows around each catalyst tube must have measuring as the activity of catalyst tube load, make the reaction gas mixtures of nitrogen of the steam of oxygen, 10 volume % of the methacrylaldehyde comprise 4.8 volume %, 7 volume % and 78.2 volume % per hour in the one way of catalyst loading space velocity by the catalyst tube that loads of 85 liters of (S.T.P.) methacrylaldehyde, obtain the acrolein conversion rate of 97 moles of % with every liter of catalyst loading.The number that rises of catalyst loading does not comprise the volume of preliminary or follow-up bed in catalyst tube that only has inert material, and only comprises the bed volume that comprises catalyst mechanograph (if desired, available inert material dilution).
When bundled tube reactor 〉=135 or 〉=150 or 〉=160 or 〉=170 or 〉=180 or 〉=200 or 〉=220 or 〉=when operating under the methacrylaldehyde space velocity of the catalyst loading of 240 liters of (S.T.P.) every liter per hours, the load of catalyst tube is even more important in the bundled tube reactor that can reach in this way.Certainly, this catalyst loading also is favourable under the lower situation of methacrylaldehyde space velocity.
Yet the methacrylaldehyde space velocity of catalyst loading is generally≤350 or≤300 or≤250 liters of (S.T.P.) every liter per hours.
Perhaps, carrying out methacrylaldehyde to the bundled tube reactor of acrylic acid incomplete oxidation can operate described in DE-A10307983, DE-A 19948523 and DE-A 19910508.
At last, also it should be noted that novel method simply mode make precursor material in rotary tube furnace the heat treated holdup time for 〉=5 hours or 〉=10 hours or 〉=15 hours or 〉=20 hours or 〉=25 hours.This holdup time is general≤and 50 hours.
Moreover, it should be noted that, this novel method especially also is applicable to preparation containing element Mo, V, two element T e and Sb's is at least a, and is selected from the multielement oxide active material of at least a element of the group of being made up of together Nb, Pb, Ta, W, Ti, Al, Zr, Cr, Mn, Ga, Fe, Ru, Co, Rh, Ni, Pd, Pt, La, Bi, B, Ce, Sn, Zn, Si, Na, Li, K, Mg, Ag, Au and In.
Heat treatment is often being carried out under 150 to 350 ℃, under preferred 250 to 350 ℃ in oxidisability (the containing oxygen) atmosphere (for example, air) at the beginning, then under the situation that does not have oxygen (for example at N
2In) under 350 to 1000 ℃ or 400 to 700 ℃ or 400 to 650 ℃, carry out.Aerial heat treatment also can be carried out continuously.
Combination preferably comprises element nb, Ta, W and/or the Ti from last group element, special preferred elements Nb.
Relevant multielement oxide active material preferably comprises the aforementioned elements combination of stoichiometry III:
Mo
1V
bM
1 cM
2 d (III)，
Wherein
M
1Be Te and/or Sb,
M
2System is selected from least a element of the group of being made up of Nb, Ta, W, Ti, Al, Zr, Cr, Mn, Ga, Fe, Ru, Co, Rh, Ni, Pd, Pt, La, Bi, Ce, Sn, Zn, Si, Na, Li, K, Mg, Ag, Au and In,
B is 0.01 to 1,
C be＞0 to 1 and
D is＞0 to 1.
Preferred M
1Be Te and M
2Be Nb, Ta, W and/or Ti.M
2Be preferably Nb.
Stoichiometric coefficient b is preferably 0.1 to 0.6.Correspondingly, the preferable range of stoichiometric coefficient c is 0.01 to 1 or 0.05 to 0.4, and the favorable values of d is 0.01 to 1 or from 0.1 to 0.6.
If stoichiometric coefficient b, c and d in aforementioned preferable range, then are particularly advantageous simultaneously.
When active material about the first prime system outside the deoxygenation during by a kind of composition the in the aforementioned elements combination, above stated specification is especially suitable.
In this situation, they are the multielement oxide active material of stoichiometry IV particularly:
Mo
1V
bM
1 cM
2 dO
n (IV)，
Variable wherein has the illustrated meaning about stoichiometry III, and n the serve as reasons valence state of the outer element of deoxygenation in (IV) and the number that frequency determined.
In addition, this novel method preferably is suitable for being prepared as follows multielement oxide active material: perhaps comprise a kind of in the aforementioned elements combination, perhaps, about the outer element of deoxygenation, formed and had the x-ray diffraction pattern that presents reflection h and i simultaneously by them, wherein the peak of h and i is in 22.2 ± 0.5 ° of the angles of diffraction (2 θ) (h) and 27.3 ± 0.5 ° (i).All relate to the data of x-ray diffraction pattern all based on the x-ray diffraction pattern that uses CuK α radiation to be produced herein, Siemens diffractometer Theta-ThetaD-5000, tube voltage: 40 kilovolts, tube current: 40 milliamperes, aperture V20 (variable), collimator V20 (variable), 0.1 millimeter in the second monochromator aperture, (2 θ) at interval measured: 0.02 ° in 0.6 millimeter in detector aperture, the Measuring Time in per step: 2.4 seconds, detector: scintillation counter.
Overall with in half eminence of these reflections can be very little or very obvious.
This novel method is particularly suited for preparing its x-ray diffraction pattern and also has the aforementioned multielement oxide active material of peak at the reflection k of 28.2 ± 0.5 ° (k) except reflection h, i.
Among the latter for preparation according to the present invention preferably wherein reflect h be in the x-ray diffraction pattern intensity maximum and be not more than those of 0.5 ° in the overall with of half eminence, and this novel method be specially adapted to reflect i and reflection k half eminence overall with simultaneously≤the intensity P of 1 ° and reflection k
kIntensity P with reflection i
iSatisfy and concern 0.2≤R≤0.85, preferred 0.3≤R≤0.85, preferred 0.4≤R≤0.85, preferred especially 0.65≤R≤0.85 even more preferably 0.67≤R≤0.75, and the material of R=0.70 to 0.75 or R=0.72 very particularly preferably, wherein R is by the defined strength ratio of following formula:
R＝P
i/(P
i+P
k)。
Aforementioned x-ray diffraction pattern does not preferably have the reflection that maximum is positioned at 2 θ=50 ± 0.3 °.
In this article, in the x-ray diffraction pattern definition of reflected intensity based on DE-A 19835247 and DE-A 10122027 described and DE-A 10051419 and DE-A 10046672 described definition.This is equally applicable to half definition of highly locating overall with.
Except reflection h, i and k, the aforesaid x-ray diffraction pattern of the multielement oxide active material that can advantageously prepare according to the present invention comprises peak position other reflection in the following angle of diffraction (2 θ):
9.0±0.4°(l)
6.7 ± 0.4 ° (o) reaches
7.9±0.4°(p)。
It is then more favourable in the reflection of the angle of diffraction (2 θ)=45.2 ± 0.4 ° (q) to comprise peak position in addition as x-ray diffraction pattern.
X-ray diffraction pattern often also comprises 29.2 ± 0.4 ° (m) and 35.4 ± 0.4 ° (n) of reflection.
If the element combinations of Formulae II I and IV definition exists mutually with pure i then is more favourable.If the catalytic activity oxide material also comprises the k phase, then its x-ray diffraction pattern also comprises its peak position in the angle of diffraction (2 θ) 36.2 ± 0.4 ° (m) and other reflection of 50 ± 0.4 ° (used term i mutually with k mutually described in DE-A 10122027 and DE-A 10119933) herein except aforementioned reflection.
Being appointed as 100 as the intensity that will reflect h, then according to the present invention, will be favourable if reflection i, l, m, n, o, p and q have following intensity on the same intensity grade:
I: from 5 to 95, often being 5 to 80, is 10 to 60 sometimes;
L: from 1 to 30;
M: from 1 to 40;
N: from 1 to 40;
O: from 1 to 30;
P: from 1 to 30, and
Q: from 5 to 60.
Comprise any aforesaid extra reflection as x-ray diffraction pattern, then its partly highly locate overall with and be generally≤1 °.
The multielement oxide active material of Formula I V prepared in accordance with the present invention or the specific area of multielement oxide active material that comprises the element combinations of Formulae II I are generally 1 to 30 meters squared per gram (BET surface area, nitrogen), especially when its x-ray diffraction pattern has described form.
The preparation of the precursor material of the multielement oxide active material that can make in this way is presented in the prior art of quoting about this material.This especially comprises DE-A 10122027, DE-A10119933, DE-A 10033121, EP-A 1192987, DE-A 10029338, JP-A2000-143244, EP-A 962253, EP-A 895809, DE-A 19835247, WO 00/29105, WO 00/29106, EP-A 529853 and EP-A 608838.In all specific embodiments of two parts of documents in the end mentioning, use spray-drying as drying means; For example, inlet temperature is 300 to 350 ℃, and outlet temperature is 100 to 150 ℃; Reverse or in the same way.The heat-treat condition of these precursor materials is described in these documents equally.
But described multielement oxide active material former state (promptly with powder type) or after being configured as suitable geometry (referring to, for example, the geometry variation of the coated catalysts of DE-A 10051419 and DE-A10122027) be used for the gas phase catalysis incomplete oxidation and/or the ammoxidation of lower hydrocarbon and rudimentary organic compound (as propylene, propane and methacrylaldehyde).They are particularly useful for making methacrylaldehyde and/or acrylic acid and by propane and/or propylene production acrylonitrile.Reaction condition is contained in the prior art of being quoted from equally.
This novel method can make tool load regularly from the bundled tube reactor of 5000 to 40000 catalyst tubes, and (catalyst comprises described catalytic activity multielement oxide material as active material, this multielement oxide material contains elements Mo, V, at least a among two element T e and the Sb and being selected from by Nb, at least a element of the group that the combination of Ta etc. is formed), when randomly drawing 12 catalyst tube rule samples, difference between active arithmetic mean of instantaneous value and the highest or the lowest activity is not more than 8 ℃, often be not more than 6 ℃, usually be not more than 4 ℃, and under favourable situation, be not more than 2 ℃.
It is if being contained in all active materials in the bundled tube reactor is to be lower than 100 or be lower than 75 or be lower than preparation in 50 batches in that precursor material is heat treated that novel method merits attention part, then also can obtain above result.The number of these batches often is 5 to 40.
Use temperature that the salt bath (mixture of the sodium nitrate of the natrium nitrosum of the potassium nitrate of 53 weight %, 40 weight % and 11 weight %) that flows around each catalyst tube must have measuring as the activity of catalyst tube load, make the reaction gas mixtures of nitrogen of the steam of oxygen, 10 volume % of the methacrylaldehyde comprise 4.8 volume %, 7 volume % and 78.2 volume % per hour in the one way of catalyst loading space velocity by the catalyst tube that loads of 85 liters of (S.T.P.) methacrylaldehyde, obtain the acrolein conversion rate of 97 moles of % with every liter of catalyst loading.The number that rises of catalyst loading does not comprise the volume of preliminary or follow-up bed in catalyst tube that only has inert material, and only comprises the bed volume that comprises catalyst mechanograph (if desired, available inert material dilution).
When bundled tube reactor 〉=135 or 〉=150 or 〉=170 or 〉=180 or 〉=200 or 〉=220 or 〉=when operating under the methacrylaldehyde space velocity of the catalyst loading of 240 liters of (S.T.P.) every liter per hours, this load of catalyst tube is even more important.It is generally≤350 or≤300 or≤250 liters of (S.T.P.) every liter per hours.
Embodiment
A) be used for manufacturing chemistry metering Mo
12V
3W
1.2Cu
2.4O
XThe preparation of precursor material of multielement oxide material
With 16.3 kilograms of hydrated copper acetates (II) (content: the CuO of 40.0 weight %) under agitation be dissolved in 274 liters the water at 25 ℃.Obtain settled solution 1.
The space is heated to 40 ℃ with 614 premium on currency independently therewith, and with 73 kilogram of four hydration ammonium heptamolybdate (MoO of 81.5 weight %
3) stirring adding, simultaneous temperature remains on 40 ℃., during time of 30 minute be heated to 90 ℃, stir simultaneously, keep this temperature, 11.3 kilograms of ammonium metavanadates and 10.7 kilogram of seven hydration ammonium paratungstate (WO of 88.9 weight % thereafter
3) stir adding continuously and with described order.Obtain settled solution 2.
Make solution 2 be cooled to 80 ℃, then solution 1 is stirred in the adding solution 2.With 130 liters of concentration is the NH under 25 ℃ of 25 weight %
3The aqueous solution adds in the mixture of gained.Stir, produce settled solution, it temporarily has 65 ℃ temperature and 8.5 pH.Other 20 liters of water under 25 ℃ are added to this solution.Make the temperature of gained solution be increased to 80 ℃ once more, use the S-50-N/R type spray dryer come from Niro-Atomizer (Copenhagen) then this solution spray drying (gas access temperature: 350 ℃, gas outlet temperature: 110 ℃) thereafter.Spray-dried powder has 2 to 50 microns particle diameter.The spray-dried powders that 60 kilograms of these amounts are made is metered in the kneader of VM 160 types (sigma type oar) that come from AMK (Aachener Misch-und Knetmaschinen Fabrik), and add 5.5 liters of acetate (≈ 100 weight % concentration, glacial acetic acid) and 5.2 premium on currency and mediate (screw speed: 20rpm).Mediate after 4 to 5 minutes, add 6.5 premium on currency again, and continue the kneading program, till through 30 minutes (mediating about 40 to 50 ℃ of temperature).To through mediate material empty in extruder, and utilize extruder (to come from Bonnot Company (Ohio), type: G 103-10/D7A-572K (6 " extruder W Packer)) be configured as (length: 1-10 centimetre of extrudate thereafter; Diameter: 6 millimeters).Extrudate was descended dry 1 hour 120 ℃ (material temperature) on belt transmission.The extrudate of drying has formed according to the heat treated precursor material of this novel method.
B) in rotary tube type furnace apparatus, utilize novel heat treatment to prepare catalytic active material
Heat-treat in rotary tube type furnace apparatus shown in Figure 1, wherein size and additional device are as described in the particular exemplary embodiments in this paper explanation, and treatment conditions are as follows:
-heat treatment utilizes 300 kilograms according to A) in preparation described material carry out in batches;
-swivelling pipe is with respect to 0 ° of the inclination angle ≈ of level;
-swivelling pipe changes the clockwise rotation with per minute 1.5;
-in whole heat treatment process, make 205 cubic metres (S.T.P.)/hour air communication cross swivelling pipe, this air-flow (behind the air that comprises at first of displacement) has following composition, and its outlet of leaving swivelling pipe further replenish 25 cubic metres (S.T.P.)/hour sealing nitrogen:
80 cubic metres (S.T.P.)/hour comprise nitrogen base load 20 and gas that in swivelling pipe, discharges
25 cubic metres (S.T.P.)/hour sealing nitrogen 11,
30 cubic metres (S.T.P.)/hour air (current divider 21), and
70 cubic metres (S.T.P.)/hour circulating air 19.
The nitrogen sealing gas is in 25 ℃ of addings.The mixture of other air-flow infeeds swivelling pipe from heater under the temperature that the material in various situations in swivelling pipe has in each situation.
-25 ℃ material temperature is increased to substantial linear 300 ℃ in 10 hours process;
Material temperature then is increased to substantial linear 360 ℃ in 2 hours process;
Then, material temperature is reduced to substantial linear 350 ℃ in 7 hours process;
Material temperature is increased to substantial linear 420 ℃ in 2 hours process then, and this material temperature was kept 30 minutes;
-correspondingly increase the nitrogen base then to load, with displacement by 30 cubic metres (S.T.P.) in the air-flow of swivelling pipe/hour air (so that finish reality heat treatment process), close the heating of swivelling pipe, and by sucking the quick cooling of surrounding air unlatching swivelling pipe, material be cooled to the temperature that is lower than 100 ℃ and finally be cooled to environment temperature in 2 hours process; Air-flow is conducted to swivelling pipe under 25 ℃;
-in whole heat treatment process, low 0.2 millibar at the pressure in the swivelling pipe of (being in close proximity to) air-flow outlet downstream than external pressure.
The oxygen content of the atmosphere in the rotary tube furnace is 2.99 volume % in heat treated all stages.Reproducibility heat treated whole during the arithmetic average of ammonia concentration of atmosphere in the rotary tube furnace be 4 volume %.
Fig. 2 shown as material temperature (℃) the amount of the ammonia that from precursor material, discharges of function, it is the percentage of the ammonia total amount that discharges in the whole heat treatment process from precursor material.
Fig. 3 has shown the concentration of ammonia in the atmosphere (volume %), wherein heat treatment as material temperature in the heat treatment process (℃) function carry out.
Fig. 4 has shown the mole as the molecular oxygen and the ammonia of the function of material temperature, and they are the every kilogram of precursor material chargings hourly that add along with adding the air-flow in the swivelling pipe when heat treatment.
C) shaping of poly-metal deoxide active material
Utilize duplexing cross-current calcification mill (biplex cross-flow calcifying mill) (BQ 500) (coming from Hosokawa-Alpine Augsburg) to grind at B) in the catalytic active material that makes, obtain fine-powder, 50% particle is 1 to 10 micron a screen cloth by mesh in the powder, and its longest dimension is higher than 50 microns particle ratio and is lower than 1%.
As described in the S1 of EP-B 714700, (4 millimeters internal diameters have 45 microns surface roughness R to the powder coated annular carrier of utilization through grinding for 7 mm outer diameter, 3 mm lengths
zThe steatite C220 that comes from Ceram Tec).Adhesive is the aqueous solution of 75 weight % water and 25 weight % glycerine.
Yet different with previous embodiment S1 is that obtain is chosen as 20 weight % (in the gross weight of carrier and active material) through the ratio of the activity of such catalysts material of coating.The ratio of powder and adhesive is adjusted into proportional.
D) test of coated catalysts
Followingly test coated catalysts in the model catalyst pipe, salt bath (mixture of the sodium nitrate of the natrium nitrosum of the potassium nitrate of 53 weight %, 40 weight % and 7 weight %) flows around this catalyst tube:
The model catalyst pipe: the V2A stainless steel, 2 millimeters wall thickness, 26 millimeters internal diameters, the center thermal sleeve that external diameter is 4 millimeters (being used to hold thermocouple), 1.56 liters of free spaces of model catalyst pipe are filled with coated catalysts.
Reaction gas mixtures has following initial composition:
4.8 the methacrylaldehyde of volume %, the oxygen of 7 volume %, the steam of 10 volume %, the nitrogen of 78.2 volume %.
With 2800 liters (S.T.P.) of model catalyst pipe filling/hour the reaction gas starting mixt.This is equivalent to the heap(ed) capacity of the catalyst loading of 86 liters of (S.T.P.) every liter per hours.Adjust the temperature of salt bath, make one way produce the acrolein conversion rate of 97 moles of %.
In in 10 experiments independent of each other, 12 model catalyst pipes that load in this way being compared to each other under each situation.
In all cases, the required salt temperature of desirable acrolein conversion rate is in 257 ± 4 ℃.The about 94.8 moles of % of selectivity of acrylic acid generation in all cases.
Embodiment 2
As described in embodiment 1, carry out all programs.Carry out but the shaping of poly-metal deoxide active material is following:
With 70 kilograms annular carriers (7.1 mm outer diameter, 3.2 mm lengths, 4.0 millimeters internal diameters; Come from the steatite of the C220 type of Ceram Tec, the surface roughness R that tool is 45 microns
zAnd in the total pore size volume of carrier bulk≤1 volume %) add coating pan (90 ° at the inclination angle of internal volume with 200 liters; Come from Germany
Hicoater) in.Coating pan is rotated with 16rpm.Then 3.8 to 4.2 liters the 75 weight % water and the aqueous solution of 25 weight % glycerine are sprayed on the carrier in 25 minutes process by nozzle.Simultaneously, during identical in, 18.1 kilograms of poly-metal deoxide active materials (specific area is 13.8 meters squared per gram) through grinding are added by the vibra shoot continuous metering in the spraying circular cone outside of atomizer nozzle.In coating process, the powder that infeeds is adsorbed on the carrier surface fully, and does not observe the coalescent of trickle oxidisability active material.After the interpolation of active material powder and water finishes, will under the rotary speed of hot-air (about 400 cubic metres/hour) under 100 ℃ (or from 80 to 120 ℃), be blown into 40 minutes (or 15 to 60 minutes) in the coating pan at 2rpm.The ratio of oxidation activity material wherein of making is counted the annular coated catalysts of 20 weight % with gross mass.With regard to a carrier surface and different carriers surface, coating layer thickness is 170 ± 50 microns.
The catalyst that applies as test as described in the embodiment 1.The gained result is suitable with gained result in embodiment 1.
Fig. 5 has also shown the distribution of pores of active material powder before it is shaped through grinding.The pore diameter that will be unit with the micron is mapped along abscissa (logarithmic scale).
With each pore diameter to the logarithm (unit milliliter/gram) of the derivative contribution of total pore size volume along right ordinate mapping (curve O).Maximum is by making the pore diameter performance of maximum contribution to total pore size volume.With each pore diameter to the integration of indivedual contributions (unit milliliter/gram) of total pore size volume along left ordinate map (curve).Terminal point is a total pore size volume.Except as otherwise noted, herein about all data of total pore size volume and diameter Determination of distribution on these total pore size volumes all with the basis that is determined as of AutoPore 9220 devices that utilize the mercury porosity assay method to use to come from Micromeritics GmbH (4040 Neu β, Germany) (bandwidth 30 dusts to 0.3 millimeter); All (measure solid through gas absorption (N about all data of the mensuration of specific area or micropore volume herein according to Brunauer-Emmet-Teller (BET) with the basis that is determined as according to DIN 66131
2) specific area).
Fig. 6 has shown that for the active material powder before being shaped, each pore diameter in range of micropores (abscissa, unit dust, logarithmic scale) is to the contribution separately of total pore size volume (unit milliliter/gram (ordinate)).
It is identical with Fig. 5 that Fig. 7 shows, but at be subsequently by mechanical curettage from the poly-metal deoxide active material (specific area of described active material is 12.9 meters squared per gram) of annular coated catalysts disengaging.
It is identical with Fig. 6 that Fig. 8 shows, but at be subsequently by mechanical curettage and from the poly-metal deoxide active material of annular coated catalysts disengaging.
As described in embodiment 1, carry out all programs.Carry out but the shaping of poly-metal deoxide active material is following:
(diameter is from 4 to 5 millimeters with 70 kilograms of ball type carriers; Come from the steatite of the C220 type of Ceram Tec, the surface roughness R that tool is 45 microns
zAnd in the total pore size volume of carrier bulk≤1 volume %) add coating pan (90 ° at the inclination angle of internal volume with 200 liters; Come from Germany
Hicoater) in.Coating pan is rotated with 16rpm.2.8 to 3.3 liters water is sprayed on the carrier in 25 minutes process by nozzle.Simultaneously, during identical in, 14.8 kilograms of poly-metal deoxide active materials through grinding are added by the vibra shoot continuous metering in the spraying circular cone outside of atomizer nozzle.In coating process, the powder of adding is adsorbed on the carrier surface fully, and does not observe the coalescent of trickle oxidation activity material.After the interpolation of powder and water finishes, will be blown into 40 minutes (or 15 to 60 minutes) in the coating pan with the rotary speed of 2rpm at the hot-air (about 400 cubic metres/hour) under 100 ℃ (or from 80 to 120 ℃).The ratio that makes the oxidation activity material is counted the spherical coated catalysts of 17 weight % with gross mass.With regard to a carrier surface and different carriers surface, coating layer thickness is 160 ± 50 microns.
Fig. 9 shows similar to Fig. 7 (specific area of scraping the poly-metal deoxide active material that takes off is 15 meters squared per gram).
Figure 10 shows similar to Fig. 8.
As among the embodiment 1 about as described in the preparation of annular coated catalysts, test spherical coated catalysts.
Herein all for example coated catalysts of preparation all be specially adapted under the high methacrylaldehyde space velocity (for example, 〉=135 to 350 liters of (S.T.P.) every liter per hours) at catalyst loading methacrylaldehyde be carried out incomplete oxidation.
Claims (19)
1. one kind has the method for in 300 ℃ to 450 ℃ material temperature the precursor material of catalytic active material being heat-treated in the rotary tube furnace that air flow stream crosses therein, described active material is at least a and elements Mo of containing element Nb and W and the multielement oxide material of V, total amount in the outer all elements of deoxygenation in the catalytic activity multielement oxide material, the molar ratio of elements Mo is 20 to 80 moles of %, be contained in Mo and the mol ratio that is contained in the V in the catalytic activity multielement oxide material in the catalytic activity multielement oxide material, Mo/V, it is 15: 1 to 1: 1, and corresponding mol ratio Mo/ (total amount of W and Nb) is 80: 1 to 1: 4, wherein
-described precursor material is obtained by the tight dried blend that the initial compounds preparation also comprises ammonium ion, and described initial compounds comprises the outer elemental composition of multielement oxide material deoxygenation as component,
-the atmosphere of heat-treating is the atmosphere that comprises following ingredients:
-in heat treatment process in the O of each time point from 0.5 to 4 volume %
2,
-at the heat treated whole period average of the reproducibility NH that is 1 to 8 volume %
3,
The steam of-its surplus and/or inert gas,
-NH in heat treatment process
3The atmosphere process is lower than the maximum of 20 volume %, and
-make at least a portion air-flow circulation of rotary tube furnace of flowing through, and do not add external NH to calcination atmosphere
3
2. according to the process of claim 1 wherein that described active material is at least a and at least a multielement oxide material that is selected from the element of the group of being made up of the combination of Nb, Ta, W, Ti, Al, Zr, Cr, Mn, Ga, Fe, Ru, Co, Rh, Ni, Pd, Pt, La, Bi, B, Ce, Sn, Zn, Si, Na, Li, K, Mg, Ag, Au and In of containing element Mo, V, two element T e and Sb.
3. according to the process of claim 1 wherein that the pressure in the rotary tube furnace is lower than environmental pressure.
4. according to the process of claim 1 wherein that the atmosphere that is prevalent in the swivelling pipe comprises composition CO
2, acetate, NO
x, NH
3, CO, SO
2And acetonitrile at least a.
5. according to the process of claim 1 wherein that the flow through cyclic part of air-flow of rotary tube furnace supplies with by cyclone cluster.
According to the process of claim 1 wherein the temperature of described precursor material when heat treatment finishes during 〉=0.5 hour and≤5 hours at least 300 ℃ of reductions.
7. according to the process of claim 1 wherein in order to adjust the total amount of the air-flow that is conducted to swivelling pipe, the principle of utilize the principle measured based on the mass velocity of Coriolis force, measuring based on the orifice plate of pressure reduction or the principle of thermal convection current.
8. according to the method for claim 1, it carries out in comprising the rotary tube type furnace apparatus of following assembly:
A) at least one recycle gas compressor;
B) discharge air compressor at least one;
C) at least one pressure reducer;
D) at least one virgin gas charging;
E) at least one heatable swivelling pipe; And
F) at least one circulating gas pipe.
9. method according to Claim 8, wherein said rotary tube type furnace apparatus also comprises at least one control valve in addition.
10. method according to Claim 8, wherein said rotary tube type furnace apparatus also comprises at least one cyclone cluster in addition.
11. according to Claim 8 to 10 each methods, wherein said rotary tube type furnace apparatus also has the device that is used for quick cooling in addition, it is made of the shell around swivelling pipe, and have the hole that can surrounding air be sucked by fan in a side, and surrounding air can be discharged by being present in flap on the shell opposite side and that have adjustable hole.
12. according to the process of claim 1 wherein holdup time 〉=5 of precursor material in rotary tube furnace hour.
13. a rotary tube type furnace apparatus, it comprises:
A) at least one recycle gas compressor;
B) discharge air compressor at least one;
C) at least one pressure reducer;
D) at least one virgin gas charging;
E) at least one heatable swivelling pipe; And
F) at least one circulating gas pipe.
14. according to the rotary tube type furnace apparatus of claim 13, it also comprises at least one control valve in addition.
15. according to the rotary tube type furnace apparatus of claim 13, it also comprises at least one cyclone cluster in addition.
16. according to each rotary tube type furnace apparatus of claim 13 to 15, it also has the device that is used for quick cooling in addition, it is made of the shell around swivelling pipe, and have the hole that can surrounding air be sucked by fan in a side, and surrounding air can be discharged by being present in flap on the shell opposite side and that have adjustable hole.
17. bundled tube reactor, it comprises 5000 to 40000 catalyst tubes that are filled with load, the catalyst of described load comprises the multielement oxide material as active material, described multielement oxide material contains at least a and elements Mo and the V of element nb and W, total amount in the outer all elements of the deoxygenation in the catalytic activity multielement oxide material, the molar ratio of elements Mo is 20 to 80 moles of %, be contained in Mo and the mol ratio that is contained in the V in the catalytic activity multielement oxide material in the catalytic activity multielement oxide material, Mo/V, it is 15: 1 to 1: 1, and corresponding mol ratio Mo/ (total amount of W and Nb) is 80: 1 to 1: 4, and described multielement oxide material can be by making according to each method of claim 1 to 12, with the methacrylaldehyde incomplete oxidation is that the load of acrylic acid catalyst tube makes when 12 catalyst tube chance samples of extraction, and the difference between arithmetic average active and the highest or the lowest activity is not more than 8 ℃.
18. bundled tube reactor, it comprises 5000 to 40000 catalyst tubes that are filled with load, the catalyst of described load comprises the multielement oxide material as active material, described multielement oxide material contains elements Mo, V, the at least a and at least a of two element T e and Sb is selected from by Nb, Ta, W, Ti, Al, Zr, Cr, Mn, Ga, Fe, Ru, Co, Rh, Ni, Pd, Pt, La, Bi, B, Ce, Sn, Zn, Si, Na, Li, K, Mg, Ag, the element of the group that the combination of Au and In is formed, and can be by making according to each method of claim 1 to 12, with the methacrylaldehyde incomplete oxidation is that the load of acrylic acid catalyst tube makes when 12 catalyst tube chance samples of extraction, and the difference between arithmetic average active and the highest or the lowest activity is not more than 8 ℃.
19. according to the bundled tube reactor of claim 17 or 18, it is operated under the methacrylaldehyde space velocity of the catalyst loading of 〉=every liter per hour 135 liters (S.T.P.).
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2003125487 DE10325487A1 (en) | 2003-06-04 | 2003-06-04 | Thermal treatment of precursor material of catalytically active material, for partial gas-phase oxidation of acrolein to acrylic acid, involves circulating gas stream flowing through rotary tube furnace |
| US60/475,501 | 2003-06-04 | ||
| DE10325487.0 | 2003-06-04 | ||
| DE10360057.4 | 2003-12-19 | ||
| US60/530,620 | 2003-12-19 |
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| DE (1) | DE10325487A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7019169B2 (en) | 2003-09-23 | 2006-03-28 | Basf Aktiengesellschaft | Preparation of (meth)acrylic acid |
| DE102007004961A1 (en) | 2007-01-26 | 2008-07-31 | Basf Se | Preparing a catalyst molded body, useful e.g. to prepare catalyst for gas phase partial oxidation of an organic compound, comprises molding a precursor mixture to a desired geometry, using graphite, and thermally treating the molded body |
| DE102008040093A1 (en) | 2008-07-02 | 2008-12-18 | Basf Se | Producing a ring like oxidic mold, useful e.g. in partial gas phase oxidation of e.g. an organic compound, comprising mechanical packing of a powdery material which is brought into the fill space of a die made of a metal compound |
| DE102008040094A1 (en) | 2008-07-02 | 2009-01-29 | Basf Se | Production of an oxidic geometric molded body used as a catalyst in a heterogeneously catalyzed partial gas phase oxidation comprises mechanically compressing a powdered material inserted into a filling chamber of a die |
| DE102008042061A1 (en) | 2008-09-12 | 2010-03-18 | Basf Se | Process for the preparation of geometric shaped catalyst bodies |
| DE102008042064A1 (en) | 2008-09-12 | 2010-03-18 | Basf Se | Process for the preparation of geometric shaped catalyst bodies |
| DE102008042060A1 (en) | 2008-09-12 | 2009-06-18 | Basf Se | Preparing catalyst molded body, useful e.g. in ammoxidation of propene to acrylonitrile, comprises mixing starting mass having fine particles of bismuth mixed oxide with another starting mass, and forming geometrical molded bodies |
| RU2012125832A (en) | 2009-12-04 | 2014-01-10 | Басф Се | OBTAINING ACETALDEHYDE AND / OR ACETIC ACID FROM BIOETHANOL |
| DE102010040923A1 (en) | 2010-09-16 | 2012-03-22 | Basf Se | Process for the preparation of acrylic acid from ethanol and formaldehyde |
| DE102013202048A1 (en) * | 2013-02-07 | 2013-04-18 | Basf Se | Preparing catalytically active composition useful for preparing a catalyst, comprises e.g. thermally treating geometrical precursor bodies formed by a mixture obtained by uniformly mixing e.g. a spray-dried powder and molybdenum oxide |
| DE102015209638A1 (en) | 2015-05-27 | 2016-07-07 | Basf Se | A process for producing a bismuth and tungsten-containing multielement oxide by co-precipitation |
| EP3770145A1 (en) | 2019-07-24 | 2021-01-27 | Basf Se | A process for the continuous production of either acrolein or acrylic acid as the target product from propene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE618872C (en) * | 1933-07-30 | 1935-09-17 | Metallgerellschaft Akt Ges | Rotary kiln |
-
2003
- 2003-06-04 DE DE2003125487 patent/DE10325487A1/en not_active Withdrawn
-
2004
- 2004-05-29 CN CNB200480015576XA patent/CN100393406C/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE618872C (en) * | 1933-07-30 | 1935-09-17 | Metallgerellschaft Akt Ges | Rotary kiln |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1798604A (en) | 2006-07-05 |
| DE10325487A1 (en) | 2004-12-23 |
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