CN1477091A - Method for preparing acrolein membrane reactor for propane oxidation and its application - Google Patents
Method for preparing acrolein membrane reactor for propane oxidation and its application Download PDFInfo
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- CN1477091A CN1477091A CNA021304742A CN02130474A CN1477091A CN 1477091 A CN1477091 A CN 1477091A CN A021304742 A CNA021304742 A CN A021304742A CN 02130474 A CN02130474 A CN 02130474A CN 1477091 A CN1477091 A CN 1477091A
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Abstract
The present invention relates to a film reactor for making propane by partially oxidated to prepare propenal. It adopts the method of mixing sol and AgBiVMoO to complex powder body to implement preparation. It utilizes AgBiVMoO to form a thin layer of uniform continuous film on alpha-Al2O3 film pipe surface, the loaded quantity of catalyst on the film pipe can be up to 50-100 mg, thickness is about 6-7 micrometers, and it has scheelite structure. When said film reactor is used for preparing propenal by propane oxidation, it makes the reaction gas propane must be contacted with catalyst layer to make it produce reaction to raise conversion rate of propane, and can make the produced propenal must be quickly separated from catalyst layer so as to prevent it from be deep-oxidated and raise selectivity of propenal.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the membrane reactor of oxidation of propane acrolein reaction.
The invention still further relates to the application of above-mentioned membrane reactor in the reaction of oxidation of propane acrolein.
Background technology
Propenal, vinylformic acid and ester class series product thereof generally are used for industries such as coating, chemical fibre, weaving, light industry, also are used for oil production, oil dope etc.In recent years, occurred some noticeable new purposes abroad, according to statistics, world's propenal, vinylformic acid overall throughput reached 6,000,000,000 pounds/year in 1997.The operational path of making propenal, vinylformic acid and ester thereof is more, and is now industrial based on propylene oxidation.Because therefore propylene cost height adopts propane cheap and easy to get to replace direct oxidation of propylene acrolein and vinylformic acid to become one of research focus of low-carbon alkanes development and use.Propane is a main component in oil field gas, Sweet natural gas, the refinery gas, and the more fuel that is used for of past on a small quantity as solvent, or as the raw material of steam cracking, is produced ethene and propylene.Abroad industrial have the propane catalytic dehydrogenation is become propylene, replenish the deficiency of propylene supply.The U.S., Britain etc. are because the propane source is more, and is cheap than propylene, and Chemicals or industrial chemicals were subject to people's attention in the middle of propane catalysis was processed into, and wherein the direct synthesis of acrolein of propane catalyzed oxidation, vinylformic acid are one of directions in exploration.In China, big gas field has been found in China western part in recent years.In the oil field gas, it is more generally to contain propane, have up to more than 10%, some oil fields of Xinjiang of China, the crude quality that produces lighter, it is also many to contain propane in the oil field gas.So, carry out direct synthesis of acrolein of propane oxidation step or vinylformic acid and have very remarkable economic efficiency and practical significance.
The popular response of fixed bed is mostly adopted in the propane reaction that present people are carried out.Because the character of propane molecule is torpescence very, be not easy usually to react, and its partial oxidation products propenal or acrylic acid character is more active than propane, are easy to take place deep oxidation.So problem aspect the filling of catalyzer exists two in fixed bed reaction: if 1 catalyst bed layer height is low excessively, because the space between the granules of catalyst is bigger, gas molecule has little time to contact with catalyzer and reacts, and just flows through from the space, has reduced the transformation efficiency of propane.If 2 beds excessive height, propenal that side reactor generated on the beds or vinylformic acid are generated CO by deep oxidation easily in the motion of beds bottom
x, reduced propenal or acrylic acid selectivity.Porous-film with catalytic activity can influence the concentration distribution of reactant and intermediate product to a certain extent, thereby the selectivity of reaction and the distribution of product are controlled.If with the way of sol-gel with catalyst cupport at α-Al
2O
3On the pipe, form the catalyst layer that skim is continuous and density of catalyst is high, be prepared into catalytic film, just can overcome catalyst loading adverse effect in the popular response on its surface.
Summary of the invention
The object of the present invention is to provide a kind of preparation method who is used for the catalytic film reactor of propane partial oxidation vinylformic acid reaction.The catalytic film of this method preparation has thin, the even and successive characteristics of catalyst layer.The AgBiVMoO catalyzer on film surface has scheelite-type structure.
Another purpose of the present invention is to provide a kind of above-mentioned application of catalytic film reactor in propane partial oxidation acrolein reaction.
For achieving the above object, a kind of membrane reactor that is used for propane partial oxidation acrolein provided by the invention adopts mixed sols and catalyst fines method.Basement membrane is α-Al
2O
3Pipe (having the mean pore size of 1.2um and 40% porosity), active ingredient is the mixed metal oxide AgBiVMoO with scheelite-type structure, its metal molar is 0.01-0.05: 0.5-1: 0.3-0.6: 0.3-0.6 than in regular turn, and the weight ratio of active ingredient and γ-AlOOH colloidal sol is 20-80: 100.The catalytic film layer thickness that this method prepares among the present invention is 6～7um, and the surface evenly also continuously.Its key step is as follows:
1) basement membrane is for having 1.2 μ m mean pore sizes, the α-Al of 40% porosity
2O
3Pipe, with surface finish, cleaning, in 400-600 ℃ of roasting 3-9 hour, two ends were coated with glaze, and the centre is a catalytic section.
2) nitrate with ammonium molybdate, Vanadium Pentoxide in FLAKES and silver and bismuth is raw material, its metal molar is 0.01-0.05: 0.5-1: 0.3-0.6: 0.3-0.6 than in regular turn, add metal content 5-10 complexing agent doubly, complexing agent can be one or more of disodium EDTA, ethylenediamine tetraacetic acid (EDTA) and citric acid; The room temperature lower magnetic force stirred after 4-6 hour, in 80-120 ℃ of heated and stirred, was evaporated to pasty state again, 280-400 ℃ roasting 3-9 hour, be warming up to 550-650 ℃ of roasting 3-9 hour, promptly get AgBiVMoO complexing powder, its particle diameter is less than 100 orders.
3) polyvinyl alcohol that adds 1-4% in γ-AlOOH colloidal sol is that the polyoxyethylene glycol of tackifier and 1-2% is a softening agent, stirs into the colloidal sol of stable homogeneous, and the granularity of γ-AlOOH colloidal sol is 19～60nm; The AgBiVMoO complexing powder that step 2 is made joins in this γ-AlOOH colloidal sol, and the weight ratio of complexing powder and colloidal sol is 20-80: 100, keep pH value of solution 3-4, and stir.
4) will put in the mixing solutions of step 3 preparation through the basement membrane that step 1 is handled, take out, be put in the dustless case under the air atmosphere seasoning 10-20 hour, again at 80-140 ℃ of dry 30-50 hour, after being warming up to 480-600 ℃ of roasting 2-6 hour gradually with the temperature rise rate of 2-5 ℃/min, slowly cooling cooling.Repeat this step, the charge capacity of the catalyzer on the film pipe reaches 200-500mg/cm
2In the acrylic acid reaction of propane system, this film has good catalytic activity and selects performance.
The present invention also provides the application of above-mentioned catalytic film in the reaction of propane partial oxidation vinylformic acid, and its temperature of reaction is 400 ℃～550 ℃, and reaction pressure is a normal pressure, and reaction velocity is 1.2 * 10
5Mlg
-1H
-1
Compare with the present invention, use the immersion process for preparing catalytic film, be about to EDTA network and the solution of basement membrane direct impregnation AgBiVMoO, the catalytic film for preparing, the network of catalyzer and solution enter into the counterdie hole, do not form rete.With the sol gel process of modifying, that is: modify γ-AlOOH colloidal sol with EDTA network and the solution of AgBiVMoO, dip-coating is to membrane surface again, and there is slight crack in the surface of the catalytic film that this method prepares, makes film imperfect.
About dipping method, modify sol gel process and the catalyst based powder method preparation of mixed solvent of the present invention catalytic film model diagram as shown in Figure 1.
Description of drawings
Below by embodiment and accompanying drawing in detail the present invention is described in detail.
Fig. 1 is the model diagram of the catalytic film of different methods preparation, and wherein: Fig. 1 a is a dipping method; Fig. 1 b is for modifying sol gel process; Fig. 1 c is the catalyst based powder method of mixed sols.
Fig. 2 is the XRD figure of the catalytic film of different methods and different loadings, wherein: the sol gel process (40%AgBiVMo) of curve a for modifying; Curve b is a dipping method; Curve c is mixed sols and catalytic powder method (40%AgBiVMo); Curve d is mixed sols and catalytic powder method (80%AgBiVMo).
Fig. 3 is the catalytic film SEM sem photograph of mixed sols and the preparation of catalyst fines method, and wherein: Fig. 3 a is a side elevational view; Fig. 3 b is top figure.
Fig. 4 is that the catalytic activity of catalytic film in the reaction of propane partial oxidation vinylformic acid of passing through the different catalysts loading of the third method preparation compares, and wherein: 1 is C among Fig. 4 a
3H
6, 2 is C
2H
4, 3 is CO
2, 4 is CO; 1 is methyl alcohol among Fig. 4 b, and 2 is propenal, and 3 is acetone, and 4 is formaldehyde.
Fig. 5 is the SEM figure by the catalytic film of dipping method preparation, and wherein: Fig. 5 a is a side elevational view; Fig. 5 b is top figure.
Fig. 6 schemes for the SEM of the catalytic film that the sol gel process by modification prepares, and wherein: Fig. 6 a is a side elevational view; Fig. 6 b is top figure.
Embodiment
The detailed process of mixed sols and catalyst fines method: adopt α-Al
2O
3Pipe is basement membrane, this basement membrane external diameter 1.14cm, and mean pore size is 1.2 μ m, and porosity is 40%, and with surface finish, cleaning, in 550 ℃ of roastings 6 hours, two ends were coated with glaze, and middle 6cm is a catalytic section;
Adopting the nitrate of ammonium molybdate, Vanadium Pentoxide in FLAKES and silver and bismuth is raw material, mol ratio between its metal is 0.01: 0.85: 0.54 in proper order: 0.45, add EDTA as complexing agent, the amount of substance of the complexing agent that adds is 10 times of metal ion content, and the room temperature lower magnetic force stirs 5 hours to complexing fully, 80 ℃ of heated and stirred, be evaporated to pasty state, in 380 ℃ of roastings 6 hours, be warming up to 600 ℃ of roastings 6 hours again, promptly get AgBiVMoO complexing powder;
The polyoxyethylene glycol that adds weight percentage and be respectively 2% polyvinyl alcohol and 1% in γ-AlOOH colloidal sol stirs the colloidal sol that forms stable homogeneous as tackifier and softening agent.AgBiVMoO network and catalyzer part body are sized to below 100 orders, join in above-mentioned treated γ-AlOOH colloidal sol, mix.The pH value of strict control solution is about 3.4.Wherein, AgBiVMoO/ (AgBiVMoO+Al
2O
3) be 40% and 80%.Make its surface form the layer of gel layer several second in the basement membrane pipe immersion solution under the room temperature.Put into the dirt seal housing seasoning after the taking-up 12 hours, and under 120 ℃ of air atmosphere dry 48 hours again, be warming up to 550 ℃ of following roastings 4 hours slowly, slowly cooling cooling with the temperature rise rate of 3 ℃/min.Repeating the catalyst loadings of aforesaid operations on the film pipe is 240mg/cm
2
Mixed metal oxide AgBiVMoO has formed the scheelite-type structure that propane partial oxidation value vinylformic acid is had catalytic activity in the catalytic film of mixed sols and the preparation of catalyst fines method.Shown in the XRD figure of Fig. 2.
The catalytic film of mixed sols and the preparation of catalyst fines method has formed the very thin successive catalytic film of one deck in the porous membrane surface, and thickness is greatly about 6-7um, and AgBiVMoO network and catalyst fines are evenly distributed in the film.See shown in the SEM figure of Fig. 3.
To be used for the reaction of propane partial oxidation acrolein by the catalytic film of mixed sols and the preparation of catalyst fines method, because AgBiVMoO has formed the crystalline structure of sheelite on the catalytic film surface, make it have certain catalytic activity to preparing propylene transformed aldehyde of propane and vinylformic acid.Have continuously in the formed Catalytic Layer in film surface, density of catalyst is high and the characteristics of very thin thickness, makes the propane molecule when seeing through, and is bound to fully contact with catalyzer react, and has improved the transformation efficiency of propane; Vinylformic acid is avoided further being oxidized in the partial oxidation products propenal of the Sheng Chenging Catalytic Layer surface that speeds away simultaneously, has improved the selectivity of propenal.Experimental result shows, in membrane catalytic reaction, because basement membrane pipe Al
2O
3Character with complete oxidation is so contain a large amount of hydrocarbon CO and CO in gaseous products
2, in addition, in gaseous products, also have dehydrogenation product propylene and a spot of ethene of part.And in liquid-phase product, for AgBiVMoO/ (AgBiVMoO+Al
2O
3) be that the selectivity of the propenal of 40% catalytic film can be up to 54.85%; AgBiVMoO/ (AgBiVMoO+Al
2O
3) be that the selectivity of the propenal of 80% catalytic film can reach 38.26%, in liquid-phase product, there are a spot of methyl alcohol, acetone and formaldehyde to exist simultaneously respectively.But because the amount of the catalyzer of load has seldom limited the transformation efficiency of propane on the film.Reaction result is seen shown in Figure 4.
Comparative example 1
Dipping method prepares the detailed process of catalytic film: will the porous support identical with embodiment 1 be immersed in AgBiVMoO network and the solution 24 hours, and took out the rear and go in the dirt seal housing.And then following 120 ℃ of dryings of air atmosphere 48 hours, so that temperature rise rate and rate of temperature fall were burnt 4 hours down at 550 ℃ slowly.Repeating the catalyst loadings of aforesaid operations on the film pipe is 240mg/cm
2XRD by Fig. 2 shows that the scheelite-type structure of AgBiVMoO can not detected in the film surface of this method preparation, has only the α-Al of basement membrane
2O
3Phase.The SEM figure of Fig. 5 further shows by dipping method do not have to form the Catalytic Layer of wanting in membrane surface.This is because network and the solution of AgBiVMoO are deep in steeping process in the middle of the hole of basement membrane, does not form Catalytic Layer.
Comparative example 2
The detailed process of the sol gel process of modifying: network and the solution of AgBiVMoO are joined in γ-AlOOH colloidal sol.Stir certain hour and make solution even, and strict control pH value of solution value does not make the aluminium glue coagulation about 3.4.AgBiVMoO/ (AgBiVMoO+Al in the solution
2O
3) be 40% and 80%.Will the basement membrane pipe identical under the room temperature immerse that make its surface form the layer of gel layer several seconds in the solution with embodiment 1.Put into dirt seal housing for some time after the taking-up, and then following 120 ℃ of dryings of air atmosphere 48 hours, so that temperature rise rate and rate of temperature fall were burnt 4 hours down at 550 ℃ slowly.Repeating the catalyst loadings of aforesaid operations on the film pipe is 240mg/cm
2XRD by Fig. 2 shows that the catalytic film surface of this method preparation is except α-Al
2O
3Mutually, there is not the scheelite-type structure of AgBiVMoO.Shown in the SEM figure of Fig. 6, as can be seen, formed one deck successive film from the figure of top in the porous membrane surface, but in the process of roasting, the film cracking.This is because the film for preparing by the sol gel process of modifying is thicker, about about 10um, so in roasting, film shrinks and causes cracking.
By above two comparison example, illustrate that having only preparation method provided by the invention is that mixed sols and catalyst fines method can be prepared required thin and successive catalytic film.
Claims (7)
1, a kind of membrane reactor preparation method who is used for propane partial oxidation acrolein, key step is as follows:
A) adopt α-Al
2O
3Pipe is basement membrane, and in 400-600 ℃ of roasting 3-9 hour, two ends were coated with glaze, and the centre is a catalytic section;
B) be raw material with ammonium molybdate, Vanadium Pentoxide in FLAKES and silver and bismuth, its metal molar is 0.01-0.05: 0.5-1: 0.3-0.6: 0.3-0.6 than in regular turn, add metal content 5-10 complexing agent doubly, the room temperature lower magnetic force stirred after 4-6 hour, in 80-120 ℃ of heated and stirred, be evaporated to pasty state again, 280-400 ℃ roasting 3-9 hour, be warming up to 550-650 ℃ of roasting 3-9 hour, and promptly got AgBiVMoO complexing powder;
Described complexing agent is one or more of disodium EDTA, ethylenediamine tetraacetic acid (EDTA) and citric acid;
C) in γ-AlOOH colloidal sol, add the tackifier of 1-4% and the softening agent of 1-2%, stir into the colloidal sol of stable homogeneous; The AgBiVMoO complexing powder that step b is made joins in this γ-AlOOH colloidal sol, and the weight ratio of complexing powder and colloidal sol is 20-80: 100, keep pH value of solution 3-4, and stir;
Described tackifier are polyvinyl alcohol, and softening agent is a polyoxyethylene glycol;
D) will put in the mixing solutions of step c preparation through the basement membrane that step a handles, take out, be put in the dustless case under the air atmosphere seasoning 10-20 hour, again at 80-140 ℃ of dry 30-50 hour, after being warming up to 480-600 ℃ of roasting 2-6 hour gradually with the temperature rise rate of 2-5 ℃/min, slowly cooling cooling.
2, preparation method as claimed in claim 1 is characterized in that, described α-Al
2O
3The pipe mean pore size is 1.2 μ m, and porosity is 40%.
3, preparation method as claimed in claim 1 is characterized in that, described ammonium molybdate, Vanadium Pentoxide in FLAKES and silver and bismuth are its nitrate.
4, preparation method as claimed in claim 1 is characterized in that, the granularity of described γ-AlOOH colloidal sol is 19～60nm.
5, preparation method as claimed in claim 1 is characterized in that, its particle diameter of AgBiVMoO complexing powder that adds among the described step c is less than 100 orders.
6, preparation method as claimed in claim 1 is characterized in that, repeats the operation of steps d, and the charge capacity of the catalyzer to the film pipe reaches 200-500mg/cm
2
7, a kind of application of membrane reactor in the reaction of oxidation of propane acrolein as claim 1 preparation.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021304742A CN1194953C (en) | 2002-08-21 | 2002-08-21 | Method for preparing acrolein membrane reactor for propane oxidation and its application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021304742A CN1194953C (en) | 2002-08-21 | 2002-08-21 | Method for preparing acrolein membrane reactor for propane oxidation and its application |
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| Publication Number | Publication Date |
|---|---|
| CN1477091A true CN1477091A (en) | 2004-02-25 |
| CN1194953C CN1194953C (en) | 2005-03-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021304742A Expired - Fee Related CN1194953C (en) | 2002-08-21 | 2002-08-21 | Method for preparing acrolein membrane reactor for propane oxidation and its application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1706548B (en) * | 2004-06-07 | 2012-08-22 | 花王株式会社 | Process for producing aldehyde |
| CN109999904A (en) * | 2019-04-29 | 2019-07-12 | 陕西延长石油（集团）有限责任公司 | A kind of catalyzing iso-butane alkene or the tert-butyl alcohol prepare catalyst of methacrolein and the preparation method and application thereof |
-
2002
- 2002-08-21 CN CNB021304742A patent/CN1194953C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1706548B (en) * | 2004-06-07 | 2012-08-22 | 花王株式会社 | Process for producing aldehyde |
| CN109999904A (en) * | 2019-04-29 | 2019-07-12 | 陕西延长石油（集团）有限责任公司 | A kind of catalyzing iso-butane alkene or the tert-butyl alcohol prepare catalyst of methacrolein and the preparation method and application thereof |
| CN109999904B (en) * | 2019-04-29 | 2022-03-01 | 陕西延长石油（集团）有限责任公司 | Catalyst for preparing 2-methylacrolein by catalyzing isobutene or tertiary butanol and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1194953C (en) | 2005-03-30 |
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