CN1697794A - Process for producing unsaturated aldehyde and unsaturated carboxylic acid - Google Patents
Process for producing unsaturated aldehyde and unsaturated carboxylic acid Download PDFInfo
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- CN1697794A CN1697794A CN 200480000348 CN200480000348A CN1697794A CN 1697794 A CN1697794 A CN 1697794A CN 200480000348 CN200480000348 CN 200480000348 CN 200480000348 A CN200480000348 A CN 200480000348A CN 1697794 A CN1697794 A CN 1697794A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
PROBLEM TO BE SOLVED: To provide a method for producing an unsaturated aldehyde and an unsaturated carboxylic acid in high yield by catalytically oxidizing an olefin with a molecular oxygen-containing gas in a gas phase, stable for a long time by dissolving problems caused by hot spots.
Description
Technical field
The gas that the present invention relates to the alkene utilization is contained molecular oxygen carries out catalytic gas phase oxidation, and is steady in a long-term and prepare the method for corresponding unsaturated aldehyde and unsaturated carboxylic acid with high yield.
Background technology
Relevant in the presence of composite oxide catalysts, utilize molecular oxygen to carry out catalytic gas phase oxidation in alkene such as propylene, iso-butylene, the method for preparing unsaturated carboxylic acids such as unsaturated aldehydes such as corresponding propenal, Methylacrylaldehyde and vinylformic acid, methacrylic acid respectively, past has proposed many schemes, and a part is in industrial enforcement.
This preparation feedback uses fixed bed multitube (fixed bed multitube) reactor to carry out, but because a large amount of thermopositive reaction take place, so be easy to generate focus (abnormal high temperature portion) especially at the inlet side of unstripped gas.Therefore the over-drastic oxidizing reaction causes yield to reduce, or because the accelerator activator inactivation produces problems such as catalyst life reduction.Especially, improve raw material olefin concentration, or when strengthening space velocity, this problem is more serious for the turnout that improves the per unit catalyzer.As a result, in fact be difficult to steady in a long-term and prepare corresponding unsaturated aldehyde and unsaturated carboxylic acid with high yield.
Past has proposed to suppress above-mentioned focus (ホ Star ト ス Port Star ト), improves the preparation method that production efficiency and catalyst life are used.For example, Patent Document 1 discloses the method for using the amount that is filled with the multiple catalyzer that changed the amount of Bi and Fe in the Mo-Bi system complex oxide catalyzer and Bi and Fe to react to the fixed-bed tube reactor that reduces towards outlet from the inlet of unstripped gas.
In addition, Patent Document 2 discloses preparation and has changed the kind of the alkali earths element that is contained and/or the active different multiple catalyzer of amount, use is filled with these catalyzer and the catalyst layer in each reaction tubes is divided into 2 layers or a plurality of reaction zones of multiwalled along tube axial direction on, the method that the fixed-bed tube reactor that improves towards the Way out catalyst activity from the inlet of unstripped gas reacts.
In addition, Patent Document 3, Patent Document 4 disclose following method: in fact do not change catalyzer and form and the different multiple catalyzer of preparation firing temperature, the catalyst layer in each reaction tubes is divided into 2 layers or a plurality of reaction zones of multiwalled along tube axial direction on, burning till with high more temperature from the near more place of the inlet side of unstripped gas, the fixed-bed tube reactor of the catalyzer of preparation reacts with having filled thus.
Yet, when adopting these prior aries,, do not satisfy though can obtain certain effect, also require fully to solve the novel method of the caused problem of focus.
Patent Document 1: the spy opens the 20001-48817 communique
Patent Document 2: specially permit No. 2809476 communique
Patent Document 3: the spy opens flat 10-168003 communique
Patent Document 4: specially permit No. 3139285 communique
Summary of the invention
In view of above-mentioned prior art, the present invention seeks to be provided under the existence of Mo-Bi system complex oxide catalyzer, when alkene especially propylene is carried out gaseous oxidation, solve the novel method of the caused problem of focus, provide steady in a long-term and prepare unsaturated aldehyde and unsaturated carboxylic acid, especially propenal and acrylic acid with high yield.
The inventor concentrates one's attention on to study in order to solve above-mentioned problem, found that by to the condition in the sintering process of preparation Mo-Bi system complex oxide catalyzer, change the amount ratio of (ambiance gas flow/catalytic amount) or change and burn till the catalyzer that number of times obtains, utilizing molecular oxygen that alkene is carried out catalytic gas phase oxidation when preparing unsaturated aldehyde and unsaturated carboxylic acid, its activity varies in size.That is, the activity that can control catalyst has by the condition that changes in above-mentioned the burning till, thus can prepare active different many catalyzer.
In addition, the inventor also finds to fill the active different multiple catalyzer that as above makes, make its reactor from inlet of unstripped gas towards the active increase of outlet in cutting apart a plurality of reaction zones that fixed-bed tube reactor forms can solve above-mentioned problem by using along specific direction.
That is, the present invention has the invention that the main idea of following feature constitutes.
(1) preparation method of unsaturated aldehyde and unsaturated carboxylic acid, this method is used the fixed bed tube-type reactor, the gas that the alkene utilization is contained molecular oxygen carries out catalytic gas phase oxidation and prepares unsaturated aldehyde and unsaturated carboxylic acid, described fixed bed tube-type reactor has been filled the composite oxide catalysts that contains molybdenum and bismuth, it is characterized in that, in this method
(A) use active different multiple catalyzer as above-mentioned composite oxide catalysts, described multiple catalyzer is to change the environmental gas flow to burn till the catalyzer that number of times makes with the amount of catalytic amount than burning till or changing,
(B) along the tube axial direction in the reactor a plurality of reaction zones are set,
(C) fill described multiple catalyzer at each reaction zone, its activity is increased towards Way out from the inlet of unstripped gas.
(2) above-mentioned (1) described preparation method is characterized in that, described composite oxide catalysts is the catalyzer with following formula (1):
Mo
aBi
bCo
cNi
dFe
eX
fY
gZ
hQ
iSi
jO
k????(1)
(in the formula, X is at least a kind of element that is selected among Na, K, Rb, Cs and the Tl, Y is at least a kind of element that is selected among B, P, As and the W, Z is at least a kind of element that is selected among Mg, Ca, Zn, Ce and the Sm, Q represents halogen, in addition, a～j represents each atoms of elements ratio, during a=12, respectively in 0.5≤b≤7, the scope of 0≤c≤10,0≤d≤10 (1≤c+d≤10), 0.05≤e≤3,0.0005≤f ≤～3,0≤g≤3,0≤h≤1,0≤i≤0.5,0≤j≤40, k is the numerical value that satisfies other element states of oxidation).
(3) above-mentioned (1) or (2) described preparation method is characterized in that, the activity that 2 kinds or multiple composite oxide catalysts have is 1 o'clock at the catalyst activity of unstripped gas inlet side, and the activity of outlet side is below 5 or 5.
(4) above-mentioned (1), (2) or (3) described preparation method, the quantity that it is characterized in that reaction zone is 2～4.
(5) any described preparation method in above-mentioned (1)～(4) is characterized in that alkene is propylene, and unsaturated aldehyde and unsaturated carboxylic acid are respectively propenal and vinylformic acid.
The invention effect
By method of the present invention, can suppress the uncontrolled reaction that take place to produce with focus or because of the over-drastic oxidizing reaction generates by product, highly selective and prepare purpose unsaturated aldehyde and unsaturated carboxylic acid with high yield.In addition, because can use catalyzer steadily in the long term, can also enhance productivity significantly.
The optimum implementation of invention
Below the present invention is at length described, among the present invention, olefin conversion, object selection rate and yield are calculated with following formula.
Olefin conversion (mole %)=(the alkene mole number of the alkene mole number/supply of having reacted) * 100
The selection rate of object (mole %)=(mole number of the unsaturated carboxylic acid of the mole number+generation of the unsaturated aldehyde of generation)/react the alkene mole number) * 100
The yield of object (mole %)=(mole number of the alkene of (mole number of the unsaturated carboxylic acid of the mole number+generation of the unsaturated aldehyde of generation)/supply) * 100
The present invention uses all catalyzer of molybdenum-bismuth-system compound oxide catalyzer.Though anyly all reach certain effect, wherein, reach significant effect when using the catalyzer of following formula (1) expression, therefore preferred.
Mo
aBi
bCo
cNi
dFe
eX
fY
gZ
hQ
iSi
jO
k????(1)
(in the formula, Mo is a molybdenum, Bi is a bismuth, Co is a cobalt, Ni is a nickel, Fe is an iron, Si is a silicon, O is an oxygen, X is selected from Na, K, Rb, at least a kind of element among Cs and the Tl, Y is selected from B, P, at least a kind of element among As and the W, Z is selected from Mg, Ca, Zn, at least a kind of element among Ce and the Sm, Q represents halogens such as chlorine atom, a～j represents each atoms of elements ratio, during a=12, respectively in 0.5≤b≤7,0≤c≤10,0≤d≤10 (1≤c+d≤10), 0.05≤e≤3,0.0005≤f≤3,0≤g≤3,0≤h≤1,0≤i≤0.5, the scope of 0≤j≤40, in addition, k is the numerical value that satisfies other element states of oxidation).
Wherein, the catalyzer that the present invention uses, Q is the chlorine atom in the preferred above-mentioned formula (1), during preferred especially a=12, the scope of 0.5≤b≤7,0≤c≤10,0≤d≤10,1≤c+d≤10,0.05≤e≤3,0.0005≤f≤3,0≤g≤3,0≤h≤1,0≤i≤0.05,0≤j≤40.
Above-mentioned composite oxide catalysts among the present invention passes through prepared in various methods.For example, the aequum of starting compound that will contain each elemental composition that constitutes catalyzer usually is suitably dissolving or decompose in aqueous medium, and after the heated and stirred, that evaporation is done is solid, dry, pulverizing is prepared.The raw material of each composition can use nitrate, ammonium salt, oxyhydroxide, oxide compound, acetate of each element etc.The mixture of the coccoid of gained, the usually preferred forming methods such as extrusion moulding, granulating and forming, compression molding that adopt are processed into arbitrary shapes such as spherical, cylindric, ring-type.Moreover, for intensity, the efflorescence degree that improves catalyzer, can in said mixture, add inorganic fibre, various whiskers etc. such as general known glass fibre.In addition, for reproducibility control catalyst rerum natura well, also can use ammonium nitrate, Mierocrystalline cellulose, starch, polyvinyl alcohol, stearic acid etc. generally as the known additive of tackiness agent.
In addition, composite oxide catalysts among the present invention can use individually, also can load with at aluminum oxide, silicon-dioxide, silica, silicon carbide, titanium oxide, magnesium oxide, zirconium sponge, silicon oxide/titanium oxide etc. and generally use on the known carrier as inert support.At this moment,, also can use aforesaid inorganic fibre etc., in addition,, also can use tackiness agents such as aforesaid ammonium nitrate for reproducibility control catalyst rerum natura well for intensity of improving catalyzer etc.
Then, above-mentioned formed body or carrier burn till under the circulation of ambiance gas, this burn till usually 400～650 ℃, preferably under 450～600 ℃ temperature, carry out usually 1～20 hour, preferably carried out 1～10 hour.The present invention is by changing the ambiance gas flow that burns till in this sintering process, or changes and burn till the active different multiple catalyzer of number of times preparation.
Research according to the inventor, about in burning till the ambiance gas volume and the amount ratio of catalytic amount, the amount of (ambiance gas volume/catalytic amount) than big condition under, can under the optionally condition that reduces not significantly object, obtain active big catalyzer.In addition, the amount at (ambiance gas volume/catalytic amount) also found than little condition under, though obtain the selectivity of object is improved the active catalyzer that suppresses.Like this, by changing the amount ratio of (ambiance gas volume/catalytic amount), the active different multiple catalyzer of preparation, but also have relation, the present invention preferably to obtain 2～4 kinds of multiple catalyzer that activity is different with the number of cutting apart of aftermentioned reactor.
The amount that changes (ambiance gas volume/catalytic amount) is when making the different catalyzer of activity, the unit of ambiance gas flow is that the unit of (ml/ branch), catalytic amount is when (ml), the amount ratio of (ambiance gas volume/catalytic amount) is preferably 0.05～100, more preferably 0.1～50, most preferably in 0.5～10 range.Above-mentioned amount is than less than 0.05 o'clock, and the replacement effect of being detained gas is little, and the gained activity of such catalysts is too little, and above-mentioned amount is than greater than 100 o'clock, increases with respect to the ambiance gas volume of catalyzer, and is unfavorable economically.
In addition, the present invention burns till the number of times preparation when changing the multiple catalyzer of olefin conversion by changing in the sintering process, burns till by the multistage that will burn till with the catalyzer that said temperature, time burn till again, burn till.Each time burnt till preferably and in a single day carried out after the cooling in the gained burned material.Carry out multistage in this wise when burning till, find the catalyzer that makes the activity that has of the catalyzer of multistage reduce more.That is, 2 sections are burnt till catalyst activity and burn till catalyzer than 1 section and reduce, and 3 sections are burnt till catalyst activity and burn till the catalyzer reduction than 2 sections.On the other hand, but find, to the selectivity raising of object along with activity of such catalysts reduces.
When adopting multistage to burn till to make active different multiple catalyzer, relation is also arranged, burn till preferred employing and carry out for 2～4 sections with the number of cutting apart of aftermentioned reactor.In addition, the 2nd section later firing condition can make temperature, time, ambiance gas flow different with the 1st section firing condition, and the 2nd section also can be adopted the same terms to burn till later on.In addition, if adopt above-mentioned multistage to burn till, then can easily prepare active different multiple catalyzer.For example, burn till again, can easily prepare active 4 kinds of different catalyzer by 2 kinds the catalyzer that activity is different.
The present invention can implement above-mentioned burning till by environment for use atmosphere firing furnace.As the ambiance firing furnace, for example, can adopt catalyzer is filled in the fixed-bed reactor, the method that heats from the outside under the circulation of ambiance gas, aforementioned fixation bed bioreactor are the methods of heat exchange type, lead to the method for ambiance gas in retort furnace, lead to the method for ambiance gas etc. to the method for the inner logical ambiance gas of tunnel furnace, to kiln inside.If consider to suppress the ambiance gas flow of delay, preferred catalyst filling in fixed-bed reactor, the method that under the circulation of ambiance gas, heats from the outside, more preferably adopt catalyst filling in the heat exchange type fixed-bed reactor, the method that under the circulation of ambiance gas, heats from the outside.Ambiance gas can use the mixed gas of rare gas elementes such as air and nitrogen except air.Consider from favourable economically viewpoint, can preferably use air.
In addition, the present invention is divided into the reactor catalyst layer of fixed bed tube-type reactor more than 2 layers or 2 layers along tube axial direction, and the reaction zone more than 2 or 2 is set.The number of cutting apart of reactor suppresses more focus more at most easily, forms 2～4 reaction zones but preferably cut apart usually.The length of the reaction zone of being cut apart not necessarily equates, can be random length.For example, when being divided into 2 sections, preceding segment length is L1, back segment length when being L2, and preferably making L1/L2 is 0.1～10, is preferably 0.3～3 especially.The length that the radical of employed reaction tubes, reaction tube diameter, catalyzer are filled etc. are according to operating condition or throughput and difference can suitably determine.
Among the present invention,, fill above-mentioned active different 2 kinds or multiple catalyzer, activity of such catalysts is increased towards Way out by the inlet of unstripped gas cutting apart a plurality of reaction zones more than 2 or 2 of formation in the above-mentioned reactor.Being example by cutting apart the situation that reactor is provided with 2 reaction zones, the active 2 kinds of different catalyzer of preparation, fill active little catalyzer at the reaction zone (hereinafter referred to as the leading portion reaction zone) of unstripped gas inlet side, fill active big catalyzer at the reaction zone (hereinafter referred to as the back segment reaction zone) of outlet side.
When the present invention fills active different 2 kinds or multiple catalyzer to a plurality of reaction zones from the inlet of unstripped gas towards outlet, the catalyst activity of unstripped gas inlet side is 1 o'clock, the catalyst activity of preferred gas outlet side is below 5 or 5, is preferably especially below 3 or 3.With respect to the catalyzer of unstripped gas inlet side, the catalyst activity of pneumatic outlet side is greater than 5 o'clock, the catalyst layer increase in temperature of the reaction zone of outlet side and bad.
In addition, when the present invention uses active different multiple catalyzer, needn't every kind the activity that has of catalyzer all big towards outlet from the unstripped gas inlet, can be the catalyzer of just being filled on the whole, activity relatively increases towards outlet from the unstripped gas inlet.In addition, in each reaction zone, not necessarily fill a kind of catalyzer, also can fill active different multiple catalyzer.Shape, the size of the catalyzer that relevant each reaction zone is filled among the present invention do not have particular restriction, can suitably select known shape, size etc.
The present invention uses in the gas phase catalytic reaction of the gas that contains molecular oxygen, can be that sinolprocess also can be a circulation method by reaction tubes, and this reaction can be implemented under the general condition of using.For example, the mixed gas that comprises rare gas element 20～80 volume % such as propylene 1～15 volume %, molecular oxygen 3～30 volume %, water vapor 0～60 volume %, nitrogen, carbon dioxide gas etc., under 250～450 ℃, the pressure of 0.1～1MPa, with space velocity (SV) 300～5000 o'clock
-1Importing internal diameter is preferably in the catalyst layer that each reaction zone of each reaction tubes of 15～50mm fills.Yet in order further to enhance productivity, the present invention also can be under the high loading reaction conditions, for example, turns round under higher material concentration or high space velocity condition.
Embodiment
Below enumerate embodiments of the invention and illustrate in greater detail the present invention, need not explain certainly, the present invention is not limited to such embodiment.In addition, following example 1, example 4 are embodiments of the invention, and example 2, example 3 and example 5, example 6 are comparative examples.
Example 1
(preparation of catalyzer 1)
Among the pure water 500ml that ammonium paramolybdate 105.5g is dissolved in heated.Iron nitrate 10.1g, Xiao Suangu 97.0g are dissolved among the pure water 100ml that heated.The limit is fully stirred on above-mentioned solution limit mixes at leisure.
Then, under heating, borax 0.96g and saltpetre 0.51g are dissolved in the 40ml pure water, and are added in the above-mentioned slurries.Add silicon-dioxide 72.9g then, fully stir.
Then, in the 20ml pure water, add nitric acid 2.7ml, and add Bismuth trinitrate 24.1g, mix.Behind this slurries heat drying, in air ambient atmosphere in 300 ℃ of thermal treatments of carrying out 1 hour.The granular solids that pulverizing obtains is machined to the tablet of diameter 5mm, high 4mm with compression molding.
Then, filling molding body 1000ml in the heat exchange type fixed-bed reactor divides bubbling air as ambiance gas with 5000ml/.From indirect heating, carry out burning till in 8 hours at 500 ℃, make composite oxide catalysts.
By the catalyzer that adds raw material calculating is the composite oxides with following atomic ratio.
Mo∶Bi∶Co∶Fe∶Na∶B∶K∶Si＝12∶1∶6.6∶0.6∶0.1∶0.2∶0.1∶24
(preparation of catalyzer 2)
Except dividing bubbling air as the ambiance gas with 1000ml/, the preparation of other and above-mentioned catalyzer 1 is identical, the preparation composite oxide catalysts.
(oxidizing reaction)
Having thermopair, diameter is that the unstripped gas inlet side of the stainless steel reaction tubes of 25mm is filled the above-mentioned catalyzer 2 of 500ml, fills 1000ml catalyzer 1 at the outlet side of unstripped gas.Enter the mouth with SV 800hr from above-mentioned reaction tubes
-1Feed the mixed gas of propylene 8 volume %, air 67 volume % and water vapor 25 volume %, carry out reaction in 1000 hours continuously.Be shown in table 1 the performance of initial reaction stage with through 1000 hours later performances.
Example 2
Except only using 1500ml catalyzer 1, other and example 1 are similarly reacted.Be shown in table 1 the performance of initial reaction stage with through 1000 hours later performances.
Example 3
Except only using 1500ml catalyzer 2, other and example 1 are similarly reacted.Be shown in table 1 the performance of initial reaction stage with through 1000 hours later performances.
Table 1
| Reaction times (hour) | Temperature of reaction (℃) | Transformation efficiency (mole %) | Selection rate (mole %) | Yield (mole %) | 1 layer of temperature of catalyzer (℃) | 2 layers of temperature of catalyzer (℃) | |
| Example 1 | Initial stage | ??310 | ??98.2 | ??95.0 | ??93.3 | ??382 | ??375 |
| ??1,000 | ??311 | ??98.1 | ??95.2 | ??93.4 | ??381 | ??378 | |
| Example 2 | Initial stage | ??300 | ??98.2 | ??93.8 | ??92.1 | ??428 | ??- |
| ??1,000 | ??305 | ??97.9 | ??93.9 | ??91.9 | ??430 | ??- | |
| Example 3 | Initial stage | ??330 | ??97.5 | ??95.3 | ??92.9 | ??- | ??402 |
| ??1,000 | ??335 | ??97.2 | ??94.8 | ??92.1 | ??- | ??405 |
Example 4
(catalyzer 3 preparations)
Among the pure water 500ml that ammonium paramolybdate 105.5g is dissolved in heated, iron nitrate 10.1g, Xiao Suangu 97.0g are dissolved among the pure water 100ml that heated.The limit is fully stirred on above-mentioned solution limit mixes at leisure.
Then, under heating, borax 0.96g and saltpetre 0.51g are dissolved in the 40ml pure water, are added in the above-mentioned slurries, add silicon-dioxide 72.9g then, fully stir.
Then, in the 20ml pure water, add nitric acid 2.7ml, and add Bismuth trinitrate 24.1g, mix.After these slurries are carried out heat drying, in air ambient atmosphere, carry out thermal treatment in 1 hour in 300 ℃.The granular solids that pulverizing obtains uses compression molding to be machined to the tablet of diameter 5mm, high 4mm.
Then, filling molding body 1000ml in the heat exchange type fixed-bed reactor divides bubbling air as ambiance gas with 2500ml/.From indirect heating, carry out burning till in 4 hours at 505 ℃, make composite oxide catalysts.
By the catalyzer that adds raw material calculating is the composite oxides that following atomic ratio is arranged.
Mo∶Bi∶Co∶Fe∶Na∶B∶K∶Si＝12∶1∶6.6∶0.6∶0.1∶0.2∶0.1∶24
(preparation of catalyzer 4)
In the heat exchange type fixed-bed reactor, fill (catalyzer 3) 1000ml.Divide bubbling air as ambiance gas with 2500ml/.From indirect heating, carry out burning till in 4 hours at 505 ℃, make composite oxide catalysts.
(oxidizing reaction)
Having thermopair, diameter is that the unstripped gas inlet side of the stainless steel reaction tubes of 25mm is filled the above-mentioned catalyzer 4 of 500ml, fills 1000ml catalyzer 3 at the unstripped gas outlet side.Enter the mouth with SV 1800hr from above-mentioned reaction tubes
-1Feed the mixed gas of propylene 8 volume %, air 67 volume % and water vapor 25 volume %, carry out reaction in 1000 hours continuously.Be shown in table 2 the performance of initial reaction stage with through the performance after 1000 hours.
Example 5
In example 4, except only using 1500ml catalyzer 3, other and example 5 are similarly reacted.Be shown in table 2 the performance of initial reaction stage with through the performance after 1000 hours.
Example 6
In example 4, except only using 1500ml catalyzer 4, other and example 5 are similarly reacted.Be shown in table 2 the performance of initial reaction stage with through the performance after 1000 hours.
Table 2
| Reaction times (hour) | Temperature of reaction (℃) | Transformation efficiency (mole %) | Selection rate (mole %) | Yield (mole %) | 3 layers of temperature of catalyzer (℃) | 4 layers of temperature of catalyzer (℃) | |
| Example 4 | Initial stage | ??311 | ??98.1 | ??94.8 | ??93.0 | ??391 | ??378 |
| ??1,000 | ??312 | ??97.9 | ??95.1 | ??93.1 | ??390 | ??380 | |
| Example 5 | Initial stage | ??305 | ??97.8 | ??93.5 | ??91.4 | ??421 | ??--- |
| ??1,000 | ??306 | ??97.7 | ??93.4 | ??91.3 | ??425 | ??--- | |
| Example 6 | Initial stage | ??322 | ??98.1 | ??94.2 | ??92.4 | ??--- | ??408 |
| ??1,000 | ??326 | ??97.9 | ??94.1 | ??92.1 | ??--- | ??412 |
Industrial applicability
The inventive method can be widely used in gas by containing molecular oxygen with the alkene footpath, especially propylene carries out catalytic gas phase oxidation, and is steady in a long-term and prepare with high yield unsaturated aldehyde, especially methacrylaldehyde and unsaturated carboxylic acid, especially acrylic acid. Prepared unsaturated aldehyde and unsaturated carboxylic acid are using in the purposes widely as the monomer of the functional resins such as the monomer of the raw material of various chemicals, common resins, water-absorbing resins, flocculating agent, tackifier etc.
Claims (5)
1. the preparation method of unsaturated aldehyde and unsaturated carboxylic acid, it is characterized in that, this method is used the fixed bed tube-type reactor, the gas that the alkene utilization is contained molecular oxygen carries out catalytic gas phase oxidation and prepares unsaturated aldehyde and unsaturated carboxylic acid, described fixed bed tube-type reactor has been filled the composite oxide catalysts that contains molybdenum and bismuth, in this method
(A) use active different multiple catalyzer as above-mentioned composite oxide catalysts, described multiple catalyzer is to change the environmental gas flow to burn till the catalyzer that number of times makes with the amount of catalytic amount than burning till or changing,
(B) along the tube axial direction in the reactor a plurality of reaction zones are set,
(C) fill described multiple catalyzer at each reaction zone, activity of such catalysts is increased towards Way out from the inlet of unstripped gas.
2. the described preparation method of claim 1 is characterized in that, described composite oxide catalysts is the catalyzer with following formula (1):
Mo
aBi
bCo
cNi
dFe
eX
fY
gZ
hQ
iSi
jO
k??????????????(1)
(in the formula, X is at least a kind of element that is selected among Na, K, Rb, Cs and the Tl, Y is at least a kind of element that is selected among B, P, As and the W, Z is at least a kind of element that is selected among Mg, Ca, Zn, Ce and the Sm, Q represents halogen, in addition, a～j represents each atoms of elements ratio, when a=12,0.5≤b≤7,0≤c≤10,0≤d≤10 (1≤c+d≤10), 0.05≤e≤3,0.0005≤f ≤～3,0≤g≤3,0≤h≤1,0≤i≤0.5,0≤j≤40, k is the numerical value that satisfies other element states of oxidation).
3. claim 1 or 2 described preparation methods is characterized in that, the activity that 2 kinds or multiple composite oxide catalysts have is 1 o'clock at the catalyst activity of unstripped gas inlet side, and the activity of outlet side is below 5 or 5.
4. claim 1,2 or 3 described preparation methods is characterized in that the quantity of reaction zone is 2～4.
5. any described preparation method in the claim 1～4 is characterized in that alkene is propylene, and unsaturated aldehyde and unsaturated carboxylic acid are respectively propenal and vinylformic acid.
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| JP2003405046 | 2003-12-03 | ||
| JP405046/2003 | 2003-12-03 |
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| CN1697794A true CN1697794A (en) | 2005-11-16 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105899481A (en) * | 2013-11-11 | 2016-08-24 | 巴斯夫欧洲公司 | Process for preparing unsaturated aldehyde and/or unsaturated carboxylic acid |
| CN113573811A (en) * | 2019-03-29 | 2021-10-29 | 日本化药株式会社 | Method for producing unsaturated aldehyde |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4970986B2 (en) * | 2007-03-08 | 2012-07-11 | 株式会社日本触媒 | Method for producing composite oxide catalyst and method for producing unsaturated aldehyde and / or unsaturated carboxylic acid using the catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| SG50687A1 (en) * | 1989-12-06 | 1998-07-20 | Nippon Catalytic Chem Ind | Process for producing methacrolein and methacrylic acid |
| JPH044048A (en) * | 1990-04-19 | 1992-01-08 | Mitsubishi Rayon Co Ltd | Production of catalyst for synthesizing unsaturated aldehyde and unsaturated acid |
| JP3139285B2 (en) * | 1994-06-20 | 2001-02-26 | 住友化学工業株式会社 | Method for producing acrolein and acrylic acid |
| JP3775872B2 (en) * | 1996-12-03 | 2006-05-17 | 日本化薬株式会社 | Method for producing acrolein and acrylic acid |
| JP3790080B2 (en) * | 2000-01-25 | 2006-06-28 | 三菱レイヨン株式会社 | Catalyst for synthesizing methacrolein and methacrylic acid, and method for producing methacrolein and methacrylic acid |
| US6645905B2 (en) * | 2001-04-25 | 2003-11-11 | Rohm And Haas Company | Annealed and promoted catalyst |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105899481A (en) * | 2013-11-11 | 2016-08-24 | 巴斯夫欧洲公司 | Process for preparing unsaturated aldehyde and/or unsaturated carboxylic acid |
| CN113573811A (en) * | 2019-03-29 | 2021-10-29 | 日本化药株式会社 | Method for producing unsaturated aldehyde |
| CN113573811B (en) * | 2019-03-29 | 2023-12-08 | 日本化药株式会社 | Process for producing unsaturated aldehyde |
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