CN102992977B - Preparation method of acrolein - Google Patents
Preparation method of acrolein Download PDFInfo
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- CN102992977B CN102992977B CN201110265247.2A CN201110265247A CN102992977B CN 102992977 B CN102992977 B CN 102992977B CN 201110265247 A CN201110265247 A CN 201110265247A CN 102992977 B CN102992977 B CN 102992977B
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Abstract
The invention relates to a preparation method of acrolein. According to the invention, a fixed-bed single-pipe reactor is adopted. A reaction raw material is preheated, and is delivered into a reactor. A Mo-Bi series multi-metal oxide catalyst is loaded in the reactor. The composition of the catalyst can be represented by the general formula (I): MoaBibFecCodCseCufSigAhBiOj (I). With the production method provided by the invention, single-pipe reactor local heat accumulation can be effectively reduced, hot spot formation can be inhibited, and catalyst sintering is prevented. The method has the characteristics of high reaction activity, high selectivity, and long service life. With the method, device long-period stable operation can be satisfied.
Description
Technical field
The present invention relates to the preparation method that a kind of propylene or selective isobutene oxidation generate corresponding unsaturated aldehyde, be particularly useful for Propylene Selectivity to be oxidized to propenal.
Background technology
At present, industrially mainly with propylene two-step oxidation legal system vinylformic acid, conventionally adopt fixed-bed reactor, propylene initial oxidation becomes propenal, and propenal is reoxidised into vinylformic acid.Propylene gas phase catalytic oxidation reaction is strong exothermal reaction, in beds, can produce focus, the heat that moment is gathered is constantly accumulated, by cause catalyst activity component loss, come off, to such an extent as to catalyst activity reduction, the lost of life, and cause, because over oxidation reacts the formation that aggravates by product, even causing uncontrolled reaction, make sintering of catalyst.
The progress > > (petrochemical complex of < < oxidation acrylic acid synthesizing process and catalyzer, the 39th the 7th phase of volume in 2010) appearance of social focus also can make catalyst damage evil, shortens the work-ing life of catalyzer.The 80000 tons/year of acroleic acid devices of take are example, and propylene oxidation is prepared and in acrolein reaction device, needed more than 25000 tubulation, acrolein oxidation to prepare in vinylformic acid reactor also to need more than 25000 tubulation, load altogether more than 100 ton of propenal, vinylformic acid catalyzer.More than 50000 reaction tubes, the filling of catalyzer guarantees not fill empty certain difficulty that has, if because focus is crossed the very fast sintering of high catalyst, again change in a short time agent, it is huge can envisioning its financial loss again; In addition, for propenal, acrylic acid production, carry out as much as possible under cold condition, because reaction needed salt bath heating, its energy consumption that maintains production is also huge spending; Due to the generation of focus, high temperature resistant to the requirement of reaction tubes tubing, for up to ten thousand reaction tubess, tubing expense is exactly a very large cost.Therefore,, if effectively suppress the generation of beds focus, can bring huge economic benefit to large-scale commercial production.
At present, there is several different methods can reduce or avoid gathering and peroxidation of focus, can be from the viewpoint of the improvement of reaction unit and the improvement of catalyzer two.Aspect catalyzer, as: Japanese patent laid-open 04-217932 has proposed a kind of method that suppresses the appearance of focus or the hot polymerization collection on focus, by preparing the multiple catalyzer with different possessive volumes, and the mode reducing to outlet one side catalyzer possessive volume from unstripped gas inlet side, fill successively reaction tubes, but the possessive volume of catalyzer is subject to the restriction of reaction tube diameter, and it is also very difficult that multiple catalysts is filled into reaction tubes.CN97191983.6 prepares the multiple catalyst-loaded catalyst layer that arranges in reaction tubes with different activities, according to the entrance from unstripped gas, to the active order uprising of outlet, arranges above-mentioned several catalyst-loaded.Also the method that has other, for example, inert substance and catalyst mix, reduce the activity of catalyzer, be loaded into reactor inlet place, Japanese Unexamined Patent Publication 10614/1972 is sneaked into heat resistanceheat resistant point to form catalyzer is inert substance with by catalyst dilution in catalyzer, and Japanese Patent Publication 36739/1987 is made catalyzer the method for tubulose.There is again the catalyst loading that unstripped gas ingress reduces by active ingredient.CN200510007929.8 provides a kind of catalyzing propone aldehyde gaseous oxidation system acrylic acid catalyzer, described catalyzer comprises molybdenum and vanadium, also comprise at least one volatile catalyst toxic component, its amount is 10 to 100ppb quality through ion chromatography measurement, this catalyzer can reduce the temperature of hot spot, and suppresses the reduction of the reaction efficiency of thermal destruction.Specific practice is that, by the volatility toxic component of specified quantitative being comprised and originally having in highly active catalyzer, catalytic activity declines momently, can reduce the temperature of hot spot.CN97104224.1 is by after dividing catalytic active component and being loaded on carrier, calcines the generation that the catalyzer of load sharing suppresses focus, and the median size of catalyzer is 4～16mm, and the median size of carrier is 3～12mm, and calcining temperature is 500～600 ℃.CN01111960.8 provides the catalyzer of a kind of Mo-W-Bi-Fe of containing, this catalyzer, by the mode that changes the kind of possessive volume calcining temperature and/or alkali metal and/or quantity and increase to outlet one side from the inlet side of unstripped gas according to catalyst activity, is filled reaction zone successively with described multiple types catalyzer.Catalyzer reaction tubes axially on be at least divided into two-layerly, this catalyzer is the multiple types catalyzer with different activities level, can be by changing calcining temperature and/or wherein kind and/or the quantity of alkali metal obtain.The appearance of focus or the hot polymerization collection on focus are effectively suppressed.CN00122609.6 provides a kind of PROPENE IN GAS PHASE OXIDATION to produce propenal and acrylic acid, use the oxide catalyst containing Mo-Bi-Fe compound, described catalyzer is filled in multitubular reactor of fixed bed, and the method can generate propenal and vinylformic acid with high stable yield in long-time.The method is characterized in that in each tubular reactor that configures vertically two or more reaction zones that each district's filling different catalysts is filled out catalyzer Bi and/or Fe content and reduced with the ratio of Mo content from gas inlet end to gas outlet end.CN03148701.7 provides a kind of supported catalyst, and this support of the catalyst has multidimensional structure, with the self supporting type multidimensional carrier structure of premolding (as foam, one-piece construction, fabric or other) or comprise Nb
2o
5, trichroite, partially stabilized zirconium white, ceramic fiber or its mixture carrier, in succession on described carrier deposition comprise any order at least one molybdenum-containing layer, at least one containing vanadium layer, at least one forms load carrier containing tellurium layer and at least one containing the catalyst composition of X layer, after roasting supported catalyst.For paraffinic hydrocarbons, be oxidized to unsaturated carboxylic acid and become unsaturated nitrile with ammoxidation of paraffins, enough transformation efficiencys and applicable selectivity are provided.CN02822228.8 discloses a kind of composite oxide catalysts, is the catalyzer that the olefin oxidation that contains molybdenum and bismuth is used, and its specific surface area is at 5～25m
2/ g, its pore volume are in the scope of 0.2～0.7cc/g, and during its pore diameter distributes, it is the more than 30% of total pore volume that fine pore (diameter) has the pore volume that the pore of 0.03～0.1 μ m accounts for, have pore volume that the pore of 0.1～1 μ m accounts for be in total pore volume more than 20% and to compare the little ratio of 0.03 μ m be below 10%.To take propenal that Mo, Bi, halogen be essential component or the composite oxide catalysts of Methylacrylaldehyde gaseous oxidation.There is above-mentioned character wherein, and be to using Mo, Bi, Fe, Si, basic metal thallium as essential component, the composite oxide catalysts that Co, Ni, Mg, Ca, Zn, Ce, Sm, halogen, P, As, W are any composition and its preparation method and using method.
All there is a problem in the method that above-mentioned inhibition focus produces, the catalyzer being filled in reaction tubes has all been diluted with various forms from the inlet to the outlet, both after having made catalyst runs some cycles, active decline also can not change thinning ratio, catalyzer also cannot provide higher activity again, not only load, dismantle, separated, reclaim catalyzer and make troubles, and can reduce the reactive behavior of catalyzer, especially industrial long-term operation catalyst activity reduction is faster, affects catalyst life.Therefore, need to use a kind of Heat stability is good, can effectively suppress the high activated catalyst of focus, to meet the needs of industrial propylene high-speed, highly selective oxidation acrolein.In addition, under hot conditions, in catalyzer, part active ingredient molybdenum loses because of distillation from catalyst surface.Washing away also of propylene, air and water vapour mixed airflow can make the loss of active component in catalyzer.For suppressing the loss of molybdenum distillation, cause active decay, CN1121504, by mixing copper component and zirconium and/or Titanium and/or the Cerium with specified particle diameter and specific surface area, can suppress dissipation effect and the over reduction of molybdenum composition; The effect that CN1445020 adds a small amount of tellurium to play to stablize free molybdic oxide and molybdic acid copper crystal structure, sublimation and the over reduction of molybdenum suppress to some extent; CN1583261 be take molybdenum, vanadium, copper, tungsten and/or niobium as main ingredient, and the composite oxides or its hopcalite that form with other element form the loss that catalyzer suppresses molybdenum.
Summary of the invention
The object of this invention is to provide the preparation method that corresponding unsaturated aldehyde is produced in a kind of propylene or selective isobutene oxidation.Different from the method for above-mentioned reduction focus, there is gradient difference from inside to exterior active concentration of component in the present invention's granules of catalyst used, can effectively reduce fixed bed single tube reactor localized heat and gather, and suppresses emerging and the loss of active ingredient molybdenum of focus.Catalyzer is easy-sintering not, and under high-speed part, this catalyzer has that activity and selectivity is high, the feature of good stability.
The method of Propylene Selectivity oxidation acrolein provided by the invention is as follows: adopt fixed bed single tube reactor; Reaction raw materials propylene, water, air more than 130 ℃ enter reactor after preheating through preheater, salt bath heating, and reaction process condition is: 300～335 ℃ of salt temperatures, preferably 305～325 ℃; Air speed 800～2200h
-1, preferred 800～1600h
-1, feed composition: propylene 7～12 volume %, air 69～73 volume %, water vapour 15～20%; It is multi-metal-oxide catalyst that Mo-Bi is housed in reactor, and the chief component of this multi-metal-oxide catalyst is by general formula (I) expression below
Mo
aBi
bFe
cCo
dCs
eCu
fSi
gA
hB
iO
j (I)
Wherein: Mo is molybdenum, Bi is bismuth, and Fe is iron, and Co is cobalt, and Cs is caesium, and Cu is copper, and Si is silicon, and silicon is the carrier adding in catalyzer, and A is at least one element being selected from zinc, manganese, lanthanum, niobium, zirconium, vanadium; B is at least one element being selected from magnesium, strontium and tungsten; O is oxygen; A, b, c, d, e, f, g, h, i represent respectively each element atomic ratio, 12≤a≤14 wherein, 2≤b≤8, preferably 2.5≤b≤6; 0.1≤c≤5, preferably 0.2≤c≤3; 0.5≤d≤5, preferably 0.5≤d≤3.5; 0.05≤e≤4, preferably 0.1≤e≤2; 0.5≤f≤3,0.5≤g≤50,0.1≤h≤3,0.1≤i≤2, j is the numerical value by the oxygen decision of each oxide compound, described catalyzer has multilayer structure, outer double-layer structure in, every layer of catalyzer chief component is identical, but the total content of one or more in silicon-dioxide, aluminum oxide or silicon carbide is different, the total content of one or more in outer silicon-dioxide, aluminum oxide or silicon carbide is than the height of internal layer parent, and in molar content, each component concentration concentration ratio internal layer parent of catalyst outer layer is low.
Catalyzer of the present invention is multilayer structure, mainly by add the materials such as different amount silicon-dioxide, aluminum oxide, silicon carbide to be achieved concentration difference at ectonexine, that is to say, the total content of one or more in outer silicon-dioxide, aluminum oxide or silicon carbide is higher than internal layer parent, in molar content, outer each constituent content is lower by 0.1～28% than this constituent content of internal layer, and preferably 0.5～15%.Catalyst inner layer of the present invention also can not add silicon.
In catalyzer of the present invention, main active ingredient comprises Mo, Bi, Fe, Co, Cs, Cu.Co mainly plays activation oxygen; In catalyzer, add basic metal Cs and can regulate the acidity of catalyzer, make catalyst components when coprecipitation reaction, be difficult for occurring to make poor catalyst activity because of particle agglomeration, adding of Cs wants appropriate, and addition too much makes (Mo+Bi) and the too small meeting of Cs ratio cause catalyst activity reduction, poor heat stability; Preferably the amount of Mo+Bi and Cs keeps certain ratio, and (a+b)/e > 10, and catalyzer has good thermostability; In the situation that bed temperature of reaction raises suddenly, short period of time inner catalyst is difficult for being sintered, after reaction some cycles, improve salt bath heating temperature, salt temperature higher than 345 ℃ of conditions under, reaction bed temperature is more than 380 ℃, active ingredient Mo, Bi, Fe, Co, Cs, Cu etc. should not run off, and it is activity stabilized that catalyzer can keep, thereby embody good thermostability; Help part or all and main active ingredient of component zinc, manganese, lanthanum, niobium, zirconium, vanadium, magnesium, strontium and tungsten, by coprecipitation reaction, good synergy can occur, make the resistant to elevated temperatures better effects if of catalyzer; The preferred lanthanum of A in the present invention (I), lanthanum and molybdenum, cobalt, copper etc. can form stable crystal phase structure, thereby suppressing part active ingredient molybdenum loses because of distillation from catalyst surface, before and after catalyst reaction, active ingredient molybdenum content is substantially constant, delay active deterioration rate, catalyst activity and good stability.0.1≤h≤2 in general formula (I).In addition, the granules of catalyst with multilayer structure reduces successively from inside to exterior active concentration of component, effectively reduces single tube reactor localized heat and gathers, and suppresses emerging of focus, and catalyst activity is stable, can bear long period steady running.
Used catalyst of the present invention adopts common preparation method, as adopted following step preparation.
First, Kaolinite Preparation of Catalyst internal layer parent:
(1) will contain Mo, Bi, the compound dissolution of Fe, Co, Cu and Cs also mixes, and forms active ingredient slurries (a);
(2) again by A in general formula (I)
hb
ieach elementary composition compound dissolution relating to also mixes, as auxiliary material slurries (b);
(3) active ingredient slurries (a) are mixed with auxiliary material slurries (b) and carry out forming internal layer parent slurries after co-precipitation, dry, moulding, roasting obtains catalyst inner layer parent;
Secondly, method according to Kaolinite Preparation of Catalyst internal layer parent slurries is prepared outer layer catalyst slurries, in outer layer catalyst slurries preparation process, add one or more in silicon-dioxide, aluminum oxide or silicon carbide, make in outer layer catalyst slurries each concentration of element lower than the concentration of this element of adjacent inner layer;
Finally, the outer layer catalyst of preparation is coated on catalyst inner layer parent successively, after roasting, obtains finished catalyst.
Catalyst inner layer parent of the present invention after moulding and outer all need to be at 350～580 ℃ after coating roasting 3～10h, compare not the catalyzer of roasting respectively, repeatedly roasting can improve activity and the stability of catalyzer.Can be that open roasting can be also enclosed roasting, calcination atmosphere can be the rare gas elementes such as helium, nitrogen, argon gas.
Catalyst layer easily chaps during thick roasting very much, for fear of be full of cracks be preferably in apply after 55～125 ℃ of oven dry, and then roasting.The outer layer catalyst bed thickness that is coated on internal layer parent is 1.0～2.5mm, preferably 1.5～2mm.
The compound of each component of catalyzer of the present invention can be used nitrate, ammonium salt, vitriol, oxide compound, oxyhydroxide, muriate, acetate of each element etc.
After catalyst inner layer parent slurries of the present invention are dried, conventionally preferably adopt the forming methods such as extrusion moulding, granulating and forming, compression molding to be processed into spherical, hollow spheres, ellipticity, cylindric, hollow circuit cylinder etc., preferably hollow circuit cylinder or spherical.
When multi-metal-oxide catalyst of the present invention applies, preferably use binding agent, make ectonexine catalyzer bonding more firm.At internal layer parent, under rolling condition, spray binding agent and infiltrate surface, then the outer layer catalyst powder for preparing of spraying, also internal layer parent can be put into the outer layer catalyst slurries that the prepare coating of rolling.Binding agent is selected from one or more in water, alcohols or ethers.Alcohols is as ethanol, propyl alcohol, butanols; Ethers is as ether and butyl ether.
Each of catalyzer of the present invention layer surface be uneven, surface irregularity preferably, is conducive to apply, and between ectonexine, bonding is more firm.
The present invention, in order to improve intensity, the efflorescence degree of catalyzer, can add one or more in glass fibre, graphite, pottery or various whisker in above-mentioned outer layer catalyst.
The present invention has bilayer structure, and internal layer also can be called internal layer parent.
The multi-metal-oxide catalyst with multilayer structure of the present invention can directly be used, and also can be carried on inert support and use.Related inert support can be one or more mixture of aluminum oxide, silicon-dioxide, silicon carbide etc.
At the initial stage of feeding intake, because catalyzer initial reaction activity is very high, so be easy to produce focus or produce heat built-up on fixed bed single tube reactor bed, catalyzer is easy to sintering, and this loses concerning suitability for industrialized production propenal vinylformic acid is very serious.In raw material, pass into a certain amount of water vapour, because specific heat of water is large, can take away a large amount of reaction heat, but water vapour input greatly often makes catalyst member active ingredient solution-off, make active decline.
The present invention has the multi-metal-oxide catalyst of multilayer structure by preparation, make granules of catalyst have gradient difference from inside to exterior active concentration of component, and the every outer active ingredient concentration of catalyzer is lower than its adjacent inner layer active ingredient concentration, like this, under high-speed reaction conditions, because the active ingredient concentration of catalyzer outside surface is low, so corresponding activity is also low, therefore can effectively suppress emerging of focus and gathering of heat, reduce the growing amount of by product (as hydrocarbon), improve the selectivity of object product.This has double-deck catalyzer and has good water repelling property.And when catalyst runs is after for some time, catalyzer has release effects, under mixed airflow long period is washed away, even if catalyst surface active component has part to run off, but because internal layer catalyst active ingredient concentration is higher, can play supplementary effect, so can keep catalyst activity lasting stability.
The method of propenal is prepared in Propylene Selectivity provided by the invention oxidation, can effectively reduce fixed bed single tube reactor localized heat and gather, and suppresses emerging and the loss of active ingredient molybdenum of focus.Catalyzer is easy-sintering not, and under high-speed part, this catalyzer has that activity and selectivity is high, the feature of good stability.
Embodiment
The method of Propylene Selectivity oxidation is described with specific embodiment, but scope of the present invention is not limited to these embodiment below.The propylene that following examples adopt is the high density propylene of propylene content >=99.6% (volume fraction).
Mole number * 100% of propylene in the total mole number/raw material of propylene conversion (%)=propylene reaction
Propenal selectivity (%)=propylene is converted into total mole number * 100% of propenal mole number/propylene reaction
Embodiment 1
The preparation of catalyzer 1
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active ingredient slurries (a)
Under agitation condition, get 183.6 grams of ammonium molybdates, 27.97 grams of cupric nitrates, 23.4 grams of cesium nitrates and be dissolved in (water temperature is more than 65 ℃) in 1000ml pure water, obtain slurries (1), then get 217 grams of Bismuth trinitrates and be dissolved in rare nitric acid, obtain solution (2).Get again 55.9 grams of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs of 77.6 grams of iron nitrates, under agitation condition, be dissolved in (water temperature is more than 65 ℃) in 1000ml pure water, obtain slurries (3).Then, slurries (1) mix with slurries (2), then add ammoniacal liquor to regulate pH value to alkalescence, obtain slurries (4), after 20 minutes, lentamente slurries (3) are added in slurries (4), and add 12 grams of silicon-dioxide, 80 ℃ of strong stirrings 2 hours simultaneously.
(2) preparation of auxiliary material slurries (b)
Under heating and stirring, 4.7 grams of ammonium meta-vanadates, 38 grams of zirconium nitrates and 15 grams of magnesium nitrates are dissolved in to (water temperature is more than 65 ℃) in 500ml pure water, be uniformly mixed.
(3) preparation of catalyst Precursors
Active ingredient slurries (a) are carried out to 1 hour post-heating of coprecipitation reaction with auxiliary material slurries (b) at 80 ℃ to be dried, in nitrogen with 160 ℃ of thermal treatments 3 hours, then through banded extruder extrusion molding, be the hollow columnar particle of φ 4.5 * 5mm, dry rear 450 ℃ of roastings 4 hours for 85 ℃, make catalyst Precursors, this catalyst Precursors consists of: Mo
13bi
5.6fe
2.4co
2.4cs
1.5cu
1.5zr
1.4v
0.5mg
1si
2.85
Step 2: Kaolinite Preparation of Catalyst is outer
(1) preparation of active ingredient slurries (a)
Preparation with active ingredient slurries (a) in embodiment 1 catalyst inner layer parent is identical.
(2) preparation of auxiliary material slurries (b)
Preparation with auxiliary material slurries (b) in embodiment 1 catalyst inner layer parent is identical.
(3) preparation of catalyst outer layer
Active ingredient slurries (a), auxiliary material slurries (b) are carried out to 50 minutes post-heating of coprecipitation reaction with 26 grams of silica powders to be dried, in nitrogen with 160 ℃ of thermal treatments 3 hours, then 450 ℃ of roastings are 4 hours, through pulverizing, grind, sieving, process to obtain catalyst outer layer powder.
Step 3: Kaolinite Preparation of Catalyst 1
The catalyst inner layer parent of step 1 preparation is placed in to round bottom container, under container rotation condition, to catalyst Precursors, spray ethanolic soln, under the condition of fully wetting catalyst inner layer parent, stop operating, put it into rapidly in the round bottom container of the outer layer catalyst powder that is placed with step 2 gained of another rotation, apply, coat-thickness is at 1.0～2.0mm, and 75 ℃ of oven dry of gained catalyzer obtain catalyzer 1 for 4 hours by 450 ℃ of roastings.Propylene oxidation method
Fixed bed single tube reactor internal diameter 25mm, inside establish thermopair, reactor feedstocks gas inlet side packs the above-mentioned catalyzer 1 of 35ml into, and reaction raw materials propylene, water, air enter reactor after 150 ℃ of preheatings of preheater, salt bath heating, oxidizing reaction processing condition are: 310 ℃ of salt bath heating temperature.From above-mentioned reaction tubes ingress with air speed 1050h
-1import the mixed gas of propylene 9 volume %, air 72 volume %, water vapour 19 volume %.React (following examples are identical with the comparative example reaction times) after 20 hours 368 ℃ of hot(test)-spot temperatures, propylene conversion 98.4%, propenal selectivity 87.1%.
Comparative example 1
The internal layer parent of catalyzer 1 of take is comparative catalyst 1, through banded extruder extrusion molding, is then the hollow columnar particle of φ 4.5 * 5mm.Propylene oxidation method is with embodiment 1.376 ℃ of hot(test)-spot temperatures, propylene conversion 98.8%, propenal selectivity 85.2%.
Comparative example 2
The skin of catalyzer 1 of take is comparative catalyst 2, through banded extruder extrusion molding, is then the hollow columnar particle of φ 4.5 * 5mm, and propylene oxidation method is with embodiment 1.367 ℃ of hot(test)-spot temperatures, propylene conversion 96.8%, propenal selectivity 85.0%.
Embodiment 2
The preparation of catalyzer 2
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active ingredient slurries (a)
Under agitation condition, get 169.5 grams of ammonium molybdates, 37.2 grams of cupric nitrates, 20.2 grams of cesium nitrates and be dissolved in (water temperature is more than 65 ℃) in 1000ml pure water, obtain slurries (1), then get 310.5 grams of Bismuth trinitrates and be dissolved in rare nitric acid, obtain solution (2).Get again 93.1 grams of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs of 97 grams of iron nitrates, under agitation condition, be dissolved in (water temperature is more than 65 ℃) in 1000ml pure water, obtain slurries (3).Then, slurries (1) mix with slurries (2), then add ammoniacal liquor to regulate pH value to alkalescence, obtain slurries (4), after 20 minutes, lentamente slurries (3) are added in slurries (4), and add 8 grams of silicon-dioxide, 80 ℃ of strong stirrings 2 hours simultaneously.
(2) preparation of auxiliary material slurries (b)
Under heating and stirring, 35.7 grams of zinc nitrates and 29.3 grams of strontium nitrates are dissolved in to (water temperature is more than 65 ℃) in 500ml pure water, be uniformly mixed.
(3) preparation of catalyst Precursors
Active ingredient slurries (a) are carried out to 1 hour post-heating of coprecipitation reaction with auxiliary material slurries (b) at 80 ℃ to be dried, in nitrogen with 160 ℃ of thermal treatments 3 hours, then with banded extruder, be squeezed into the ball shape that diameter is 2mm, dry rear 500 ℃ of roastings 4 hours for 90 ℃, make catalyst Precursors, this catalyst Precursors consists of:
Mo
12Bi
8Fe
3Co
4Cs
1.3Cu
2Zn
1.5Sr
1.4
Step 2: Kaolinite Preparation of Catalyst is outer
(1) preparation of active ingredient slurries (a)
Preparation with active ingredient slurries (a) in embodiment 2 catalyst inner layer parents is identical.
(2) preparation of auxiliary material slurries (b)
Preparation with auxiliary material slurries (b) in embodiment 2 catalyst inner layer parents is identical.
(3) preparation of catalyst outer layer
Active ingredient slurries (a), auxiliary material slurries (b) are carried out answering 50 minutes post-heating dry after co-precipitation with 46 grams of silica powders, in nitrogen with 160 ℃ of thermal treatments 3 hours, then 500 ℃ of roastings are 4 hours, through pulverizing, grind, sieving, process to obtain catalyst outer layer powder.
Step 3: Kaolinite Preparation of Catalyst 2
The catalyst inner layer parent of step 1 preparation is placed in to round bottom container, under container rotation condition, to catalyst Precursors, spray ethanolic soln, fully wetting catalyst inner layer parent, put it into rapidly in the round bottom container of the catalyst outer layer that is placed with step 2 gained of another rotation, apply, coat-thickness stops applying when 0.5～2.0mm, and 95 ℃ of oven dry of gained catalyzer obtain catalyzer 2 for 3 hours by 500 ℃ of roastings.
Propylene oxidation method
In fixed bed single tube reactor, pack the above-mentioned catalyzer 2 of 35ml into, 315 ℃ of salt bath heating temperature.From above-mentioned reaction tubes ingress with air speed 1500h
-1import the mixed gas of propylene 11 volume %, air 74 volume %, water vapour 15 volume %.372 ℃ of hot(test)-spot temperatures, propylene conversion 98.2%, propenal selectivity 86.8%.
Comparative example 3
The internal layer parent of catalyzer 2 of take is comparative catalyst 3, makes the ball that diameter is 4mm, and propylene oxidation method is with embodiment 2.380 ℃ of hot(test)-spot temperatures, propylene conversion 98.7%, propenal selectivity 85.6%.
Comparative example 4
The skin of catalyzer 2 of take is comparative catalyst 4, makes the ball that diameter is 4mm, and propylene oxidation method is with embodiment 2.371 ℃ of hot(test)-spot temperatures, propylene conversion 97.1%, propenal selectivity 85.9%.
Embodiment 3
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active ingredient slurries (a)
Under agitation condition, get 198 grams of ammonium molybdates, 37.2 grams of cupric nitrates, 15.6 grams of cesium nitrates and be dissolved in (water temperature is more than 65 ℃) in 1000ml pure water, obtain slurries (1), then get 116.4 grams of Bismuth trinitrates and be dissolved in rare nitric acid, obtain solution (2).Get again 48.5 grams of iron nitrates, 104.8 grams of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs, under agitation condition, be dissolved in (water temperature is more than 65 ℃) in 1000ml pure water, obtain slurries (3).Then, slurries (1) mix with slurries (2), then add ammoniacal liquor to regulate pH value to alkalescence, obtain slurries (4), after 20 minutes, lentamente slurries (3) are added in slurries (4), and add 14 grams of silicon-dioxide, 80 ℃ of strong stirrings 2 hours simultaneously.
(2) preparation of auxiliary material slurries (b)
Under heating and stirring, 11.9 grams of zinc nitrates and 19.9 grams of ammonium phosphowolframates are dissolved in to (water temperature is more than 65 ℃) in 500ml pure water, then add 10.6 grams of Niobium Pentxoxides, be uniformly mixed.
(3) preparation of catalyst Precursors
Active ingredient slurries (a) and auxiliary material slurries (b) are carried out answering 50 minutes post-heating dry after co-precipitation, in nitrogen with 160 ℃ of thermal treatments 3 hours, then with banded extruder, be squeezed into the ball shape that diameter is 2mm, oven dry was by 550 ℃ of roastings 3 hours, make catalyst Precursors, this catalyst Precursors consists of:
Mo
14Bi
3Fe
1.5Co
4.5Cs
1Cu
2Nb
1Zn
0.5W
1
Step 2 Kaolinite Preparation of Catalyst is outer
(1) preparation of active ingredient slurries (a)
Preparation with active ingredient slurries (a) in embodiment 2 catalyst inner layer parents is identical.
(2) preparation of auxiliary material slurries (b)
Preparation with auxiliary material slurries (b) in embodiment 2 catalyst inner layer parents is identical.
(3) preparation of catalyst outer layer
Active ingredient slurries (a), auxiliary material slurries (b) are carried out answering 50 minutes post-heating dry after co-precipitation with 26 grams of silicon oxide powders and 16 grams of alumina powders, in nitrogen with 160 ℃ of thermal treatments 3 hours, then 550 ℃ of roastings are 3 hours, through pulverizing, grind, sieving, process to obtain catalyst outer layer powder.
Step 3: Kaolinite Preparation of Catalyst 3
The catalyst inner layer parent of step 1 preparation is placed in to round bottom container, under container rotation condition, to catalyst Precursors, spray diethyl ether solution, under the condition of fully wetting catalyst inner layer parent, stop operating, put it into rapidly in the round bottom container of the catalyst outer layer that is placed with step 2 gained of another rotation, apply, coat-thickness is at 1.0～2.0mm, and gained catalyzer is dried and within 3 hours, obtained catalyzer 3 by 550 ℃ of roastings.
Propylene oxidation method
In fixed bed single tube reactor, pack the above-mentioned catalyzer 3 of 35ml into, 305 ℃ of salt bath heating temperature.From above-mentioned reaction tubes ingress with air speed 850h
-1import the mixed gas of propylene 8 volume %, air 68.5 volume %, water vapour 23.5 volume %.369 ℃ of hot(test)-spot temperatures, propylene conversion 98.3%, propenal selectivity 85.7%.
Comparative example 5
The internal layer parent of catalyzer 3 of take is comparative catalyst 5, makes the ball that diameter is 4mm, and propylene oxidation method is with embodiment 3.381 ℃ of hot(test)-spot temperatures, propylene conversion 98.9%, propenal selectivity 84.3%.
Comparative example 6
The skin of catalyzer 3 of take is comparative catalyst 6, but the amount of caesium is 78 grams, and comparative catalyst 6 consists of: Mo
14bi
3fe
1.5co
4.5cs
5cu
2nb
1zn
0.5w
1
Make the ball that diameter is 4mm, propylene oxidation method is with embodiment 3.370 ℃ of hot(test)-spot temperatures, propylene conversion 96.5%, propenal selectivity 83.7%.
Embodiment 4
Step 1: Kaolinite Preparation of Catalyst internal layer parent
Preparation process with embodiment 1 catalyst inner layer parent is identical, just gets 190.7 grams of ammonium molybdates, 55.8 grams of cupric nitrates, 28 grams of cesium nitrates, 271.7 grams of Bismuth trinitrates, 129 grams of iron nitrates, 35 grams of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs, 7.9 grams of potassium manganates, 22.1 grams of magnesium nitrates and 18.7 grams of ammonium meta-vanadates and 10 grams of silicon-dioxide.Catalyst Precursors consists of:
Mo
13.5Bi
7Fe
4Co
1.5Cs
1.8Cu
3Mg
1.5Mn
0.5V
2
Step 2: Kaolinite Preparation of Catalyst is outer
Preparation process with step 1 catalyst inner layer is identical, just adds 32 grams of silicon-dioxide.
Step 3: Kaolinite Preparation of Catalyst 4
Preparation process with embodiment 1 catalyzer 1 is identical.
Propylene oxidation method
In fixed bed single tube reactor, pack the above-mentioned catalyzer 4 of 35ml into, 310 ℃ of salt bath heating temperature.From above-mentioned reaction tubes ingress with air speed 1600h
-1import the mixed gas of propylene 9 volume %, air 70 volume %, water vapour 21 volume %.369 ℃ of hot(test)-spot temperatures, propylene conversion 98.5%, propenal selectivity 86.5%.
Embodiment 5
Identical with catalyzer 5 embodiment 1 catalyzer 1 internal layer parent preparation processes, add 15.5 grams of cerous nitrates, internal layer adds 10 grams of silicon-dioxide and 4 grams of powdered graphites; Skin adds 58 grams of silicon-dioxide.Catalyzer 5 parents consist of: Mo
13bi
3fe
1co
3cs
0.5cu
1ce
0.5v
1mg
2
Propylene oxidation method
In fixed bed single tube reactor, pack the above-mentioned catalyzer 5 of 30ml into, 325 ℃ of salt bath heating temperature.From above-mentioned reaction tubes ingress with air speed 1400h
-1import the mixed gas of propylene 12 volume %, air 73 volume %, water vapour 15 volume %.373 ℃ of hot(test)-spot temperatures, propylene conversion 98.5%, propenal selectivity 88.1%.
Comparative example 7
The internal layer catalyst of catalyzer 5 of take is comparative catalyst 7, is the hollow columnar particle of φ 4.5 * 5mm through banded extruder extrusion molding.Propylene oxidation method is with embodiment 5.384 ℃ of hot(test)-spot temperatures, propylene conversion 99.1%, propenal selectivity 84.9%.
Embodiment 6
Preparation process with embodiment 5 catalyzer 5 is identical, just adds 15 grams of magnesium nitrates, and internal layer adds 12 grams of silicon-dioxide; Skin adds 28 grams of silicon-dioxide.Consisting of of catalyzer 6 parents:
Mo
13.5Bi
4Fe
3.5Co
1Cs
0.2Cu
0.8Sr
0.5V
1.5Mg
1
Embodiment 7
Preparation process with embodiment 5 catalyzer 5 is identical, just adds 23.4 grams of ammonium meta-vanadates, and internal layer adds 14 grams of silicon-dioxide; Skin adds 43 grams of silicon-dioxide.Catalyzer 7 parents consist of:
Mo
14Bi
3Fe
1.5Co
4.5Cs
0.1Cu
2V
2.5Sr
1
Embodiment 8
Preparation process and raw material with embodiment 5 catalyzer 5 are identical, just add 13 grams of lanthanum nitrates, and internal layer adds 6 grams of silicon-dioxide; Skin adds 13 grams of silicon-dioxide.Catalyzer 8 parents consist of:
Mo
13Bi
4Fe
0.45Co
3.5Cs
0.07Cu
1.2La
0.5Sr
0.4
Propylene oxidation method
Fixed bed single tube reactor internal diameter 25mm, inside establishes thermopair, and reactor feedstocks gas inlet side packs 35ml catalyzer 6,7 or 8 into, 312 ℃ of salt bath heating temperature.From above-mentioned reaction tubes ingress with air speed 1000h
-1import the mixed gas of propylene 10 volume %, air 73 volume %, water vapour 17 volume %.Hot(test)-spot temperature is respectively 371 ℃, 370 ℃ and 372 ℃, and propylene conversion is respectively 98.5%, 98.4% and 98.6%, and propenal selectivity is respectively 86.9%, 86.6% and 87.3%.
Catalyzer 6,7 and 8 reactions improved salt temperature to 340 ℃ after 100 hours, were down to 312 ℃ after 5 hours again, reacted propylene conversion after 20 hours and were respectively 98.4%, 98.2% and 98.4%, and propenal selectivity is respectively 86.5%, 86.2% and 87.1%.Catalyzer is after the pyroreaction of 345 ℃, and catalyst activity component is difficult for running off, and before and after reaction, the content of active ingredient molybdenum is substantially constant, can reach fresh live catalyst activity level, catalyzer Heat stability is good.
Comparative example 8
The internal layer catalyst of catalyzer 8 of take is comparative catalyst 8, is the hollow columnar particle of φ 4.5 * 5mm through banded extruder extrusion molding.Propylene oxidation method is with embodiment 8.385 ℃ of hot(test)-spot temperatures, propylene conversion 99.3%, propenal selectivity 84.1%.React and improve salt temperature to 340 ℃ after 100 hours, be down to 312 ℃ after 5 hours again, reacting propylene conversion after 20 hours is 97.8%, and propenal selectivity is 84.9%.
Comparative example 8 catalyzer can not effectively suppress focus, poor selectivity, and through pyroreaction rear catalyst poor heat stability, under the washing away of the mixed airflows such as water vapour, activity obviously declines.
Claims (10)
1. a method for propylene oxidation acrolein, adopts fixed bed single tube reactor, it is characterized in that:
Reaction raw materials propylene, water, air more than 130 ℃ enter reactor after preheating through preheater, salt bath heating, and reaction process condition is: 300～335 ℃ of salt temperatures, air speed 800～2200h
-1, feed composition: propylene 7～12 volume %, air 69～73 volume %, water vapour 15～20 volume %; It is multi-metal-oxide catalyst that Mo-Bi is housed in reactor, and the chief component of this multi-metal-oxide catalyst represents by leading to formula I below
Mo
aBi
bFe
cCo
dCs
eCu
fSi
gA
hB
iO
j (Ⅰ)
Wherein: Mo is molybdenum, Bi is bismuth, and Fe is iron, and Co is cobalt, and Cs is caesium, and Cu is copper, and Si is silicon, and silicon is the carrier adding in catalyzer, and A is at least one element being selected from zinc, manganese, lanthanum, niobium, zirconium, vanadium; B is at least one element being selected from magnesium, strontium and tungsten; O is oxygen; A, b, c, d, e, f, g, h, i represent respectively each element atomic ratio, wherein 12≤a≤14,2≤b≤8,0.1≤c≤5,0.5≤d≤5,0.05≤e≤4,0.5≤f≤3,0.5≤g≤50,0.1≤h≤3,0.1≤i≤2, j is the numerical value by the oxygen decision of each oxide compound, described catalyzer has interior outer double-layer structure, the total content of outer silicon-dioxide is than the height of internal layer parent, and in molar content, each component concentration concentration ratio internal layer parent of catalyst outer layer is low.
2. the method for propylene oxidation acrolein according to claim 1, is characterized in that 305～325 ℃ of salt temperatures.
3. the method for propylene oxidation acrolein according to claim 1, is characterized in that air speed 800～1600h
-1.
4. the method for propylene oxidation acrolein according to claim 1, is characterized in that 2.5≤b≤6 in the logical formula I of used catalyst, 0.2≤c≤3,0.5≤d≤3.5,0.1≤e≤2.
5. the method for propylene oxidation acrolein according to claim 1, is characterized in that used catalyst has multilayer structure, and in molar content, outer each constituent content is lower by 0.1～28% than this constituent content of internal layer.
6. the method for propylene oxidation acrolein according to claim 1, is characterized in that outer each constituent content of used catalyst is lower by 0.5～15% than this constituent content of internal layer.
7. the method for propylene oxidation acrolein according to claim 1, is characterized in that (a+b)/e > 10 in logical formula I.
8. according to the method for propylene oxidation acrolein described in claim 1～7 any one, it is characterized in that the preparation of used catalyst comprises the steps:
First, Kaolinite Preparation of Catalyst internal layer parent:
(1) will contain Mo, Bi, the compound dissolution of Fe, Co, Cu and Cs also mixes, and forms active ingredient slurries (a);
(2) will lead to A in formula I again
hb
ieach elementary composition compound dissolution relating to also mixes, as auxiliary material slurries (b);
(3) active ingredient slurries (a) are mixed with auxiliary material slurries (b) and carry out forming internal layer parent slurry after co-precipitation, dry, moulding, roasting obtains catalyst inner layer parent;
Secondly, according to the method for Kaolinite Preparation of Catalyst internal layer parent slurries, prepare outer layer catalyst slurry, in outer layer catalyst slurry preparation process, add silicon-dioxide;
Finally, the outer layer catalyst of preparation is coated on catalyst inner layer parent successively, after roasting, obtains finished catalyst.
9. the method for propylene oxidation acrolein according to claim 8, it is characterized in that used catalyst internal layer parent after moulding and outer after coating at 300～580 ℃ roasting 3～10h, adopt open roasting or enclosed roasting, calcination atmosphere is helium, nitrogen or argon gas.
10. the method for propylene oxidation acrolein according to claim 8, is characterized in that using binding agent, binding agent to be selected from one or more in alcohols or ethers when used catalyst applies.
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| CN105195166A (en) * | 2015-10-23 | 2015-12-30 | 中国海洋石油总公司 | Method for preparing acrolein catalyst by propylene oxidation |
| CN107321371A (en) * | 2017-05-27 | 2017-11-07 | 镇江四联机电科技有限公司 | A kind of preparation method of acrylic acid catalyst |
| CN110280256A (en) * | 2019-07-10 | 2019-09-27 | 兰州科润化工技术有限公司 | A kind of catalyst and preparation method thereof being used to prepare methacrylaldehyde |
| CN114425355B (en) * | 2020-09-27 | 2023-08-15 | 中国石油化工股份有限公司 | Catalyst for preparing methacrolein by fixed bed, preparation method and application |
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| CN1388104A (en) * | 2001-05-30 | 2003-01-01 | 三菱丽阳株式会社 | Process for producing (methyl)acrolein and/or (methyl) acrylic acid |
| CN1697814A (en) * | 2004-04-01 | 2005-11-16 | 三菱化学株式会社 | Process for producing (meth)acrylic acid or (meth)acrolein |
| CN1882385A (en) * | 2003-11-18 | 2006-12-20 | 巴斯福股份公司 | Preparation of acrolein by heterogeneously catalyzed partial gas phase oxidation of propene |
| CN101385978A (en) * | 2007-09-12 | 2009-03-18 | 上海华谊丙烯酸有限公司 | Catalyst for synthesizing methylacrolein and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1388104A (en) * | 2001-05-30 | 2003-01-01 | 三菱丽阳株式会社 | Process for producing (methyl)acrolein and/or (methyl) acrylic acid |
| CN1882385A (en) * | 2003-11-18 | 2006-12-20 | 巴斯福股份公司 | Preparation of acrolein by heterogeneously catalyzed partial gas phase oxidation of propene |
| CN1697814A (en) * | 2004-04-01 | 2005-11-16 | 三菱化学株式会社 | Process for producing (meth)acrylic acid or (meth)acrolein |
| CN101385978A (en) * | 2007-09-12 | 2009-03-18 | 上海华谊丙烯酸有限公司 | Catalyst for synthesizing methylacrolein and preparation method thereof |
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