CN105233822A - Super-gravity catalyst for oxidizing and esterifying aldehyde into carboxylate ester and application of super-gravity catalyst - Google Patents
Super-gravity catalyst for oxidizing and esterifying aldehyde into carboxylate ester and application of super-gravity catalyst Download PDFInfo
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- CN105233822A CN105233822A CN201410330869.2A CN201410330869A CN105233822A CN 105233822 A CN105233822 A CN 105233822A CN 201410330869 A CN201410330869 A CN 201410330869A CN 105233822 A CN105233822 A CN 105233822A
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Abstract
The present invention discloses a super-gravity catalyst for oxidizing and esterifying aldehyde into carboxylate ester and an application of the super-gravity catalyst. Reaction materials are a vapour-phase or liquid-phase propenal material, alcohol and air; the reaction pressure is 0.1-5 MPa; a reaction is kept to be performed under a liquid-phase condition; and a supported nano-Au/Sb2O3 catalyst is loaded into a super-gravity reaction kettle. Rotational speed of the super-gravity rotary reaction kettle is 300-3000 r/min, and dwell time of the solution in the super-gravity rotary reaction kettle does not exceed 5 minutes. The super-gravity catalyst provided by the present invention has the characteristics of being soft in a reaction, simple in an operation and high in yield, thereby increasing reaction stability and process economical efficiency.
Description
Technical field
The invention belongs to hypergravity oxidative esterification catalysis technical field, relate in particular to a kind of use Au/Sb
2o
3solid catalyst, is adopted high-gravity technology, is prepared the technique of acrylate by acrolein oxidation esterification.
Background technology
Acrylic acid is one of important derivatives of propylene, and its esterification products is widely used and comprises coating, super absorbent resin, flocculant and washing assisant etc.Existing acrylic acid process has three kinds, namely the petroleum path in more than 40 years of commercial Application as Selective Oxidation of Propylene, low-carbon alkanes route and selective oxidation of propane and biomass glycerol route.
Existing industrial acrylate processes comprises three steps: 1) propylene oxidation acrolein acrylic acid two-step penetration method, and adopt Mo-Bi catalyst, reaction temperature is at 280 ~ 350 DEG C; 2) acrolein oxidation is acrylic acid, and adopt MoVW catalyst, reaction temperature is at 240 ~ 300 DEG C; 3) esterification, the acrylic acid namely produced to be reacted to alcohols by esterification catalyst and produces corresponding ester after refining.The first two steps oxidation reaction of said process adopts shell and tube reactor, this selective oxidation belongs to strong exothermal reaction, the more difficult control of reactor hot(test)-spot temperature, particularly second step oxidizing process slightly temperature runaway catalyst namely lose activity, the stable operation how ensureing to react, to improve acrylic acid yield and reduce accessory substance be the difficult problem in this field all the time.Propane route and propylene route similar, the difference of the catalyst that uses neither be very large, no longer repeated description.
In view of the operating difficulties of the day by day exhausted of petroleum resources and this process industry route, take glycerine as the concern as companies such as Japanese chemical drug, Mitsubishi, BASFs that the living beings route of raw material causes numerous world-class company.Glycerine route comprises two steps, i.e. preparing acrolein by dehydrating glycerin and prepared by acrolein oxidation acrylic acid two steps.Dehydrating glycerin process relatively easily realizes, as adopted the acidic catalysts such as phosphotungstic acid, ferric phosphate and zirconia, phosphorus vanadium (VPO) catalyst is adopted as CN102066001A discloses, reaction temperature 280 DEG C, glycerine: oxygen: water=10:10:80 (mol), GHSV are 330hr
-1, the conversion ratio of glycerine is 100%, and the selective of methacrylaldehyde is 79.8%, acrylic acid selective be 0.5%.But as described in CN101563311, glycerine second step acrolein oxidation still needs the selective oxidation catalyst adopting traditional propylene or propane route, remains a unmanageable strong exothermal reaction.Therefore, the second step of the glycerine route process route that still needs selection one relatively gentle.
Also some researchers have reported that the direct carboxylate of employing oxidative esterification route, as (ACS.Catal.) such as SuzukiK. discloses AuNi/SiO
2-Al
2o
3catalyst, the under the same reaction conditions Au (0.1mol%) of low content and Pd (0.5mol%) two kinds of catalyst of high-load, the conversion ratio of aldehyde is respectively 20% and 63%, and the selective of ester is respectively 40% and 97%.It is 32.8% that JP2005008557 discloses the conversion ratio adopting Au catalyst MAL.But the yield of the ester class of said process is relatively low, still need larger raising to meet its economy.
Therefore, need to develop a kind of for methacrylaldehyde be converted into acrylate reaction temperature and, the oxidative esterification catalyst that simple to operate and yield is higher and technique thereof.
Summary of the invention
It is hypergravity catalyst and the application thereof of carboxylate for oxidation of aldehydes esterification that the problem to be solved in the present invention there is provided a kind of, have reaction temperature and, the feature that simple to operate and yield is higher, thus improve stability and the process economy of reaction.
Concrete technical scheme is as follows:
It is the hypergravity catalyst of carboxylate for oxidation of aldehydes esterification that an object of the present invention there is provided a kind of.
Described catalyst is at Sb by nanometer Au load
2o
3formed; By Au deposition sedimentation at Sb
2o
3on dust carrier, carry out drying afterwards, the powder of gained is mixed mutually with Alpha-alumina, after extrusion forming, form supported nano-Au/Sb
2o
3.The content of described Au is 0.001 ~ 5wt%, preferably 0.01 ~ 0.1wt%; The specific surface of described Alpha-alumina is 0.1 ~ 300m
2/ g, is preferably 1.0 ~ 30m
2/ g, described baking temperature is 80 ~ 350 DEG C, preferably 120 ~ 250 DEG C.
Described deposition sedimentation is technology known in the field, be specially (1) dipping or spraying: at 20 ~ 80 DEG C, with alkali lye, golden precursor solution pH is adjusted to 6 ~ 10, make golden precursor sol, flood separately with the golden precursor sol made or spray carrier, or with other main active components, help active component solution jointly to flood or spray carrier, place 1 ~ 48 hour; (2) precipitate: from solution, the presoma of the presoma of gold or the presoma of gold and other components is deposited on described carrier as precipitating reagent with alkali lye; (3) ammonia salt soaks: soak the carrier after precipitation with ammonia salting liquid, obtain catalyst precursor; (4) wash: deionized water washs described catalyst precursor, until Cl
-content is lower than 100ppm; (5) dry and roasting: dry and calcined catalyst presoma, sintering temperature 150 ~ 600 DEG C.
Described molding mode, can select extrusion, compressing tablet or other molding modes.
Described Alpha-alumina mainly plays carrier supported effect, also can select carborundum, talcum powder and molecular sieve etc.
Since (Chem.Lett. (1987) 405) such as Haruta finds that Au (is less than 10nm, be generally 2 ~ 4nm) at special nano effect, this area conducts extensive research this catalyst, thinks that carrier and preparation method are the key influence factors of nano-Au catalyst.Large more options CeO
2, TiO
2, Al
2o
3, Fe oxide or composite oxides, but the stability of Au catalyst is still difficult to solve.Report is not yet had to adopt Sb at present
2o
3as the carrier of Au catalyst.
It is the hypergravity catalytic reaction of carboxylate for oxidation of aldehydes esterification that second object of the present invention is to provide a kind of, reaction mass is the methacrylaldehyde material of gas phase or liquid phase, alcohols and air, under reaction pressure 0.1 ~ 5MPa, carry out, by aforesaid supported nano-Au/Sb under reaction remains on liquid-phase condition
2o
3catalyst packing is in hypergravity reactor.The rotating speed of hypergravity revolving reaction still is 300 ~ 3000r/min, and the time of staying of solution in hypergravity revolving reaction still is no more than 5 minutes.
Hypergravity catalytic reaction is different from traditional homogeneous catalysis and heterogeneous catalysis, belong to catalytic reaction process reinforcement technique, the liquid distribution trough that process in reaction mass is equipped with catalyst obtains high speed dispersion, realize gas-liquid two-phase in fully efficient mass transfer, heat transfer contact, while raising conversion ratio, and time of contact greatly reduces, also greatly suppress the generation of side reaction.
Described alcohols can select the one in methyl alcohol, ethanol, butanols, ethylene glycol and octanol, particular methanol.
Described methacrylaldehyde material, optionally comes from propylene oxidation, oxidation of propane or glycerine gas-phase dehydration and the gas-phase propene aldehyde gaseous phase materials obtained, and also can select glycerin liquid phase dehydration and the liquid propylene aldehyde material obtained.
The present invention has following beneficial effect:
1. reaction temperature and, reaction at 0.1 ~ 5MPa, can be carried out under liquid-phase reaction condition.
2. catalytic perfomance is excellent, and under evaluating at 1000 hours, the conversion ratio of methacrylaldehyde is more than 80%, and the yield of methyl acrylate is more than 70%.
3. compared with traditional handicraft, course of reaction simplifies to some extent, and byproduct compounds reduces, and improves the economy of technique.
Detailed description of the invention
Method of testing
XRD (X-raydiffraction, X-ray diffraction): the XpertMPD type X-ray diffractometer analysis of catalyst phase structure adopting Dutch Philips company, radiation source is CuK α, and sweep limits is 20 ~ 80 DEG C, adopts Scherrer formula to calculate size of microcrystal.
Specific surface is tested: the physical adsorption appearance adopting the Nova3000e of Kang Ta company of the U.S., carries out specific surface area analysis.At liquid nitrogen temperature-196 DEG C, use N
2determination of adsorption method surface area and pore-size distribution, sample vacuumizes pretreatment and is less than 10 to pressure at 300 DEG C
-3pa, assay method is static method.BET method is adopted to calculate specific surface according to adsorption isotherm.
Following examples describe the present invention's citing specifically, but the present invention is not limited to these embodiments.Gold chloride in embodiment, copper nitrate, antimony oxide, manganese nitrate, zinc nitrate, sodium carbonate, ammoniacal liquor, zirconium oxychloride and aluminum nitrate, be analysis pure, recovers chemical reagent Co., Ltd purchased from Tianjin; Silicon carbide ceramics (α-SiC) and high-specific surface area carborundum (β-SiC), purchased from Pingxiang Rui Ze silicon materials Co., Ltd.Embodiment 1:
Get the Sb of 100 grams respectively
2o
3, the NaOH aqueous solution adding 0.1mol/L regulates 1.0 × 10
-4the pH value of the chlorauric acid solution of mol/L is 7, and solution temperature remains on 60 DEG C, stirs 15min; Adding carrier when stirring, flood this carrier, then the NaOH solution adjust ph adding 0.1mol/L being 7, stir 120min, soak half an hour with the weak aqua ammonia of 0.1mol/L, then wash 6 removing Cl by the deionized water of 70 DEG C
-to dozens of ppm, then at 80 DEG C dry 12 hours, roasting 6 hours at 350 DEG C after extruded moulding.Obtained 0.02wt%Au/Sb respectively
2o
3catalyst 1
#.
Embodiment 2:
Other are with embodiment 1, obtained 0.05wt%Au/Sb
2o
3catalyst 2
#.
Embodiment 3:
Other are with embodiment 1, obtained 0.095wt%Au/Sb
2o
3catalyst 3
#.
Embodiment 4:
Other are with embodiment 1, obtained 0.48wt%Au/Sb
2o
3catalyst 4
#.
Embodiment 5: comparative example
Other are with embodiment 1, obtained 0.05wt%Au/ZrO2 catalyst 5
#.
Embodiment 6: comparative example
Other are with embodiment 1, obtained 0.05wt%Au/TiO2 catalyst 6
#.
Embodiment 7: comparative example
Other are with embodiment 1, obtained 0.05wt%Au/ α-Al
2o
3catalyst 7
#.
The contrast of catalyst
With the catalyst prepared by embodiment 1 ~ 7, carry out hypergravity oxidative esterification test evaluation respectively 1000 hours.
In hypergravity stirred autoclave, add 200mL catalyst, MAL mass fraction is that the MAL-methanol solution of 25% is with the flow velocity continuous feed of 1000mL/s.Mass fraction be 2% NaOH-methanol solution with the flow velocity continuous feed of 500mL/s with and the mode of flowing joins supergravity reactor carries out neutralizing and maintain pH value to 7.0 ± 0.3 of reaction system, air is blown into the speed of 1500mL/s, reaction pressure is 3MPa, under the reaction temperature of 80 DEG C, successive reaction prepares methyl methacrylate, and supergravity reactor rotor speed is 2000rpm.By hypergravity revolving reaction still feed liquid out, sampling is analyzed.Experimental result is in table 1
Table 1 result of the test
As seen from Table 1,1 ~ 4 is contrasted
#with 5 ~ 7
#catalyst take antimony oxide as the catalyst of carrier, catalyst activity and yield higher, and be catalyst almost non-activity with other.
The contrast of different process:
With the catalyst prepared by embodiment 1, carry out reaction evaluating under the following conditions.
Appreciation condition is as follows:
A) in hypergravity stirred autoclave, add 200mL catalyst, reaction pressure is 5MPa, and under the reaction temperature of 150 DEG C, successive reaction prepares methyl methacrylate, and supergravity reactor rotor speed is 3000rpm.By hypergravity revolving reaction still feed liquid out, sampling is analyzed.
B) in hypergravity stirred autoclave, add 200mL catalyst, reaction pressure is 0.1MPa, and under the reaction temperature of 60 DEG C, successive reaction prepares methyl methacrylate, and supergravity reactor rotor speed is 300rpm.By hypergravity revolving reaction still feed liquid out, sampling is analyzed.
C) in convention stir reactor, add 200mL catalyst, reaction pressure is 5MPa, and under the reaction temperature of 150 DEG C, successive reaction prepares methyl methacrylate, and conventional reactor rotor speed is 3000rpm.By convention stir reactor feed liquid out, sampling is analyzed.
D) in stirred autoclave, add 200mL catalyst, reaction pressure is 0.1MPa, and under the reaction temperature of 60 DEG C, successive reaction prepares methyl methacrylate, and reactor rotating speed of agitator is 300rpm.By convention stir reactor feed liquid out, sampling is analyzed.
Table 2 humid test result
As seen from Table 2, hypergravity technique and common process, under identical reaction temperature and pressure, hypergravity technique is far superior to common process, and this may be because the strengthening transmission effect of hypergravity improves reactivity worth.
Claims (6)
1. be a hypergravity catalyst for carboxylate for oxidation of aldehydes esterification, it is characterized in that this catalyst is at Sb by Au deposition sedimentation
2o
3on dust carrier, carry out drying afterwards, roasting becomes supported nano-Au/Sb
2o
3catalyst; The content of described Au is 0.001 ~ 5wt%, and described baking temperature is 80 ~ 350 DEG C.
2. according to claim 1 a kind of be the hypergravity catalyst of carboxylate for oxidation of aldehydes esterification, it is characterized in that the content of described Au is 0.01 ~ 0.1wt%, described baking temperature is 120 ~ 250 DEG C.
3. one kind is the hypergravity catalytic reaction of carboxylate for oxidation of aldehydes esterification, it is characterized in that the catalyst used in hypergravity reactor described in claim 1, reaction mass is the methacrylaldehyde material of gas phase or liquid phase, alcohol and air, under reaction pressure 0.1 ~ 5MPa, carry out under reaction remains on liquid-phase condition.
4. according to claim 3 a kind of be the hypergravity catalytic reaction of carboxylate for oxidation of aldehydes esterification, described methacrylaldehyde material is it is characterized in that to be selected from propylene oxidation, oxidation of propane or glycerine gas-phase dehydration and the gas-phase propene aldehyde gaseous phase materials obtained, or glycerin liquid phase dehydration and the liquid propylene aldehyde material obtained.
5. according to claim 3 a kind of be the hypergravity catalytic reaction of carboxylate for oxidation of aldehydes esterification, it is characterized in that described alcohol is selected from the one in methyl alcohol, ethanol, butanols, ethylene glycol and octanol.
6. according to claim 3 a kind of be the hypergravity catalytic reaction of carboxylate for oxidation of aldehydes esterification, it is characterized in that the rotating speed of hypergravity reactor is 300 ~ 3000r/min.
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|---|---|---|---|
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|---|---|---|---|
| CN201410330869.2A CN105233822B (en) | 2014-07-11 | 2014-07-11 | A kind of hypergravity catalyst for being used for oxidation of aldehydes esterification for carboxylate and its application |
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Cited By (3)
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| CN112473707A (en) * | 2019-09-12 | 2021-03-12 | 北京化工大学 | Preparation method of vanadium-phosphorus-oxygen catalyst for regulating crystal face and butane oxidation application |
| WO2022015680A1 (en) * | 2020-07-14 | 2022-01-20 | Dow Global Technologies Llc | Process and catalyst for oxidative esterication with mechanically strong and chemically resistant catalyst |
| CN115532280A (en) * | 2021-06-30 | 2022-12-30 | 中国石油化工股份有限公司 | Catalyst for continuously preparing methyl methacrylate by oxidative esterification and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112473707A (en) * | 2019-09-12 | 2021-03-12 | 北京化工大学 | Preparation method of vanadium-phosphorus-oxygen catalyst for regulating crystal face and butane oxidation application |
| CN112473707B (en) * | 2019-09-12 | 2023-01-20 | 北京化工大学 | Preparation method of vanadium-phosphorus-oxygen catalyst for regulating crystal face and butane oxidation application |
| WO2022015680A1 (en) * | 2020-07-14 | 2022-01-20 | Dow Global Technologies Llc | Process and catalyst for oxidative esterication with mechanically strong and chemically resistant catalyst |
| CN115532280A (en) * | 2021-06-30 | 2022-12-30 | 中国石油化工股份有限公司 | Catalyst for continuously preparing methyl methacrylate by oxidative esterification and preparation method and application thereof |
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