CN105233822B - A kind of hypergravity catalyst for being used for oxidation of aldehydes esterification for carboxylate and its application - Google Patents
A kind of hypergravity catalyst for being used for oxidation of aldehydes esterification for carboxylate and its application Download PDFInfo
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- CN105233822B CN105233822B CN201410330869.2A CN201410330869A CN105233822B CN 105233822 B CN105233822 B CN 105233822B CN 201410330869 A CN201410330869 A CN 201410330869A CN 105233822 B CN105233822 B CN 105233822B
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Abstract
The invention discloses a kind of for hypergravity catalyst of the oxidation of aldehydes esterification for carboxylate and its application, reaction mass is methacrylaldehyde material, alcohols and the air of gas phase or liquid phase, under 0.1~5MPa of reaction pressure, reaction, which is maintained under liquid-phase condition, to be carried out, by supported nano-Au/Sb2O3Catalyst packing is in hypergravity reactor.The rotating speed of hypergravity revolving reaction kettle is 300~3000r/min, and residence time of the solution in hypergravity revolving reaction kettle is no more than 5 minutes.The present invention, which has, reacts the characteristics of gentle, simple to operate and yield is higher, so as to improve the stability of reaction and process economy.
Description
Technical field
The invention belongs to hypergravity oxidative esterification catalysis technical field, relates in particular to one kind and uses Au/Sb2O3Solid
Catalyst, using high-gravity technology, the technique that acrylate is prepared by acrolein oxidation esterification.
Background technology
Acrylic acid is one of important derivatives of propylene, its esterification products be widely used including coating, super absorbent resin,
Flocculant and washing assisant etc..Existing acrylic acid process has three kinds, i.e. the petroleum path such as third in more than 40 years of commercial Application
Alkene selective oxidation, low-carbon alkanes route are selective oxidation of propane and biomass glycerol route.
Existing industrial acrylate processes include three steps：1) propylene oxidation acrolein acrylic acid two-step penetration method, is used
Mo-Bi catalyst, reaction temperature is at 280~350 DEG C；2) acrolein oxidation is acrylic acid, using MoVW catalyst, reaction temperature
At 240~300 DEG C；3) esterification, i.e., caused acrylic acid passes through esterification catalyst after refined and alcohols reaction produces
Corresponding ester.The first two steps oxidation reaction of said process uses shell and tube reactor, and the selective oxidation belongs to strong exothermal reaction, instead
Answer the more difficult control of device hot(test)-spot temperature, particularly second step oxidizing process slightly temperature runaway catalyst to lose activity, how to ensure anti-
Stable operation, raising acrylic acid yield and the reduction accessory substance answered are the problem in the field all the time.Propane route and propylene route
Similar, used catalyst difference is nor very greatly, be not repeated to describe.
In view of the operating difficulties of the increasingly depleted of petroleum resources and the process industry route, the biomass using glycerine as raw material
Route causes the concern of such as Japanese chemical drug, Mitsubishi, BASF company of numerous world-class companys.Glycerine route includes
Two steps of two steps, i.e. preparing acrolein by dehydrating glycerin and prepared by acrolein oxidation acrylic acid.Dehydrating glycerin process is relatively easy
Realize, phosphotungstic acid, ferric phosphate and zirconium oxide acidic catalyst are such as used, as CN102066001A is disclosed using phosphorus vanadium
(VPO) catalyst, in 280 DEG C of reaction temperature, glycerine：Oxygen：Water=10：10：80 (mol), GHSV 330hr-1, the conversion of glycerine
Rate is 100%, and the selectivity of methacrylaldehyde is 79.8%, and the selectivity of acrylic acid is 0.5%.But as CN101563311 institutes
State, glycerine second step acrolein oxidation stills need the selective oxidation catalyst using traditional propylene or propane route, is still
One unmanageable strong exothermal reaction.Therefore, the second step of glycerine route still needs one relatively mild technique of selection
Route.
Also some researchers have reported that using the direct carboxylate of oxidative esterification route, such as Suzuki K. (ACS.Catal.)
Disclose AuNi/SiO2-Al2O3Catalyst, the under the same reaction conditions Au (0.1mol%) of the low content and Pd of high content
(0.5mol%) two kinds of catalyst, the conversion ratio of aldehyde is respectively 20% and 63%, and the selectivity of ester is respectively 40% and 97%.
JP2005008557, which is disclosed, uses the conversion ratios of Au catalyst MALs as 32.8%.But the receipts of the esters of said process
Rate is relatively low, it is still desirable to which larger raising is to meet its economy.
Therefore, it is necessary to develop it is a kind of for methacrylaldehyde be converted into acrylate reaction is gentle, simple to operate and yield compared with
High oxidative esterification catalyst and its technique.
The content of the invention
The problem to be solved in the present invention there is provided it is a kind of for it is oxidation of aldehydes esterification for carboxylate hypergravity catalyst and
It is applied, and is had and is reacted the characteristics of gentle, simple to operate and yield is higher, so as to improve the stability of reaction and process economicses
Property.
Concrete technical scheme is as follows：
An object of the present invention there is provided a kind of hypergravity catalyst for oxidation of aldehydes esterification for carboxylate.
The catalyst is to be supported on Sb by nanometer Au2O3Formed；By Au deposition sedimentations in Sb2O3On dust carrier, it
After be dried, the powder of gained is mixed with Alpha-alumina, after pressurized shaping formed supported nano-Au/Sb2O3.Institute
The Au stated content is 0.001~5wt%, preferably 0.01~0.1wt%；The ratio surface of described Alpha-alumina be 0.1~
300m2/ g, preferably 1.0~30m2/ g, described drying temperature are 80~350 DEG C, preferably 120~250 DEG C.
Described deposition sedimentation technology well known in the art, it is specially (1) dipping or spraying：At 20~80 DEG C,
Golden precursor solution pH is adjusted to 6~10 with alkali lye, golden precursor sol is made, is individually soaked with manufactured golden precursor sol
Stain or spraying carrier, or with other main active components, help active component solution to impregnate or spray carrier jointly, placement 1~48 is small
When；(2) precipitate：By the use of alkali lye as precipitating reagent from solution by gold presoma or gold presoma and other components presoma
It is deposited on described carrier；(3) ammonia salt is soaked：With the carrier after ammonia salt solution immersion precipitation, catalyst precursor is obtained；
(4) wash：Deionized water washs the catalyst precursor, until Cl-Content is less than 100ppm；(5) dry and be calcined：Dry
With calcined catalyst presoma, 150~600 DEG C of sintering temperature.
Described molding mode, extrusion, tabletting or other molding modes may be selected.
Described Alpha-alumina primarily serves carrier supported effect, and carborundum, talcum powder and molecular sieve etc. also can be selected.
Since Haruta etc. (Chem.Lett. (1987) 405) has found Au (being less than 10nm, generally 2~4nm) special
Nano effect, this area conducts extensive research to the catalyst, it is believed that carrier and preparation method are nano-Au catalysts
Key influence factor.Big more options CeO2、TiO2、Al2O3, Fe oxides or composite oxides, but the stability of Au catalyst
Still it is difficult to solve.Not yet have been reported that using Sb at present2O3Carrier as Au catalyst.
Second object of the present invention is to provide a kind of hypergravity catalytic reaction for oxidation of aldehydes esterification for carboxylate, instead
Methacrylaldehyde material, alcohols and air of the material for gas phase or liquid phase are answered, under 0.1~5MPa of reaction pressure, reaction is maintained at liquid
Carried out under the conditions of phase, by foregoing supported nano-Au/Sb2O3Catalyst packing is in hypergravity reactor.Hypergravity rotation is anti-
The rotating speed for answering kettle is 300~3000r/min, and residence time of the solution in hypergravity revolving reaction kettle is no more than 5 minutes.
Hypergravity catalytic reaction is different from traditional homogeneous catalysis and heterogeneous catalysis, belongs to catalytic reaction process and strengthens skill
Art, liquid distribution trough of the process equipped with catalyst in reaction mass obtain scattered at a high speed, realize gas-liquid two-phase fully efficiently
Mass transfer, heat transfer contact, while conversion ratio is improved, and time of contact greatly reduces, also significantly suppress side reaction generation.
One kind in methanol, ethanol, butanol, ethylene glycol and octanol, preferably methanol may be selected in described alcohols.
Described methacrylaldehyde material, it is optional to come from propylene oxidation, oxidation of propane or gas phase obtained by glycerine gas-phase dehydration
Methacrylaldehyde gaseous phase materials, liquid propylene aldehyde material obtained by glycerine liquid-phase dehydration also may be selected.
The invention has the advantages that：
1. reaction is gentle, reaction can be carried out in 0.1~5MPa under liquid-phase reaction condition.
2. catalytic perfomance is excellent, under evaluation in 1000 hours, the conversion ratio of methacrylaldehyde is more than 80%, acrylic acid first
The yield of ester is more than 70%.
3. compared with traditional handicraft, course of reaction is simplified, and byproduct compounds are reduced, and improves the economy of technique.
Embodiment
Method of testing
XRD (X-ray diffraction, X-ray diffraction)：Penetrated using the X pert MPD types X of Dutch Philips companies
Line diffractometer analysis of catalyst phase structure, radiation source are CuK α, and scanning range is 20~80 DEG C, using Scherrer formula come
Calculate size of microcrystal.
Compare surface test：Using the Nova3000e of Kang Ta companies of U.S. physical adsorption appearance, specific surface area analysis is carried out.
At -196 DEG C of liquid nitrogen temperature, N is used2Determination of adsorption method surface area and pore-size distribution, sample vacuumize pretreatment extremely at 300 DEG C
Pressure is less than 10-3Pa, assay method are static method.Calculated according to adsorption isotherm using BET method and compare surface.
Following examples are citing descriptions more detailed to the present invention, but the invention is not limited in these embodiments.
Gold chloride, copper nitrate, antimony oxide, manganese nitrate, zinc nitrate, sodium carbonate, ammoniacal liquor, zirconium oxychloride and nitric acid in embodiment
Aluminium, it is that analysis is pure, recovers chemical reagent Co., Ltd purchased from Tianjin；Silicon carbide ceramics (α-SiC) and high specific area carbon
SiClx (β-SiC), purchased from Pingxiang Rui Ze silicon materials Co., Ltd.Embodiment 1：
100 grams of Sb is taken respectively2O3, add 0.1mol/L NaOH aqueous solution regulation 1.0 × 10-4Mol/L gold chloride
The pH value of solution is 7, and solution temperature is maintained at 60 DEG C, stirs 15min；Carrier is added in the case of stirring, impregnates the carrier,
The NaOH solution regulation pH value for adding 0.1mol/L is 7, stirs 120min, soaks half an hour with 0.1mol/L weak aqua ammonia,
Again 6 removing Cl are washed with 70 DEG C of deionized water-To dozens of ppm, then dried 12 hours at 80 DEG C, after extruded moulding
It is calcined 6 hours at 350 DEG C.0.02wt%Au/Sb is made respectively2O3Catalyst 1#。
Embodiment 2：
0.05wt%Au/Sb is made with embodiment 1 in other2O3Catalyst 2#。
Embodiment 3：
0.095wt%Au/Sb is made with embodiment 1 in other2O3Catalyst 3#。
Embodiment 4：
0.48wt%Au/Sb is made with embodiment 1 in other2O3Catalyst 4#。
Embodiment 5：Comparative example
0.05wt%Au/ZrO2 catalyst 5 is made with embodiment 1 in other#。
Embodiment 6：Comparative example
0.05wt%Au/TiO2 catalyst 6 is made with embodiment 1 in other#。
Embodiment 7：Comparative example
0.05wt%Au/ α-Al are made with embodiment 1 in other2O3Catalyst 7#。
The contrast of catalyst
With the catalyst prepared by embodiment 1~7, hypergravity oxidative esterification test evaluation is carried out respectively 1000 hours.
200mL catalyst is added in hypergravity stirred autoclave, MAL mass fraction is 25% methyl-prop
Olefine aldehydr-methanol solution is with 1000mL/s flow velocity continuous feed.The NaOH- methanol solutions that mass fraction is 2% are with 500mL/s's
Flow velocity continuous feed is added to supergravity reactor in a manner of cocurrent and neutralize the pH value of maintenance reaction system to 7.0 ± 0.3,
Air is blown into 1500mL/s speed, reaction pressure 3MPa, successive reaction prepares methyl-prop under 80 DEG C of reaction temperature
E pioic acid methyl ester, supergravity reactor rotor speed are 2000rpm.The feed liquid that hypergravity revolving reaction kettle is come out, sampling are carried out
Analysis.Experimental result is shown in Table 1
The result of the test of table 1
As seen from Table 1,1~4 is contrasted#With 5~7#Catalyst, the catalyst using antimony oxide as carrier, catalyst activity
It is higher with yield, and it is almost inactive using other as catalyst.
The contrast of different process：
With the catalyst prepared by embodiment 1, reaction evaluating is carried out under the following conditions.
Appreciation condition is as follows：
A) 200mL catalyst, reaction pressure 5MPa, in 150 DEG C of reaction temperature are added in hypergravity stirred autoclave
The lower successive reaction of degree prepares methyl methacrylate, and supergravity reactor rotor speed is 3000rpm.By hypergravity revolving reaction
The feed liquid that kettle comes out, sampling are analyzed.
B) 200mL catalyst, reaction pressure 0.1MPa, in 60 DEG C of reaction temperature are added in hypergravity stirred autoclave
The lower successive reaction of degree prepares methyl methacrylate, and supergravity reactor rotor speed is 300rpm.By hypergravity revolving reaction
The feed liquid that kettle comes out, sampling are analyzed.
C) 200mL catalyst, reaction pressure 5MPa, in 150 DEG C of reaction temperature are added in convention stir reactor
Lower successive reaction prepares methyl methacrylate, and conventional reactor rotor speed is 3000rpm.Convention stir reactor is come out
Feed liquid, sampling analyzed.
D) 200mL catalyst is added in stirred autoclave, reaction pressure 0.1MPa, is connected under 60 DEG C of reaction temperature
Continuous reaction prepares methyl methacrylate, and reactor rotating speed of agitator is 300rpm.The feed liquid that convention stir reactor is come out,
Sampling is analyzed.
The humid test result of table 2
As seen from Table 2, hypergravity technique and common process, under identical reaction temperature and pressure, hypergravity technique is remote
It is much better than common process, this is probably because the reinforcing transmission effect of hypergravity improves reactivity worth.
Claims (6)
1. a kind of hypergravity catalyst for oxidation of aldehydes esterification for carboxylate, it is characterised in that the catalyst is that Au depositions is heavy
Form sediment in Sb2O3On dust carrier, it is dried afterwards, is fired into supported nano-Au/Sb2O3Catalyst；Described Au content
For 0.001~5wt%, described drying temperature is 80~350 DEG C.
A kind of 2. hypergravity catalyst for oxidation of aldehydes esterification for carboxylate according to claim 1, it is characterised in that
Described Au content is 0.01~0.1wt%, and described drying temperature is 120~250 DEG C.
3. a kind of hypergravity catalytic reaction for oxidation of aldehydes esterification for carboxylate, it is characterised in that make in hypergravity reactor
With the catalyst described in claim 1, reaction mass is methacrylaldehyde material, alcohol and the air of gas phase or liquid phase, in reaction pressure
Under 0.1~5MPa, reaction, which is maintained under liquid-phase condition, to be carried out.
4. a kind of hypergravity catalytic reaction for oxidation of aldehydes esterification for carboxylate according to claim 3, its feature exist
In described methacrylaldehyde material selected from gas-phase propene aldehyde gas gas-phase objects obtained by propylene oxidation, oxidation of propane or glycerine gas-phase dehydration
Material, or liquid propylene aldehyde material obtained by glycerine liquid-phase dehydration.
5. a kind of hypergravity catalytic reaction for oxidation of aldehydes esterification for carboxylate according to claim 3, its feature exist
In the one kind of described alcohol in methanol, ethanol, butanol, ethylene glycol and octanol.
6. a kind of hypergravity catalytic reaction for oxidation of aldehydes esterification for carboxylate according to claim 3, its feature exist
In the rotating speed of hypergravity reactor be 300~3000r/min.
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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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| 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 |
| EP4182075A1 (en) * | 2020-07-14 | 2023-05-24 | 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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| CN1485133A (en) * | 2003-01-22 | 2004-03-31 | 中国科学院过程工程研究所 | New pattern catalyst for preparing methyl methacrylate by one-step oxidation-esterification from methylacrolein |
| CN1516619A (en) * | 2001-06-04 | 2004-07-28 | ��ʽ�����ձ���ý | Catalyst for carboxylic ester production and process for producing carboxylic ester |
| CN1524614A (en) * | 2003-09-12 | 2004-09-01 | 中国科学院过程工程研究所 | Catalyst for one step oxidation esterification of unsaturated aldehyde to produce unsaturated carboxylate |
| CN101073776A (en) * | 2006-05-15 | 2007-11-21 | 北京化工大学 | Catalyst for producing methyl-acrylate from methyl-acrolein and its production |
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2014
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| CN1516619A (en) * | 2001-06-04 | 2004-07-28 | ��ʽ�����ձ���ý | Catalyst for carboxylic ester production and process for producing carboxylic ester |
| CN1485133A (en) * | 2003-01-22 | 2004-03-31 | 中国科学院过程工程研究所 | New pattern catalyst for preparing methyl methacrylate by one-step oxidation-esterification from methylacrolein |
| CN1524614A (en) * | 2003-09-12 | 2004-09-01 | 中国科学院过程工程研究所 | Catalyst for one step oxidation esterification of unsaturated aldehyde to produce unsaturated carboxylate |
| CN101073776A (en) * | 2006-05-15 | 2007-11-21 | 北京化工大学 | Catalyst for producing methyl-acrylate from methyl-acrolein and its production |
Non-Patent Citations (2)
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