CN105170134B - The catalyst of MAL air oxidation synthesizing methyl acrylic acid and application - Google Patents
The catalyst of MAL air oxidation synthesizing methyl acrylic acid and application Download PDFInfo
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- CN105170134B CN105170134B CN201510605948.4A CN201510605948A CN105170134B CN 105170134 B CN105170134 B CN 105170134B CN 201510605948 A CN201510605948 A CN 201510605948A CN 105170134 B CN105170134 B CN 105170134B
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- catalyst
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- acrylic acid
- methyl acrylic
- synthesizing methyl
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The catalyst of MAL air oxidation synthesizing methyl acrylic acid, it is characterised in that catalytic component is calculated as with atomicity：Mo1、Va、Tib、Oc；A values scope is 0~0.4 or 0.05~0.15；B values scope is 8~30 or 15~22.It is an advantage of the invention that：Using fixed-bed process, with air oxidation MAL synthesizing methyl acrylic acid, partial tail gas recycled；Using nano-titanium oxide as carrier, with MoO3、V2O5For active component, reaction temperature is declined to a great extent to 180~220 DEG C, and MAA is obtained in high yield.
Description
Technical field
The present invention relates to the catalyst field of synthesizing methyl acrylic acid, and in particular to one kind with MAL, air
For raw material, fixed-bed process synthesizing methyl acrylic acid and catalyst.
Background technology
Methacrylic acid and its esters are important engineering material and basic organic synthesis raw material, and domestic scale reaches million tons
Level, any technological progress can all produce great economic benefit.Current technique is important or acetone cyanohydrin route：Acetone and hydrogen cyanide
HCN reacts, and generates acetone cyanohydrin, then with sulphuric acid hydrolysis, generate methacrylic acid（MAA）, producing ammonium sulfate byproduct.This process costs compared with
Height, equipment corrosion is serious, pollutes larger, a large amount of useless ammonium sulfate of by-product.MAL reoxidizes synthesis MAA, there is a large amount of
Patent report（Such as CN 1647854A, CN1273232A, JP57-171443）, using the heteropoly acid containing Mo, reaction temperature is general
At 320~360 DEG C, yield is 70~84%, but catalyst preparation is complicated, and yield is not high, and the life-span is shorter.
The content of the invention
The purpose of the present invention provides MAL air aiming at the deficiency of existing synthesizing methyl acrylic acid process
The catalyst of oxidative synthesis methacrylic acid and application.
The catalyst of MAL air oxidation synthesizing methyl acrylic acid, catalytic component is calculated as with atomicity：
Mo1VaTibOc；
A values scope is 0~0.4；
B values scope is 8~30；
The summation of c oxygen atoms for needed for meeting each element oxide.
The processing method of catalyst is:
A, ammonium molybdate or molybdenum oxide be dissolved in ammoniacal liquor, molybdenum solution is made;
B, vanadic anhydride or ammonium metavanadate be dissolved in oxalic acid, vanadium solution is made；
C, molybdenum solution, vanadium solution and Wastewater by Nanometer Anatase titanium dioxide are put into kneader are kneaded into cream；
D, by mixed material aerobic conditions be calcined, 580~800 DEG C of catalyst calcination temperature;6~15h of calcination time, roasting
Burn till powder；
E, powder is added to pure water extruded moulding.
Catalyst is used for the synthesis of MAL air oxidation synthesizing methyl acrylic acid；Synthesis technique is：With methyl-prop
Olefine aldehydr and air are raw material, the loaded particles catalyst in fixed bed, 180~220 DEG C of temperature；0.03~0.1MPa of pressure, oxygen
It is combined to methacrylic acid.
Catalyst after inactivation is with 400~480 DEG C of oxygen-containing water vapour on-line regenerations, standard state volume ratio:Air capacity: steam
Amount=0.05~0.1: 1.
MAL load is that 60~120g/ rises catalyst h.
Nano titanium oxide come from anatase titanium dioxide metatitanic acid, metatitanic acid calcining heat be 400~550 DEG C, granularity be 80~
150nm, surface area is 60~120m2/g。
Mixing air gas velocity containing tail gas is 0.4~1 m3/ liter catalyst h.
Fresh air and exhaust gas volumes ratio：Fresh air: tail gas=1: 0.1~1.5.
It is an advantage of the invention that：Using fixed-bed process, with air oxidation MAL synthesizing methyl acrylic acid, part
Circulation of tail gas is applied mechanically；Using nano-titanium oxide as carrier, with MoO3、V2O5For active component, reaction temperature declines to a great extent to 180~
220 DEG C, MAA is obtained in high yield.
Embodiment
The catalyst of MAL air oxidation synthesizing methyl acrylic acid, catalytic component is calculated as with atomicity：
Mo1VaTibOc；
Agent component is calculated as with atomicity：
Mo1、Va、Tib、Oc；
A values scope is 0~0.4；
B values scope is 8~30；
The summation of c oxygen atoms for needed for meeting each element oxide.
The processing method of catalyst is:
A, ammonium molybdate or molybdenum oxide be dissolved in ammoniacal liquor, molybdenum solution is made;
B, vanadic anhydride or ammonium metavanadate be dissolved in oxalic acid, vanadium solution is made；
C, molybdenum solution, vanadium solution and Wastewater by Nanometer Anatase titanium dioxide are put into kneader are kneaded into cream；
D, by mixed material aerobic conditions be calcined, 580~800 DEG C of catalyst calcination temperature;6~15h of calcination time, roasting
Burn till powder；
E, powder is added to pure water extruded moulding.
Catalyst is used for the synthesis of MAL air oxidation synthesizing methyl acrylic acid；Synthesis technique is：With methyl-prop
Olefine aldehydr and air are raw material, the loaded particles catalyst in fixed bed, 180~220 DEG C of temperature；0.03~0.1MPa of pressure, oxygen
It is combined to methacrylic acid.
Catalyst after inactivation is with 400~480 DEG C of oxygen-containing water vapour on-line regenerations, standard state volume ratio:Air capacity: steam
Amount=0.05~0.1: 1.
MAL load is that 60~120g/ rises catalyst h.
Nano titanium oxide come from anatase titanium dioxide metatitanic acid, metatitanic acid calcining heat be 400~550 DEG C, granularity be 80~
150nm, surface area is 60~120m2/g。
Mixing air gas velocity containing tail gas is 0.4~1 m3/ liter catalyst h.
Fresh air and exhaust gas volumes ratio：Fresh air: tail gas=1: 0.1~1.5.
Specific embodiment:
With circulation fused salt 180~220 DEG C of catalyst temperature of control, it is pumped into quantitative MAL and gasifies, roots blower
The stable air containing tail gas is pressed into, condensed absorbent obtains MAA, and partial tail gas is recycled, the discharge of another part tail gas clean-up.
Catalyst after inactivation with 400~480 DEG C of oxygen-containing steam regenerations, after catalyst regeneration activity almost not under
Drop.
The present invention is implemented using fixed-bed process, fixed bed specification（Not limited to this specification）：Tubulation φ 38 × 3.0 ×
3000,114 altogether, the ㎏ of loading catalyst 270, fused salt heat exchanging, temperature-controlled precision ± 1 DEG C.
Catalyst preparation process is described as follows：
（1）Following table raw material is put into kneader, appropriate pure water is added and mediates repeatedly uniformly：
A. the ㎏ of Wastewater by Nanometer Anatase titanium dioxide 243；
B. the ㎏ of ammonium molybdate 30.24 or the ㎏ of molybdenum oxide 25.7 are dissolved in the ammoniacal liquor of 60 ㎏ 20%；
C. the ㎏ of vanadic anhydride 1.30 or the ㎏ of ammonium metavanadate 1.67 are dissolved in the mixed solution of 3.25 ㎏ oxalic acid and 10 liters of water
In.
（2）Mixed material is calcined in aerobic conditions, 300~400 DEG C of temperature, 8~10h of time；
（3）Plus pure water extruded moulding, can be the arbitrary shapes such as elliposoidal, column, open column shape, plum blossom-shaped；
（4）Drying；
（5）In rotary kiln, 700 DEG C of 8~9h of calcining.
Obtain Mo1.0VaTibOcThe ㎏ of catalyst 270 is used for fixed-bed process.
It is as follows for fixed-bed process process specific embodiment：
（1）Control 195 ± 1 DEG C of fixed bed catalyst temperature, 170 ± 10 DEG C of premixing unstrpped gas temperature, fixed bed pressure
Power 0.045MPa, opens cooling heat exchanger and exhaust purifier；
（2）Fresh air flow 95m3/h（Standard state）, exhaust flow 95m3/h（Standard state）；
（3）Continuous-stable feeds intake：27 ㎏ of MAL/h；
（4）Condensation collection product, content and purity are determined with gas chromatogram fixative.
（5）As a result：
Embodiment 1：
Embodiment 2：
On the basis of embodiment 1, reduction catalyst temperature is other constant to 170 DEG C：
Embodiment 3：
On the basis of embodiment 1, rise catalyst temperature is other constant to 220 DEG C：
Embodiment 4：
After the basis of embodiment 1 operation 240h：
Embodiment 5：
On the basis of embodiment 3, stop throwing MAL, 430 DEG C, water flowing steam 5.3m3/h（Standard state）And air
0.53 m3/h（Standard state）Mixed gas regenerates activation of catalyst：
| MAL conversion ratio | 99.6% |
| Accessory substance acetone molar ratio | 0.9% |
| MAL molar yield | 97.8% |
Embodiment 6：
On the basis of embodiment 1, change catalyst composition, it is other constant：
Embodiment 7：
On the basis of embodiment 1, change catalyst composition, it is other constant：
Claims (8)
1. the catalyst of MAL air oxidation synthesizing methyl acrylic acid, it is characterised in that catalytic component is in terms of atomicity
For：
Mo1VaTibOc；
A values scope is 0~0.4；
B values scope is 8~30；
The summation of c oxygen atoms for needed for meeting each element oxide.
2. the catalyst of MAL air oxidation synthesizing methyl acrylic acid according to claim 1, it is characterised in that
The processing method of catalyst is:
A, ammonium molybdate or molybdenum oxide be dissolved in ammoniacal liquor, molybdenum solution is made;
B, vanadic anhydride or ammonium metavanadate be dissolved in oxalic acid, vanadium solution is made；
C, molybdenum solution, vanadium solution and Wastewater by Nanometer Anatase titanium dioxide are put into kneader are kneaded into cream；
D, mixed material is calcined in aerobic conditions, 580~800 DEG C of catalyst calcination temperature, 6~15h of calcination time is fired into
Powder；
E, powder is added to pure water extruded moulding.
3. the catalyst of MAL air oxidation synthesizing methyl acrylic acid according to claim 1 or 2, its feature exists
It is used for the synthesis of MAL air oxidation synthesizing methyl acrylic acid in catalyst；Synthesis technique is：With MAL and
Air is raw material, the loaded particles catalyst in fixed bed, 180~220 DEG C of temperature；0.03~0.1MPa of pressure, oxidative synthesis
Methacrylic acid.
4. the catalyst of MAL air oxidation synthesizing methyl acrylic acid according to claim 1 or 2, its feature exists
In the catalyst after inactivation with 400~480 DEG C of oxygen-containing water vapour on-line regenerations, standard state volume ratio is:Air capacity: quantity of steam=
0.05~0.1: 1.
5. the catalyst of MAL air oxidation synthesizing methyl acrylic acid according to claim 3, it is characterised in that
MAL load is that 60~120g/ rises catalyst h.
6. the catalyst of MAL air oxidation synthesizing methyl acrylic acid according to claim 3, it is characterised in that
Nano titanium oxide comes from anatase titanium dioxide metatitanic acid, and metatitanic acid calcining heat is 400~550 DEG C, and granularity is 80~150nm, surface
Product is 60~120m2/g。
7. the catalyst of MAL air oxidation synthesizing methyl acrylic acid according to claim 3, it is characterised in that
Mixing air gas velocity containing tail gas is 0.4~1 m3/ liter catalyst h.
8. the catalyst of MAL air oxidation synthesizing methyl acrylic acid according to claim 3, it is characterised in that
Fresh air and exhaust gas volumes ratio：Fresh air: tail gas=1: 0.1~1.5.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510605948.4A CN105170134B (en) | 2015-09-22 | 2015-09-22 | The catalyst of MAL air oxidation synthesizing methyl acrylic acid and application |
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| CN201510605948.4A CN105170134B (en) | 2015-09-22 | 2015-09-22 | The catalyst of MAL air oxidation synthesizing methyl acrylic acid and application |
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| CN105170134A CN105170134A (en) | 2015-12-23 |
| CN105170134B true CN105170134B (en) | 2017-07-21 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1025611B (en) * | 1974-11-12 | 1978-08-30 | Montedison Spa | PROCEDURE FOR THE PREPARATION OF UNSATURATED CARBOXYLIC ACIDS BY CATALYTIC OXIDATION IN THE GASEOUS PHASE OF THE CORRESPONDING ALDEHYDES |
| JP3972718B2 (en) * | 2002-04-16 | 2007-09-05 | 住友化学株式会社 | Method for regenerating catalyst for methacrylic acid production |
| CN100333834C (en) * | 2004-06-11 | 2007-08-29 | 谷育英 | Composite metal oxide for unsaturated aldehyde selective oxidation and preparing method thereof |
| EP1987877A3 (en) * | 2007-03-29 | 2010-10-13 | Nippon Shokubai Co., Ltd. | Oxide catalyst, process for producing acrolein or acrylic acid and process for producing water-absorbent resin |
| EP2832718B1 (en) * | 2012-03-29 | 2020-01-08 | Nippon Shokubai Co., Ltd. | Process for producing acrylic acid using fixed-bed multitubular reactor |
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