CN103721744A - Hydrophobic catalyst for producing methyl methacrylate with one-step oxidative esterification and preparation method of hydrophobic catalyst - Google Patents
Hydrophobic catalyst for producing methyl methacrylate with one-step oxidative esterification and preparation method of hydrophobic catalyst Download PDFInfo
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- CN103721744A CN103721744A CN201310755293.XA CN201310755293A CN103721744A CN 103721744 A CN103721744 A CN 103721744A CN 201310755293 A CN201310755293 A CN 201310755293A CN 103721744 A CN103721744 A CN 103721744A
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Abstract
The invention discloses a novel preparation method of a catalyst PdxMy/SDB based on hydrophobic carrier SDB-loaded elements such as palladium, bismuth, lead and iron. The catalyst composition is PdxMy/SDB, wherein M is one or more of auxiliary metal elements Pb, Bi and Fe; x and y are mass fractions of the elements relative to a carrier; the mass fraction of Pd is 1%-6%; the mass fraction of the auxiliary metal elements is 0.1%-3%. The hydrophobic catalyst disclosed by the invention is applied to production of methyl methacrylate (MMA) with one-step oxidative esterification of methylacrolein (MAL). The reaction can be carried out at low temperature, and by-products can be effectively reduced; a plurality of metals are gradually and orderly loaded and restored on the hydrophobic carrier in the novel catalyst preparation method, so that the metals are effectively and fully restored, and the synergistic effect of the metals is enhanced. Therefore, the hydrophobic catalyst has the high MAL conversion rate of 98.2%, and the high MMA selectivity of 98.6%, and is low in energy consumption and good in stability.
Description
Technical field
The present invention relates to produce for oxidation step esterification hydrophobic catalyst and the preparation method of methyl methacrylate, a kind of by metering system aldehyde oxidation esterification production methyl methacrylate Pd
xm
ythe preparation method that/SDB hydrophobic catalyst is new.
Background technology
Methyl methacrylate (MMA) is most important industrialization product in methyl acrylic ester, is mainly used to produce lucite (polymethyl methacrylate, PMMA).MMA also can be used for surface coating industry, polyvinyl chloride resin modifier.Along with scientific and technological progress, MMA is for high-technology fields such as LCDs optical plate, optical fiber, CD, lens, medicine functional material in recent years.
The main production method of MMA is still acetone cyanohydrin (ACH) route at present, but the method exists raw material hydrogen cyanide to buy difficulty, the problems such as the difficult treatment of accessory substance ammonium sulfate.C4 route is combined proposition by mitsubishi rayon and Japanese MMA monomer company.This method, take isobutene or its hydrate tert-butyl alcohol as initial feed, is prepared methacrylic acid through two-step oxidation, and then methacrylic acid reacts with methanol esterification and produces MMA, and weak point is that yield is lower.
Japan Asahi Kasei Corporation has developed the technique by MAL direct oxidation esterification MMA processed at first, and has carried out small-scale trial production.This technique, without methacrylic acid step, has been avoided the generation of the side reactions such as methacrylic acid polymerization effectively, and equipment is simple, Atom economy is high, therefore causes various countries scientific research personnel's broad research.The key of one-step technology is to prepare novel catalyst, the catalyst of development mainly contains gas-phase oxidation catalyst (BR1415636 at present, US4088822, US4440946), palladium series catalyst (JP5148184, JP2001233828, JP2003260357, US6348619,), the several types such as golden series catalysts (JP2000154164, JP2003192632, JP2003361086).Wherein vapor phase oxidative esterification reaction temperature is higher, produces a large amount of accessory substances, the easier inactivation of catalyst.It is lower that monometallic Pd catalyst has conversion ratio, and meet the easier inactivation of water.It is five yuan of resin catalysts that patent CN101073784 adopts palladium, has avoided the inhibitory action of water in reaction.But the general preparation method who adopts many metals loads simultaneously reduction of multimetal reforming catalyst, reduces insufficiently, is prone to metal agglomeration phenomenon, affects catalytic activity.
Summary of the invention
The invention provides a kind of preparation method who is produced methyl methacrylate hydrophobic catalyst by the esterification of metering system aldehyde oxidation.Technical scheme of the present invention is as follows:
The hydrophobic catalyst of producing methyl methacrylate for oxidation step esterification, catalyst consists of Pd
xm
y/ SDB; Wherein M is one or more in promoter metal Pb, Bi, Fe element; X, y are respectively the mass fraction of every kind of element with respect to carrier: the mass fraction of Pd is 1-6%, and the mass fraction of promoter metal component is 0.1-3%.
Described carrier is hydrophobic material, is SDVB copolymer SDB.
For oxidation step esterification, produce the preparation method of the hydrophobic catalyst of methyl methacrylate, active component Pd and other one or more assistant metal element loads are reduced on hydrophobic carrier SDB, step is as follows:
(1) according to catalyst, contain each metal component mass fraction, take out required PdCl
2quality, be dissolved in organic solvent, be placed in 70 ℃ of-80 ℃ of stirred in water bath and dissolve; By pretreated carrier incipient impregnation in living solution 12 hours; The carrier having flooded is placed in to the dry 4-6h of vacuum drying chamber, and infrared lamp is dried 2-4h until solvent is dried completely;
(2) dried product packs quartz ampoule into, is placed in catalyst reduction stove, first the logical high pure nitrogen air in tube of rushing, start to heat up, 10～20 ℃/min of programming rate, rises to and stops logical nitrogen after assigned temperature and change logical high-purity hydrogen reduction simultaneously, hydrogen flowing quantity 20-30ml/min, reduction; Then stop heating, cooling, changing hydrogen is nitrogen, is cooled to room temperature takes out with nitrogen protection, makes catalyst finished product.
(3) take out one or more of required promoter metal compound quality, be dissolved in organic solvent, be placed in 70-80 ℃ of stirred in water bath and dissolve; By pretreated carrier incipient impregnation in living solution 12 hours; The carrier having flooded is placed in to the dry 4-6h of vacuum drying chamber, and infrared lamp is dried 2-4h until solvent is dried completely, and by the method reduction of step (2); Promoter metal load is reduced on hydrophobic carrier SDB.
The promoter metal order that described load is reduced on hydrophobic carrier SDB is Pd, Pb, Bi and Fe.
In described auxiliary element Pb, Bi, Fe, required metallic compound comprises chloride, nitrate, sulfate or acetate.
Described reduction temperature is 120-250 ℃, and the recovery time is 4-12 hour.
In the present invention, the selective S computing formula of the conversion ratio C of MAL and methyl methacrylate is as follows:
The catalyst that the hydrophobic carrier that the present invention introduces overcomes current use in use occurs to meet the active phenomenon obviously declining of water, can form larger lifting to catalyst performance, improves catalyst service life.New method for preparing catalyst adopts progressively load method of reducing successively of many metals, the precipitation of avoiding various slaines to contact and to produce, the hydrophobic catalyst that the present invention adopts, produces methyl methacrylate (MMA) for the esterification of MAL (MAL) oxidation step.Reaction can be carried out at low temperatures, can effectively reduce the generation of accessory substance.New method for preparing catalyst adopt many metals progressively successively load reduce on hydrophobic carrier, make effectively fully reduction of metal, strengthen intermetallic synergy, there is high MAL conversion ratio 98.2% and high MMA selective 98.6%, and energy consumption is low, good stability.
The specific embodiment
Below by embodiment, the invention will be further described.
Embodiment 1
Accurately take 0.500g PdCl
2be dissolved in 30ml DMF (DMF), 70 ℃ of stirred in water bath are dissolved, and obtain peony transparency liquid, and pretreated SDB carrier 10g be impregnated in living solution to 12 hours.The carrier having flooded is placed in to the dry 6h of 90 ℃ of vacuum drying chambers, infrared lamp is dried 4h, until solvent is dried completely, dried product packs quartz ampoule into, is placed in catalyst reduction stove, the first logical high pure nitrogen air in tube of rushing, start to heat up, 10 ℃/min of programming rate, rises to 200 ℃ and stops logical nitrogen and change logical high-purity hydrogen reduction simultaneously, hydrogen flowing quantity 30ml/min, reduces 10 hours.Finally stop heating, changing hydrogen is nitrogen, is cooled to room temperature takes out with nitrogen protection, accurately takes 0.364g (CH
3cOO)
2pb, repeats above-mentioned dip loading and reduction step, makes catalyst finished product Pd
3%pb
2%/ SDB.
Embodiment 2
Accurately take 0.500g PdCl
2be dissolved in 30ml DMF (DMF), 70 ℃ of stirred in water bath are dissolved, and obtain peony transparency liquid, and pretreated SDB carrier 10g be impregnated in living solution to 12 hours.The carrier having flooded is placed in to the dry 6h of 90 ℃ of vacuum drying chambers, infrared lamp is dried 4h, until solvent is dried completely, dried product packs quartz ampoule into, is placed in catalyst reduction stove, the first logical high pure nitrogen air in tube of rushing, start to heat up, 10 ℃/min of programming rate, rises to 180 ℃ and stops logical nitrogen and change logical high-purity hydrogen reduction simultaneously, hydrogen flowing quantity 30ml/min, reduces 10 hours.Finally stop heating, changing hydrogen is nitrogen, is cooled to room temperature takes out with nitrogen protection, accurately takes respectively 0.182g (CH
3cOO)
2pb and 0.185g BiCl
3, according to Pb, the order of Bi repeats above-mentioned dip loading and reduction step, makes catalyst finished product Pd
3%pb
1%bi
1.2%/ SDB.
Embodiment 3
Accurately take 0.500g PdCl
2be dissolved in 30ml DMF (DMF), 80 ℃ of stirred in water bath are dissolved, and obtain peony transparency liquid, and pretreated SDB carrier 10g be impregnated in living solution to 12 hours.The carrier having flooded is placed in to the dry 5h of 90 ℃ of vacuum drying chambers, infrared lamp is dried 4h, until solvent is dried completely, dried product packs quartz ampoule into, is placed in catalyst reduction stove, the first logical high pure nitrogen air in tube of rushing, start to heat up, 10 ℃/min of programming rate, rises to 220 ℃ and stops logical nitrogen and change logical high-purity hydrogen reduction simultaneously, hydrogen flowing quantity 20ml/min, reduces 12 hours.Finally stop heating, changing hydrogen is nitrogen, is cooled to room temperature and takes out, more accurately take respectively 0.182g (CH with nitrogen protection
3cOO)
2pb, 0.462g BiCl
3with 0.722g Fe (NO
3)
3, according to Pb, Bi, the load of order repeated impregnations and the reduction step of Fe, make catalyst finished product Pd
3%pb
1%bi
3%fe
1%/ SDB.
Embodiment 4
Accurately take 0.500g PdCl
2be dissolved in 30ml DMF (DMF), 70 ℃ of stirred in water bath are dissolved, and obtain peony transparency liquid, and pretreated SDB carrier 10g be impregnated in living solution to 12 hours.The carrier having flooded is placed in to the dry 6h of 90 ℃ of vacuum drying chambers, infrared lamp is dried 4h, until solvent is dried completely, dried product packs quartz ampoule into, is placed in catalyst reduction stove, the first logical high pure nitrogen air in tube of rushing, start to heat up, 15 ℃/min of programming rate, rises to 200 ℃ and stops logical nitrogen and change logical high-purity hydrogen reduction simultaneously, hydrogen flowing quantity 30ml/min, reduces 10 hours.Finally stop heating, changing hydrogen is nitrogen, is cooled to room temperature and takes out, more accurately take respectively 0.182g (CH with nitrogen protection
3cOO)
2pb, 0.185g BiCl
3with 0.433g Fe (NO
3)
3, according to Pb, Bi, the load of order repeated impregnations and the reduction step of Fe, make catalyst finished product Pd
3%pb
1%bi
1.2%fe
0.6%/ SDB.
Comparative example 1
By 0.500g PdCl
2, 3g red fuming nitric acid (RFNA) is dissolved in 50mL distilled water, adds a certain amount of sodium carbonate to without Bubble formation after dissolving, then adds 10g CaCO
3carrier, stirs 1h under normal temperature, adds 40mL5wt%NaOH5wt% formalin, at 70 ℃, stirs 30min, filters, and washes filter cake with water, obtains black solid.Separately get 0.16g Pb (NO
3)
2, 0.464g Bi (NO
3)
2, 0.433g Fe (NO
3)
31.78g red fuming nitric acid (RFNA) is dissolved in 30mL water, adds above-mentioned made black solid after dissolving, under normal temperature, stirs 1h, adds 25mL5wt%NaOH5wt% formalin, at 70 ℃, stirs 30min, filters, and washes filter cake with water.Filter cake is 60 ℃ of dry 10h under vacuum condition, are ground to Powderedly, make catalyst P d
3%pb
1%bi
2%fe
0.6%/ CaCO
3.
Comparative example 2
Accurately take 0.500g PdCl
2, 0.182g (CH
3cOO)
2pb, 0.185g BiCl
3with 0.433g Fe (NO
3)
3, to mix and be dissolved in 30ml DMF (DMF), 70 ℃ of stirred in water bath are dissolved, and obtain peony transparency liquid, and pretreated SDB carrier 10g be impregnated in living solution to 12 hours.The carrier having flooded is placed in to the dry 6h of 90 ℃ of vacuum drying chambers, infrared lamp is dried 4h, until solvent is dried completely, dried product packs quartz ampoule into, is placed in catalyst reduction stove, the first logical high pure nitrogen air in tube of rushing, start to heat up, 15 ℃/min of programming rate, rises to 200 ℃ and stops logical nitrogen and change logical high-purity hydrogen reduction simultaneously, hydrogen flowing quantity 30ml/min, reduces 10 hours.Finally stop heating, changing hydrogen is nitrogen, is cooled to room temperature takes out with nitrogen protection, makes catalyst finished product Pd
3%pb
1%bi
1.2%fe
0.6%/ SDB.(dipping simultaneously).
Comparative example 3
Accurately take 0.500g PdCl
2be dissolved in 30ml DMF (DMF), 70 ℃ of stirred in water bath are dissolved, and obtain peony transparency liquid, and pretreated SDB carrier 10g be impregnated in living solution to 12 hours.The carrier having flooded is placed in to the dry 6h of 90 ℃ of vacuum drying chambers, infrared lamp is dried 4h, until solvent is dried completely, dried product packs quartz ampoule into, is placed in catalyst reduction stove, the first logical high pure nitrogen air in tube of rushing, start to heat up, 15 ℃/min of programming rate, rises to 200 ℃ and stops logical nitrogen and change logical high-purity hydrogen reduction simultaneously, hydrogen flowing quantity 30ml/min, reduces 10 hours.Finally stop heating, changing hydrogen is nitrogen, is cooled to room temperature and takes out, more accurately take respectively 0.182g (CH with nitrogen protection
3cOO)
2pb, 0.185g BiCl
3with 0.433g Fe (NO
3)
3, just according to Bi, Pb, the load of order repeated impregnations and the reduction step of Fe, make catalyst finished product Pd
3%bi
1.2%pb
1%fe
0.6%/ SDB.
Comparative example 4
Accurately take 0.500g PdCl
2be dissolved in 30ml DMF (DMF), 70 ℃ of stirred in water bath are dissolved, and obtain peony transparency liquid, and pretreated SDB carrier 10g be impregnated in living solution to 12 hours.The carrier having flooded is placed in to the dry 5h of 90 ℃ of vacuum drying chambers, infrared lamp is dried 4h, until solvent is dried completely, dried product packs quartz ampoule into, is placed in catalyst reduction stove, the first logical high pure nitrogen air in tube of rushing, start to heat up, 20 ℃/min of programming rate, rises to 200 ℃ and stops logical nitrogen and change logical high-purity hydrogen reduction simultaneously, hydrogen flowing quantity 30ml/min, reduces 10 hours.Finally stop heating, changing hydrogen is nitrogen, is cooled to room temperature and takes out, more accurately take respectively 0.182g (CH with nitrogen protection
3cOO)
2pb, 0.185g BiCl
3with 0.433g Fe (NO
3)
3, just according to Fe, Pb, the load of order repeated impregnations and the reduction step of Bi, make catalyst finished product Pd
3%fe
0.6%pb
1%bi
1.2%/ SDB.
Embodiment 5
In the reactor with condenser pipe, add absolute methanol and MAL, its mol ratio is 40:1, add respectively the catalyst of embodiment 1-4 and comparative example 1-4, catalyst addition is 3%, reactor oxygen gas flow rate 0.53m/h, subzero 20 ℃ of ethanol condensing refluxes for tail gas, stirring reaction under 50 ℃ of conditions, react and leach fast catalyst after 6 hours, the reactant liquor of obtaining is analyzed.The results are shown in Table one
Embodiment 6
In the reactor with condenser pipe, add absolute methanol and MAL, its mol ratio is 40:1, add the catalyst of embodiment 4, catalyst addition is 3%, reactor oxygen gas flow rate 0.53m/h, subzero 20 ℃ of ethanol condensing refluxes for tail gas, stirring reaction under 60 ℃ of conditions, react and leach fast catalyst after 6 hours, the reactant liquor of obtaining is analyzed.。The results are shown in Table one
Embodiment 7
In the reactor with condenser pipe, add absolute methanol and MAL, its mol ratio is 50:1, add the catalyst of embodiment 4, catalyst addition is 3%, reactor oxygen gas flow rate 0.53m/h, subzero 20 ℃ of ethanol condensing refluxes for tail gas, stirring reaction under 50 ℃ of conditions, react and leach fast catalyst after 6 hours, the reactant liquor of obtaining is analyzed.The results are shown in Table one
Embodiment 8
In the reactor with condenser pipe, add absolute methanol and MAL, its mol ratio is 40:1, add the catalyst of embodiment 4, catalyst addition is 3%, reactor oxygen gas flow rate 0.53m/h, subzero 20 ℃ of ethanol condensing refluxes for tail gas, stirring reaction under 50 ℃ of conditions, react and leach fast catalyst after 6 hours, the reactant liquor of obtaining is analyzed.After catalyst Reusability 5 times, MMA productive rate is still more than 95%.The results are shown in Table two.
Table one embodiment 1-6 evaluating catalyst result
Table two embodiment 8 evaluating catalyst results
| Sequence number | Catalyst | MAL conversion ratio % | The selective % of MMA |
| 1 | Pd 3%Pb 1%Bi 1.2%Fe 0.6%/SDB | 98.2 | 98.6 |
| 2 | Pd 3%Pb 1%Bi 1.2%Fe 0.6%/SDB | 98.0 | 98.5 |
| 3 | Pd 3%Pb 1%Bi 1.2%Fe 0.6%/SDB | 97.8 | 98.4 |
| 4 | Pd 3%Pb 1%Bi 1.2%Fe 0.6%/SDB | 97.5 | 97.6 |
| 5 | Pd 3%Pb 1%Bi 1.2%Fe 0.6%/SDB | 97.3 | 96.9 |
Claims (6)
1. the hydrophobic catalyst of producing methyl methacrylate for oxidation step esterification, is characterized in that: catalyst consists of Pd
xm
y/ SDB; Wherein M is one or more in promoter metal Pb, Bi, Fe element; X, y are respectively the mass fraction of every kind of element with respect to carrier: the mass fraction of Pd is 1-6%, and the mass fraction of promoter metal component is 0.1-3%.
2. hydrophobic catalyst according to claim 1, is characterized in that described carrier is hydrophobic material, is SDVB copolymer SDB.
3. the preparation method of catalyst according to claim 1, is characterized in that active component Pd and other one or more assistant metal element loads to reduce on hydrophobic carrier SDB, and step is as follows:
(1) according to catalyst, contain each metal component mass fraction, take out required PdCl
2quality, be dissolved in organic solvent, be placed in 70 ℃ of-80 ℃ of stirred in water bath and dissolve; By pretreated carrier incipient impregnation in living solution 12 hours; The carrier having flooded is placed in to the dry 4-6h of vacuum drying chamber, and infrared lamp is dried 2-4h until solvent is dried completely;
(2) dried product packs quartz ampoule into, is placed in catalyst reduction stove, first the logical high pure nitrogen air in tube of rushing, start to heat up, 10～20 ℃/min of programming rate, rises to and stops logical nitrogen after assigned temperature and change logical high-purity hydrogen reduction simultaneously, hydrogen flowing quantity 20-30ml/min, reduction; Then stop heating, cooling, changing hydrogen is nitrogen, is cooled to room temperature takes out with nitrogen protection, makes catalyst finished product.
(3) take out one or more of required promoter metal compound quality, be dissolved in organic solvent, be placed in 70-80 ℃ of stirred in water bath and dissolve; By pretreated carrier incipient impregnation in living solution 12 hours; The carrier having flooded is placed in to the dry 4-6h of vacuum drying chamber, and infrared lamp is dried 2-4h until solvent is dried completely, and by the method reduction of step (2); Promoter metal load is reduced on hydrophobic carrier SDB.
4. method as claimed in claim 3, is characterized in that the promoter metal order that load is reduced on hydrophobic carrier SDB is Pd, Pb, Bi and Fe.
5. method as claimed in claim 3, is characterized in that selecting required metallic compound in auxiliary element Pb, Bi, Fe to comprise chloride, nitrate, sulfate or acetate.
6. preparation method according to claim 3, is characterized in that reduction temperature is 120-250 ℃, and the recovery time is 4-12 hour.
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| CN105722816A (en) * | 2013-12-20 | 2016-06-29 | 赢创罗姆有限公司 | Process for preparing unsaturated esters proceeding from aldehydes by direct oxidative esterification |
| CN107074727A (en) * | 2014-10-31 | 2017-08-18 | 罗门哈斯公司 | Oxidative esterification method for manufacturing methyl methacrylate |
| CN107824199A (en) * | 2017-11-20 | 2018-03-23 | 山东理工大学 | Magnetic Nano Au catalyst of the step oxidative esterification synthetic ester of aldehydes one and its preparation method and application |
| CN109894135A (en) * | 2017-12-11 | 2019-06-18 | 南京理工大学 | Nitrating carbon black loadings palladium bismuth alloy catalyst and its preparation method and application |
| CN113019464A (en) * | 2021-03-11 | 2021-06-25 | 哈尔滨工程大学 | Preparation method of spherical SDB hydrophobic carrier with controllable size and Pt/SDB hydrophobic catalyst |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105722816A (en) * | 2013-12-20 | 2016-06-29 | 赢创罗姆有限公司 | Process for preparing unsaturated esters proceeding from aldehydes by direct oxidative esterification |
| CN105722816B (en) * | 2013-12-20 | 2018-01-23 | 赢创罗姆有限公司 | The method that beta-unsaturated esters are prepared from aldehyde is esterified by direct oxidation |
| CN107074727A (en) * | 2014-10-31 | 2017-08-18 | 罗门哈斯公司 | Oxidative esterification method for manufacturing methyl methacrylate |
| CN107824199A (en) * | 2017-11-20 | 2018-03-23 | 山东理工大学 | Magnetic Nano Au catalyst of the step oxidative esterification synthetic ester of aldehydes one and its preparation method and application |
| CN107824199B (en) * | 2017-11-20 | 2020-02-07 | 山东理工大学 | Magnetic nano gold catalyst for synthesizing ester by aldehyde one-step oxidative esterification and preparation method and application thereof |
| CN109894135A (en) * | 2017-12-11 | 2019-06-18 | 南京理工大学 | Nitrating carbon black loadings palladium bismuth alloy catalyst and its preparation method and application |
| CN109894135B (en) * | 2017-12-11 | 2021-10-01 | 南京理工大学 | Nitrogen-doped carbon black loaded palladium-bismuth alloy catalyst and preparation method and application thereof |
| CN113019464A (en) * | 2021-03-11 | 2021-06-25 | 哈尔滨工程大学 | Preparation method of spherical SDB hydrophobic carrier with controllable size and Pt/SDB hydrophobic catalyst |
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Application publication date: 20140416 |