CN102350373B - Catalyst for synthetizing acetic acid through methanol carbonylation - Google Patents
Catalyst for synthetizing acetic acid through methanol carbonylation Download PDFInfo
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- CN102350373B CN102350373B CN2011102981501A CN201110298150A CN102350373B CN 102350373 B CN102350373 B CN 102350373B CN 2011102981501 A CN2011102981501 A CN 2011102981501A CN 201110298150 A CN201110298150 A CN 201110298150A CN 102350373 B CN102350373 B CN 102350373B
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- catalyst
- bipyridyl
- iridium
- acetic acid
- complex
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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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Abstract
The invention relates to a catalyst for synthetizing acetic acid through methanol carbonylation. In the catalyst, iridium is taken as a central ion and a 2,2-bipyridyl iridium complex of 2,2-bipyridyl is taken as a ligand. The preparation method thereof comprises the following steps: dissolving equimolal 2,2-bipyridyl and IrCl3 or Ir(OAc)3 in absolute ethyl alcohol, thereby preparing a solution; under a condition of nitrogen protection, mixing two solutions, heating and causing a mixture to flow back; and cooling an acquired solution, adding excessive diethyl ether, depositing, filtering and drying, and finally acquiring the 2,2-bipyridyl iridium complex. The catalyst provided by the invention is a double teeth type iridium complex, which is more stable when a methanol carbonylation method is used for generating the acetic acid. Catalyst loss can be reduced to the lowest, recycling rate of the catalyst is promoted and total production cost is reduced.
Description
Technical field
The present invention relates to produce with methanol carbonylation the catalyst of acetic acid, relating in particular to iridium is the composition catalyst of central ion.
Background technology
Acetic acid is (CH
3COOH is abbreviated as AcOH or HAc) important industrial chemicals that a kind of purposes is extremely wide, one of main method of producing acetic acid is a methanol carbonylation, this method is with methyl alcohol (CH
3OH) and carbon monoxide (CO) be raw material, act at catalyst (and promoter and/or co-catalyst auxiliary) and produce acetic acid.Because catalyst prepares in the acetic acid process in methanol carbonylation and played key effect, therefore, it is the constantly important topics of research of people always.For example; For making catalyst have higher catalytic activity; Someone has just proposed with iridium (Ir) is the composition catalyst of central ion; Notification number is that the catalyst that CN101703946B, name are called in " copolymer-iridium catalyst of used for preparing acetic acid through carbonylation reaction " is exactly one of them, and this prior art is the pyridine carboxylic acid compounds around the part of central ion Ir.Its reaction mechanism and advantage are; The Electronic Negative of activated centre ion Ir is electrically changed; And this variation meeting produces positive influences to the ability of the feedback π key between Ir and the CO; Be gripping N altogether the feedback π key that forms between Ir and the CO is strengthened on its pyridine ring, and then make this catalyst have advantages of high catalytic activity.In addition, because the existence of ligand molecular is arranged, can make with Ir is that the active body at center is in asymmetrical state, and this helps co-catalyst iodomethane (CH
3I) oxidation addition has also been played booster action to the raising of catalyst activity.Yet, because this catalyst is a monodentate type coordination structure; Especially in its coordination structure except that containing N → Ir coordinate bond, also contain in catalytic reaction the very easily O → Ir coordinate bond of fracture, this has just brought the deficiency of the less stable of this catalyst.So the catalyst that can reclaim with recycle will reduce, and cause the increasing of total production cost.
Summary of the invention
The objective of the invention is, the catalyst with acetic acid synthesis from methanol carbonylation that a kind of stability is better, cyclic utilization rate is higher is provided.
Realizing the technical scheme of said purpose, is a kind of like this catalyst with acetic acid synthesis from methanol carbonylation, and the aspect identical with prior art is; This catalyst is to be the complex of central ion with iridium; The part of said complex is 2, and 2-bipyridyl, said catalyst are 2; 2-bipyridyl complex of iridium, its structural formula is:
Wherein: X=(Cl
3)
-3, [(OAc)
3]
-3
Its improvements are that this catalyst is prepared from through following steps:
(1) with 2, the 2-bipyridyl is dissolved in the absolute ethyl alcohol, to be mixed with solution;
(2) will be with 2, the 2-bipyridyl has the IrCl of equal molar part
3Or Ir (OAc)
3Be dissolved in the absolute ethyl alcohol, also be mixed with solution;
(3) under nitrogen protection and stirring, step (1) gained solution is added in step (2) the gained solution lentamente; After this, continue under the nitrogen protection state, heating-up temperature remains between 80～100 ℃, refluxes 30～60 minutes;
(4) step (3) gained solution is cooled to room temperature, adds excessive ether sedimentation then, filter, get 2 after the drying, the catalyst of 2-bipyridyl complex of iridium.
Can find out that from scheme the present invention with iridium is the part of the complex of central ion, and is different with prior art, what part was selected is 2, the 2-bipyridyl.Because 2, the 2-bipyridyl is a bidentate type cheland, so the coordinate bond that combines between this part and the central ion Ir is the N → Ir σ coordinate bond of bidentate type, catalyst of the present invention is a bidentate type complex of iridium just also.Compare with monodentate type complex of iridium, catalyst of the present invention is more stable when methanol carbonylation.Owing to when preparation catalyst of the present invention, also increased nitrogen protection; Also promptly under anaerobic condition, carry out; So; Just thoroughly stopped in bidentate type complex of iridium of the present invention, O → Ir coordinate bond to occur,, just further guaranteed the stability of catalyst of the present invention again owing to the O → Ir coordinate bond that has not had in catalytic reaction, very easily to rupture.In brief, catalyst of the present invention has promptly kept the advantage of composition catalyst, on its basis, improves stability again, can the loss of catalyst be dropped to minimumly, improves its cyclic utilization rate, reduces total production cost.
Below in conjunction with the specific embodiment the present invention is described further.
The specific embodiment
A kind of catalyst with acetic acid synthesis from methanol carbonylation, this catalyst are to be the complex of central ion with iridium, and the part of said complex is 2, and 2-bipyridyl, said catalyst are 2,2-bipyridyl complex of iridium, and its structural formula is:
Wherein: X=(Cl
3)
-3, [(OAc)
3]
-3
In the present invention, this catalyst is to prepare as follows:
(1) with 2,2-bipyridyl (having another name called 2, the 2'-bipyridyl) is dissolved in absolute ethyl alcohol (C
2H
5OH) in, to be mixed with solution;
(2) will be with 2, the 2-bipyridyl has the IrCl of equal molar part
3(iridous chloride or abbreviation iridium chloride) or Ir (OAc)
3［ acetic acid iridium (III) or abbreviation acetic acid iridium ］ is dissolved in the absolute ethyl alcohol, also is mixed with solution;
(3) at nitrogen (N
2) protection and stirring under, step (1) gained solution is added in step (2) the gained solution lentamente; After this, continue under the nitrogen protection state, heating-up temperature remains between 80～100 ℃; Reflux and (it will be apparent to those skilled in the art that the purpose and the effect that add reactant lentamente were, and guaranteed normally carrying out of chemical reaction in 30～60 minutes; For example, avoid unnecessary production of by-products.So, the time of said in this step " adding lentamente ", should be more 2 to guarantee finally can to produce, the catalyst of 2-bipyridyl complex of iridium is degree);
(4) step (3) gained solution is cooled to room temperature, adds excessive ether ［ (C then
2H
5)
2O ］ deposition, filter, get 2 after the drying, the catalyst of 2-bipyridyl complex of iridium.It will be apparent to those skilled in the art that in chemical reaction or physical change process, excessively use wherein a kind of material, is in order to let the another kind of material can complete reaction or physical change all takes place.In this step,, its objective is that the catalyst of 2-bipyridyl complex of iridium all extracts in order after deposition, can to have synthesized 2 to all with excessive ether sedimentation.So said excessive it " amount " should be to reach this purpose degree of being.
The present invention has passed through verification experimental verification.
It will be apparent to those skilled in the art that in the step (1) and step (2) of preparation catalyst method of the present invention, will equate 2 of molar part earlier, 2-bipyridyl, IrCl
3Or Ir (OAc)
3Be dissolved in respectively in the absolute ethyl alcohol, actual is as reaction medium, to let 2,2-bipyridyl and IrCl with this organic solvent of absolute ethyl alcohol
3Or Ir (OAc)
3All be dispersed in the organic solvent, all participate in reaction in order to reaching the total overall reaction thing as far as possible---so the consumption of absolute ethyl alcohol should be to reach this purpose degree of being.Usually, dissolve 1 molar part 2, the absolute ethyl alcohol consumption of 2-bipyridyl should be no less than 100 molar part; Dissolve the IrCl of 1 molar part
3Or Ir (OAc)
3The absolute ethyl alcohol consumption, also should be no less than 300 molar part.
Those skilled in the art are clear equally; Said " reflux " time in the step (3) of preparation catalyst method of the present invention; Also should all participate in reaction in order to reaching the total overall reaction thing as far as possible, obtain at most 2, the catalyst of 2-bipyridyl complex of iridium is degree.Under time permission situation, can strive for catalyst production near 100% as far as possible; 45 minutes average times spent of this verification experimental verification, with 2,2-bipyridyl and IrCl
3The productive rate of the catalyst that reaction obtains, average out to 96.5%; With 2,2-bipyridyl and Ir (OAc)
3The productive rate of the catalyst that reaction obtains, average out to 95.6%.
In view of the front has all disclosed quite clearly (comprising that some those skilled in the art through limited routine test, can confirm) to catalyst of the present invention and preparation thereof, so no longer disclose the verification experimental verification of preparation catalyst of the present invention; And, particularly reclaim verification experimental verification with recycle catalyst of the present invention only to verification experimental verification with Catalyst Production acetic acid of the present invention, do to disclose more in detail.
During checking, to by 2,2-bipyridyl and IrCl
3Prepared 2,2-bipyridyl complex of iridium and by 2,2-bipyridyl and Ir (OAc)
3Prepared 2,2-bipyridyl complex of iridium has been done the test of preparation acetic acid respectively.Its step is following:
(1) respectively with two kind 2,2-bipyridyl complex of iridium and methyl alcohol, promoter ruthenic chloride (RuCl
3) ［ perhaps use ruthenium acetate (C
6H
9O
6Ru) or osmium chloride (OsCl
3), its effect is indifference almost ］, co-catalyst iodomethane, methyl acetate (C
3H
6O
2) and water, in the zirconium matter of packing into the autoclave, and fully mix to constitute acetic acid synthesized reaction system;
Wherein, the consumption of promoter ruthenic chloride in this reaction system is with the Mass Calculation of institute's containing metal (Ru); Be two kind 2, in the 2-bipyridyl complex of iridium five times of contained iridium, two kind 2; The quality of contained iridium in the 2-bipyridyl complex of iridium is 300 ppm of this reaction system quality; Other components are respectively with respect to the mass ratio of this reaction system: methyl alcohol 65%, iodomethane 12%, methyl acetate 15%, surplus are water.During concrete the checking, get methyl alcohol 25.0g, the consumption of all the other components is a benchmark with the methanol usage, calculates according to said ratio;
(2) the said autoclave of sealing and with the air in this autoclave of carbon monoxide displacement; After this, temperature is risen to 190 ℃, the pressure of carbon monoxide rises to 3.5MPa, produces acetic acid to carry out methanol carbonylation; 3 hours reaction time;
(3) way of distillation separating acetic acid, water, methyl acetate, co-catalyst iodomethane and 2,2-bipyridyl complex of iridium, ruthenic chloride.With gas chromatograph analysis (GC1100), select Porapak-Q stainless steel packed column for use, thermal conductivity cell detector is analyzed the product after purifying.Calculate methanol conversion then, carbonylation selectivity, acetic acid selectivity and acetic acid productive rate.
(4) with 2 of recovery, 2-bipyridyl complex of iridium is made catalyst, repeats above-mentioned steps (1)～(3) four times.
Checking is the result see the following form:
By 2,2-bipyridyl and IrCl
3Prepared catalyst
| Catalyst utilizes number of times | 1 | 2 | 3 | 4 | 5 |
| Methanol conversion % | 99.8 | 99.71 | 99.8 | 99.69 | 99.49 |
| Acetic acid selectivity (%) | 82.2 | 82.22 | 84 | 83.95 | 82.6 |
| Carbonylation selectivity (%) | 83.7 | 87.15 | 86.9 | 85.93 | 86.0 |
| Acetic acid productive rate mol/Lh | 5.20 | 5.19 | 5.20 | 5.11 | 5.10 |
By 2,2-bipyridyl and Ir (OAc)
3Prepared catalyst
| Catalyst utilizes number of times | 1 | 2 | 3 | 4 | 5 |
| Methanol conversion % | 99.8 | 99.9 | 99.73 | 99.8 | 99.55 |
| Acetic acid selectivity (%) | 84.2 | 83.22 | 84.3 | 83.25 | 82.1 |
| Carbonylation selectivity (%) | 87.7 | 87.15 | 86.9 | 85.0 | 84.43 |
| Acetic acid productive rate mol/Lh | 5.27 | 5.21 | 5.27 | 5.09 | 5.12 |
In the last table, number of times 1 is to use for the first time, and number of times 2,3,4,5 is for recycling.As can be seen from the above table, 2,2-bipyridyl iridium complex catalyst has stability preferably, and after through 5 circulation catalysis, catalytic activity does not have obvious decline.
Claims (1)
1. catalyst with acetic acid synthesis from methanol carbonylation, this catalyst is to be the complex of central ion with iridium, and the part of said complex is 2, and 2-bipyridyl, said catalyst are 2,2-bipyridyl complex of iridium, its structural formula is:
Wherein: X=(Cl
3)
-3, [(OAc)
3]
-3
It is characterized in that this catalyst is prepared from through following steps:
(1) with 2, the 2-bipyridyl is dissolved in the absolute ethyl alcohol, to be mixed with solution;
(2) will be with 2, the 2-bipyridyl has the IrCl of equal molar part
3Or Ir (OAc)
3Be dissolved in the absolute ethyl alcohol, also be mixed with solution;
(3) under nitrogen protection and stirring, step (1) gained solution is added in step (2) the gained solution lentamente; After this, continue under the nitrogen protection state, heating-up temperature remains between 80～100 ℃, refluxes 30～60 minutes;
(4) step (3) gained solution is cooled to room temperature, adds excessive ether sedimentation then, filter, get 2 after the drying, the catalyst of 2-bipyridyl complex of iridium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102981501A CN102350373B (en) | 2011-09-28 | 2011-09-28 | Catalyst for synthetizing acetic acid through methanol carbonylation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102981501A CN102350373B (en) | 2011-09-28 | 2011-09-28 | Catalyst for synthetizing acetic acid through methanol carbonylation |
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| Publication Number | Publication Date |
|---|---|
| CN102350373A CN102350373A (en) | 2012-02-15 |
| CN102350373B true CN102350373B (en) | 2012-12-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2118310C1 (en) * | 1993-03-31 | 1998-08-27 | Асетекс Шими | Method for production of carboxylic acids or appropriate esters thereof |
| JPH10245359A (en) * | 1997-03-05 | 1998-09-14 | Mitsubishi Gas Chem Co Inc | Production of carboxylic acid and ester |
| US20090247783A1 (en) * | 2008-04-01 | 2009-10-01 | Eastman Chemical Company | Carbonylation process |
| CN101890369B (en) * | 2010-06-30 | 2012-05-23 | 重庆大学 | Liquid-solid phase loaded catalyst used in production of acetic acid and preparation method thereof |
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2011
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Granted publication date: 20121205 Termination date: 20130928 |