CN101890369A - Liquid-solid phase loaded catalyst used in production of acetic acid and preparation method thereof - Google Patents
Liquid-solid phase loaded catalyst used in production of acetic acid and preparation method thereof Download PDFInfo
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- CN101890369A CN101890369A CN 201010213068 CN201010213068A CN101890369A CN 101890369 A CN101890369 A CN 101890369A CN 201010213068 CN201010213068 CN 201010213068 CN 201010213068 A CN201010213068 A CN 201010213068A CN 101890369 A CN101890369 A CN 101890369A
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Abstract
The invention relates to a liquid-solid phase loaded catalyst used in the production of acetic acid and a preparation method thereof. In the catalyst, carbon fiber or glass fiber is used as a main carrier. The preparation method comprises the following steps of: removing a surface coating from the carbon fiber or the glass fiber; performing electrochemical oxidation on the carbon fiber and introducing hydroxyl into the surface of the carbon fiber; performing a coupling reaction on the carbon fiber or the glass fiber and a silane coupling agent; loading catalytic active ingredients such as rhodium, iridium and the like on the surface of the catalyst carrier through chemical bonds after reaction; and performing carbonylation on catalytic methanol to obtain the acetic acid. Verification proves that the catalyst of the invention has high stability, a process for separating the catalyst from a liquid product is simple and high catalytic activity is kept. Therefore, the catalyst is a catalyst product for efficient carbonylation for the preparation of acetic acid, which has the advantages of stable property, and simple product preparation.
Description
Technical field
The present invention relates to produce the loaded catalyst of acetic acid with the methanol carbonylation liquid-solid phase.
Background technology
In Processes for Producing Acetic Acid, methanol carbonylation is one of main method, and this method is with methyl alcohol (CH
3OH) and carbon monoxide (CO) be raw material, with Noble Metal Rhodium (Rh) or iridium (Ir) etc. as catalyst.Divide from technology, homogeneous catalyst and loaded catalyst are arranged again.Because the latter loads on the respective carrier, the former is the sort of to cause noble metal active component precipitation, inactivation easily so can overcome, and then the deficiency that causes noble metal catalyst to run off.According to the residing environment of catalyst in the course of reaction, can be divided into gas solid method and liquid-solid phase method again with loaded catalyst catalytic production acetic acid.Compare with gas solid method, the loaded catalyst that is fit to liquid-solid phase production acetic acid has higher activity.Produce in the loaded catalyst of acetic acid in liquid-solid phase, at present can commercial applications be to be the immobilized rhodium of carrier with the polyvinylpyridine, the patent No. is that the scheme that US 5334755, name are called " methyl alcohol and carbon monoxide supported catalyst production acetic acid " (Process for the production of acetic acid from methanol and carbon monoxide using supported rhodium catalyst) is exactly one of them.But, because the carrier polyvinylpyridine is under the high-temperature and high-pressure conditions of catalytic reaction, there is softening and decomposition to a certain degree, so its less stable, specifically be exactly, except that the order of severity than the homogeneous catalyst that does not have carrier better, noble metal runs off or the problem of inactivation, still can take place frequently.
Summary of the invention
First purpose of the present invention is that the loaded catalyst of a kind of stability liquid-solid phase production preferably acetic acid is provided.
Second purpose of the present invention is that a kind of preparation method who obtains the loaded catalyst of the liquid-solid phase production acetic acid of realizing first purpose is provided.
The scheme that realizes described first goal of the invention is the loaded catalyst that a kind of like this liquid-solid phase is produced acetic acid, with the aspect of prior art be, it is to produce the used catalyst of acetic acid with methanol carbonylation, and its catalytic activity component is rhodium or iridium, and the carrier of load rhodium or iridium is a solid.Its improvements are, this carrier be through with the silane coupler coupling reaction after carbon fiber or glass fibre.
The scheme that realizes described second goal of the invention is the preparation method that a kind of like this liquid-solid phase is produced the loaded catalyst of acetic acid, its prepared catalyst is a loaded catalyst of realizing the liquid-solid phase production acetic acid of first goal of the invention, and this method comprises the steps:
(1) carrier preliminary treatment
It is that successively by extracting and supersound washing, the time is to remove face coat degree of being in 1: 1 the mixed solution that described carbon fiber or glass fibre are immersed acetone and benzinum volume ratio; Then, dry between 80 ℃～100 ℃;
Independent electrochemical oxidation carbon fiber: in the ammonium bicarbonate aqueous solution of 5wt%, be anode with the carbon fiber, the metal platinized platinum is a negative electrode, and electrical current density is 0.5～1A/g, time 3～5min;
(2) carrier surface modification
Will be through carbon fiber or the glass fibre after step (1) is handled, be immersed in the silane coupler aqueous solution of 1～2wt% and carry out coupling reaction; Wherein, described silane coupler is gamma-aminopropyl-triethoxy-silane or N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane; Processing time is 30～180min;
(3) supported catalyst active component
Carbon fiber or glass fibre after the modification that step (2) is obtained are immersed in and are dissolved with rhodium or iridium active component, and concentration is in the solution of 0.5～1.0mol/L, stirs 30～60min under 50～60 ℃ of conditions; Filter the back and successively water and absolute ethyl alcohol are fully washed, by washes clean fully, oven dry is the loaded catalyst that the liquid-solid phase of accomplished first purpose is produced acetic acid up to the catalytic active component of the non-bonding combination of carbon fiber or fiberglass surfacing.
From the scheme that realizes first goal of the invention as can be seen, the carrier that liquid-solid phase of the present invention is produced the loaded catalyst of acetic acid has not been the sort of under high-temperature and high-pressure conditions in the prior art, there has been the polyvinylpyridine of softening and decomposition to a certain degree, but under high-temperature and high-pressure conditions, can not soften and decompose, promptly have the carbon fiber or the glass fibre of good stability.
Because, carbon fiber or glass fibre, after reacting with coupling agent, its fiber surface has been introduced the atom of a certain amount of electron rich, as: N, O, P, S atom; The transfer that these atomic energy are crossed by electronics forms chemical bond in conjunction with rhodium or iridium, has played " bridge formation " effect between carrier and catalytic active species rhodium or iridium.Because rhodium or iridium are by the coordinate bond combination, therefore, not only its active component rhodium or iridium very high with the carrier combination stability under HTHP, promptly in course of reaction, do not come off, and, the catalytic activity that is not less than similar liquid-solid phase loaded catalyst is arranged again being applied to produce in the technology of acetic acid with methanol carbonylation.In addition, because carbon fiber or glass fibre itself are exactly existing industrialization commodity, do not need independent preparation again, so the cost of the loaded catalyst of liquid-solid phase production acetic acid of the present invention is also relatively low.
From the scheme that realizes second goal of the invention as can be seen, preparation process in this method invention is simple relatively, after the modification of carbon fiber or glass fibre through step (2), their surface has generated an electron rich atom or a group that combines with the active component of rhodium or iridium surely, so catalytic active component is not that physical absorption is at carrier surface, but by the chemical bond combination, have than high bond strength, in catalytic reaction, be not easy to come off.
Experimental verification shows, catalyst of the present invention can be under 150～210 ℃ of CO dividing potential drop 2.0～5.0MPa, temperature well the catalysis methanol carbonylation produce acetic acid, and in repeatedly catalysis is tested, the catalyst activity component does not have obviously come off (less than 10ppm), catalytic activity is basicly stable, and catalyst separation is simple.
In a word, the present invention is that a kind of stable in properties, product separate the catalyst article that simple, efficient carbonylation is produced acetic acid.
The present invention is further illustrated below in conjunction with the specific embodiment.
The specific embodiment
One, a kind of liquid-solid phase is produced the loaded catalyst of acetic acid, and it is to produce the used catalyst of acetic acid with methanol carbonylation, and its catalytic activity component is rhodium or iridium, and the carrier of load rhodium or iridium is a solid.This carrier of the present invention be through with the silane coupler coupling reaction after carbon fiber or glass fibre.
Two, a kind of liquid-solid phase is produced the preparation method of the loaded catalyst of acetic acid, and its prepared catalyst is a loaded catalyst of realizing the liquid-solid phase production acetic acid of first goal of the invention, and this method comprises the steps:
(1) carrier preliminary treatment
It is that successively by extracting and supersound washing, the time is to remove face coat degree of being in 1: 1 the mixed solution that described carbon fiber or glass fibre are immersed acetone and benzinum volume ratio; Then, dry between 80 ℃～100 ℃;
Independent electrochemical oxidation carbon fiber: in the ammonium bicarbonate aqueous solution of 5wt%, be anode with the carbon fiber, the metal platinized platinum is a negative electrode, and electrical current density is 0.5～1A/g, and (actual oxidization time is introduced maximum hydroxyl degree of being with carbon fiber surface to time 3～5min; Glass fibre does not need the electrochemical oxidation step process, because of fiberglass surfacing contains a certain amount of hydroxyl, can react with coupling agent, and carbon fiber surface before being untreated does not have active group, can not react with coupling agent);
(2) carrier surface modification
Will be through carbon fiber or the glass fibre after step (1) is handled, be immersed in the silane coupler aqueous solution of 1～2wt% and carry out coupling reaction; Wherein, described silane coupler is gamma-aminopropyl-triethoxy-silane or N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane; Processing time is 30～180min; (specify, coupling agent with carbon fiber and glass fibre reaction in, the consumption of coupling agent is all excessive more than 100%, guarantee carbon fiber or glass fibre can be farthest and coupling agent react)
(3) supported catalyst active component
Carbon fiber or glass fibre after the modification that step (2) is obtained are immersed in and are dissolved with rhodium or iridium active component, and concentration is in the solution of 0.5～1.0mol/L, stirs 30～60min under 50～60 ℃ of conditions; Filter the back and successively water and absolute ethyl alcohol are fully washed, by washes clean fully, oven dry is the loaded catalyst that the liquid-solid phase of accomplished first purpose is produced acetic acid up to the catalytic active component of the non-bonding combination of carbon fiber or fiberglass surfacing.
The present invention has passed through verification experimental verification
One, preparation checking
Concrete operations and see the following form with each routine different piece:
Two, compliance test result:
Above-mentioned preparation is verified that the liquid-solid phase of four examples produces the loaded catalyst of acetic acid, be put in respectively in the zirconium matter autoclave; Add content respectively and be methyl alcohol 65wt%, iodomethane 12wt%, methyl acetate 15wt%, and the solution of water 8wt%; Sealing back is with air in the carbon monoxide displacement still, in CO dividing potential drop 3.0MPa, temperature is under 200 ℃ the condition, react calculating acetic acid productive rate 3 hours.Compliance test result the results are shown in following table.
Specify, in catalyst, in the related carrier, all in the mentioned scope of the specific embodiment, it will be apparent to those skilled in the art that in most of the cases, catalyst repeatedly in the catalytic process acetic acid productive rate exist necessarily and fluctuate, can think permissible variation.
As can be seen, carbon fiber or fiberglass carrier have stability preferably from verify example, and in 5 catalysis experimentations of every group repetition, catalyst activity does not have obvious decline; And detect by atomic absorption spectrophotometry, precious metal concentration is lower than 10ppm in the liquid product, illustrates that carrier has good stability to the catalyst activity component.
Claims (2)
1. a liquid-solid phase is produced the loaded catalyst of acetic acid, it is to produce the used catalyst of acetic acid with methanol carbonylation, its catalytic activity component is rhodium or iridium, the carrier of load rhodium or iridium is a solid, it is characterized in that, this carrier be through with the silane coupler coupling reaction after carbon fiber or glass fibre.
2. the preparation method that liquid-solid phase is produced the loaded catalyst of acetic acid is characterized in that, its prepared catalyst is the loaded catalyst that the described liquid-solid phase of claim 1 is produced acetic acid, and this method comprises the steps:
(1) carrier preliminary treatment
It is that successively by extracting and supersound washing, the time is to remove face coat degree of being in 1: 1 the mixed solution that described carbon fiber or glass fibre are immersed acetone and benzinum volume ratio; Then, dry between 80 ℃～100 ℃;
The independent described carbon fiber of electrochemical oxidation: in the ammonium bicarbonate aqueous solution of 5wt%, be anode with the carbon fiber, the metal platinized platinum is a negative electrode, and electrical current density is 0.5～1A/g, time 3～5min;
(2) carrier surface modification
Will be through carbon fiber or the glass fibre after step (1) is handled, be immersed in the silane coupler aqueous solution of 1～2wt% and carry out coupling reaction; Wherein, described silane coupler is gamma-aminopropyl-triethoxy-silane or N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane; Processing time is 30～180min;
(3) supported catalyst active component
Carbon fiber or glass fibre after the modification that step (2) is obtained are immersed in and are dissolved with rhodium or iridium active component concentration is in the solution of 0.5～1.0mol/L, stir 30～60min under 50～60 ℃ of conditions; Filter the back and successively water and absolute ethyl alcohol are fully washed, by washes clean fully, oven dry promptly obtains the described liquid-solid phase loaded catalyst of claim 1 up to the catalytic active component of the non-bonding combination of carbon fiber or fiberglass surfacing.
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| CN201010213068XA CN101890369B (en) | 2010-06-30 | 2010-06-30 | Liquid-solid phase loaded catalyst used in production of acetic acid and preparation method thereof |
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| CN201010213068XA CN101890369B (en) | 2010-06-30 | 2010-06-30 | Liquid-solid phase loaded catalyst used in production of acetic acid and preparation method thereof |
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| CN101890369A true CN101890369A (en) | 2010-11-24 |
| CN101890369B CN101890369B (en) | 2012-05-23 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350373A (en) * | 2011-09-28 | 2012-02-15 | 重庆大学 | Catalyst for synthetizing acetic acid through methanol carbonylation and preparation method thereof |
| CN102366724A (en) * | 2011-12-01 | 2012-03-07 | 重庆大学 | Catalyst system for synthesizing acetic acid through carbonylation of methanol and application |
| CN102808325A (en) * | 2012-07-10 | 2012-12-05 | 西北工业大学 | Surface modifying method of PBO (polybenzoxazole) fiber |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5334755A (en) * | 1992-04-24 | 1994-08-02 | Chiyoda Corporation | Process for the production of acetic acid from methanol and carbon monoxide using supported rhodium catalyst |
| CN1115689A (en) * | 1995-03-31 | 1996-01-31 | 中国科学院化学研究所 | Gas-solid phase carbonylation catalyst and its prepn |
| CN1807380A (en) * | 2006-02-23 | 2006-07-26 | 华南理工大学 | Alcohol liquid phase catalytic oxidation method and catalyst reactivation method |
-
2010
- 2010-06-30 CN CN201010213068XA patent/CN101890369B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5334755A (en) * | 1992-04-24 | 1994-08-02 | Chiyoda Corporation | Process for the production of acetic acid from methanol and carbon monoxide using supported rhodium catalyst |
| CN1115689A (en) * | 1995-03-31 | 1996-01-31 | 中国科学院化学研究所 | Gas-solid phase carbonylation catalyst and its prepn |
| CN1807380A (en) * | 2006-02-23 | 2006-07-26 | 华南理工大学 | Alcohol liquid phase catalytic oxidation method and catalyst reactivation method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350373A (en) * | 2011-09-28 | 2012-02-15 | 重庆大学 | Catalyst for synthetizing acetic acid through methanol carbonylation and preparation method thereof |
| CN102366724A (en) * | 2011-12-01 | 2012-03-07 | 重庆大学 | Catalyst system for synthesizing acetic acid through carbonylation of methanol and application |
| CN102366724B (en) * | 2011-12-01 | 2013-05-15 | 重庆大学 | Catalyst system for synthesizing acetic acid through carbonylation of methanol and application |
| CN102808325A (en) * | 2012-07-10 | 2012-12-05 | 西北工业大学 | Surface modifying method of PBO (polybenzoxazole) fiber |
| CN102808325B (en) * | 2012-07-10 | 2014-06-11 | 西北工业大学 | Surface modifying method of PBO (polybenzoxazole) fiber |
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| CN101890369B (en) | 2012-05-23 |
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