CN102366724A - Catalyst system for synthesizing acetic acid through carbonylation of methanol and application - Google Patents
Catalyst system for synthesizing acetic acid through carbonylation of methanol and application Download PDFInfo
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- CN102366724A CN102366724A CN2011103929317A CN201110392931A CN102366724A CN 102366724 A CN102366724 A CN 102366724A CN 2011103929317 A CN2011103929317 A CN 2011103929317A CN 201110392931 A CN201110392931 A CN 201110392931A CN 102366724 A CN102366724 A CN 102366724A
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Abstract
The invention provides a catalyst system for synthesizing acetic acid through carbonylation of methanol and application. The catalyst system comprises a main catalyst IrCl3.3H2O, a cocatalyst CH3I, a halogen salt of transition metals CoCl2.6H2O, NiCl2.6H2O, CuCl2.2H2O, ZnCl2 or ZnI2, and ionic liquid [BMIM]Tf2N or [Bupy]Tf2N used as a polarity regulator. The mass of the catalyst system accounts for less than 61% of the mass of a whole reaction system, and the mass concentration of CH3OH is no less than 39% on a basis of the reaction system; no water is need to be added in the catalyst system and the reaction system in the invention, thereby improving the activity and stability of the catalyst system and truly providing great convenience for simplification of subsequent separation of acetic acid from water. Compared to the prior art, the invention has the advantage of substantially reduced total production cost.
Description
Technical field
The present invention relates to the acetic acid synthesized catalyst system of methanol carbonylation and the method for application thereof.
Background technology
Acetic acid is a kind of important Organic Chemicals, and one of its main production method is a methanol carbonylation.This method is with methyl alcohol (CH
3OH) and carbon monoxide (CO) be raw material, the catalyst system and catalyzing effect that constitutes at catalyst, promoter and/or co-catalyst is production acetic acid down.Because catalyst system and catalyzing has played key effect in the acetic acid synthesized process of methanol carbonylation, therefore, how to improve catalyst system to acetic acid synthesized various influences, people are constantly exploring always.For example; Publication No. is that CN101954295A, name are called in the patent application of " catalyst system of synthesizing acetic acid by methanol low-pressure carbonylation and application thereof "; Just comprised " reducing the water content in the reaction system "; To overcome water to the exploration of entire reaction adverse effect (as: when in the reactant water being arranged as far as possible; Very easily cause the generation of this side reaction of water gas reaction and the difficulty that increases later stage product separation phase); So the means that in its catalyst system, only add the water of " being 4%～6% by weight percentage " have been adopted in this patent application, also obtained the beneficial effect of minimizing water gas reaction really with " separating technology that is follow-up acetic acid and water provides great facility ".Yet; Owing in its catalyst system, still added the water of " being 4%～6% by weight percentage " after all; Therefore, reduce water gas reaction and said " great facility is provided "---finally be presented as the effect that reduces cost, just still more limited.In addition, in contained other components of this catalyst system lithium iodide and hydroiodic acid are arranged, they are also unfavorable to reducing cost---and the price of lithium iodide is more expensive, is unfavorable for reducing cost; Hydroiodic acid is relatively large to the corrosion of agitated reactor, has increased anticorrosion cost again.Moreover the reaction minimum temperature of this reaction system is 170 ℃, though condition is calculated relatively gentleness, still has improved space.So the total production cost of using this catalyst system is still higher.
Summary of the invention
First purpose of the present invention provides the catalyst system that when using, can reduce the acetic acid synthesis from methanol carbonylation of total production cost.
Second purpose of the present invention provides the catalyst system of said first goal of the invention of Application and implementation, and then can reduce the acetic acid synthesized method of total production cost.
Realizing the technical scheme of said first goal of the invention, is a kind of like this catalyst system of acetic acid synthesis from methanol carbonylation, and the aspect identical with prior art is to comprise major catalyst IrCl in this catalyst system
33H
2O (hydrate of iridous chloride) and co-catalyst CH
3I (iodomethane), its improvements are that the interior polar modifier ionic liquid in addition of said catalyst system also has the transition metal halogen in the said co-catalyst; Wherein, said ionic liquid is [BMIM] Tf
2N (the two fluoroform sulfimide salt of 1-butyl-3-methylimidazole) or [Bupy] Tf
2N (the two fluoroform sulfimide salt of N-butyl-pyridinium), said transition metal halogen is CoCl
26H
2O (hydrate of cobalt chloride), NiCl
26H
2O (hydrate of nickel chloride), CuCl
22H
2O (hydrate of copper chloride), ZnCl
2(zinc chloride) or ZnI
2(zinc iodide); When being applied to this catalyst system in the acetic acid synthesized reaction system, with respect to this reaction system, the total mass concentration of said catalyst system accounts for below 61%, wherein, and IrCl
33H
2Mass concentration in Ir (iridium) among the O is 500～1500ppm, IrCl
33H
2The mol ratio of O and said transition metal halogen is 5～10, said CH
3The mass concentration of I is 25%～35%, said ion liquid mass concentration is 25%～35%.
Realizing the technical scheme of said second goal of the invention, is a kind of like this method of acetic acid synthesis from methanol carbonylation, and the aspect identical with prior art be, it is with CH
3OH (methyl alcohol) is equipped with the synthetic method that contains catalyst system in the reaction system of primary raw material, and its step comprises:
(1) with said CH
3All components in OH and the catalyst system is all packed in the agitated reactor, and fully mixes to constitute acetic acid synthesized reaction system;
(2) the said agitated reactor of sealing and with the air in this agitated reactor of CO displacement; Adjust the pressure of CO then,, under stirring, carry out methanol carbonylation to produce acetic acid to the agitated reactor heating; Its improvements are:
Said catalyst system is for realizing the catalyst system of said first goal of the invention;
CH described in the step (1)
3OH is no less than 39% with respect to the mass concentration of said reaction system;
140～160 ℃ of reaction temperatures in step (2), the pressure that charges into CO remains between 2.5～3MPa, and the reaction time is no longer proceeded down degree of being with methanol carbonylation.
From scheme, can find out; All need not add entry in catalyst system of the present invention and the acetic acid synthesized reaction system; So, by in the reactant just do not existed with the adverse effect of water, so just greatly reduced water gas reaction; Reduced the content of water in products simultaneously, real for simplifying follow-up acetic acid and separating of water great facility being provided.All do not use lithium iodide and hydroiodic acid in catalyst system of the present invention and the reaction system, more expensive because of the former in the prior art, the latter has the deficiency of relatively large corrosion also to obtain overcoming to agitated reactor.It can also be seen that from scheme the reaction temperature of the present invention when acetic acid synthesized is 140～160 ℃, its maximum temperature is still hanged down 10 ℃ than the minimum temperature of prior art; Reaction pressure is between 2.5～3MPa, and also low (reaction pressure of prior art is 2.8～3.2MPa) to its mean value than the mean value of prior art.In addition, the ionic liquid in the catalyst system of the present invention can guarantee that product more easily separates with catalyst; The transition metal halogen can well dissolve in the liquid-phase reaction system that the present invention relates to, and can improve the catalytic activity of major catalyst and keep the high activity of whole reaction system.Therefore, compared with prior art, sum up in the point that on the total production cost and say that the present invention reduces manyly than prior art.
Below in conjunction with the specific embodiment the present invention is further described.
The specific embodiment
One, a kind of catalyst system of acetic acid synthesis from methanol carbonylation comprises major catalyst IrCl in this catalyst system
33H
2O and co-catalyst CH
3I in the present invention, also has the polar modifier ionic liquid in the said catalyst system, also have the transition metal halogen in the said co-catalyst; Wherein, said ionic liquid is [BMIM] Tf
2N or [Bupy] Tf
2N, said transition metal halogen is CoCl
26H
2O, NiCl
26H
2O, CuCl
22H
2O, ZnCl
2Or ZnI
2When being applied to this catalyst system in the acetic acid synthesized reaction system, with respect to this reaction system, the total mass concentration of said catalyst system accounts for below 61%, wherein, and IrCl
33H
2Mass concentration in Ir among the O is 500～1500ppm, IrCl
33H
2The mol ratio of O and said transition metal halogen is 5～10, said CH
3The mass concentration of I is 25%～35%, said ion liquid mass concentration is 25%～35%.
Two, a kind of method of acetic acid synthesis from methanol carbonylation, it is with CH
3OH is equipped with the synthetic method that contains catalyst system in the reaction system of primary raw material, and its step comprises:
(1) with said CH
3All components in OH and the catalyst system is all packed in the agitated reactor, and fully mixes to constitute acetic acid synthesized reaction system;
(2) the said agitated reactor of sealing and with the air in this agitated reactor of CO displacement; Adjust the pressure of CO then,, under stirring, carry out methanol carbonylation to produce acetic acid to the agitated reactor heating;
In the present invention, above-mentioned catalyst system is the described catalyst system of this specific embodiment first;
CH described in the step (1)
3OH is no less than 39% with respect to the mass concentration of said reaction system;
140～160 ℃ of reaction temperatures in step (2), the pressure that charges into CO remains between 2.5～3MPa, and the reaction time is no longer proceeded down degree of being with methanol carbonylation.
Obviously, in practice, only there are above-mentioned two steps can't directly obtain required acetic acid.In view of step thereafter is well known to those skilled in the art already, so only do simple the disclosure.Specifically: after the reaction of step (2) stops, letting agitated reactor naturally cool to room temperature; Open agitated reactor, after the conventional way of distillation of usefulness from obtain liquid product, isolates all components and accessory substance in the catalyst system, promptly obtain principal product acetic acid.
The present invention has passed through verification experimental verification.
Checking is carried out in the zirconium matter autoclave of 500mL.The method of preparation catalyst system and acetic acid synthesis from methanol carbonylation is identical with the step in this specific embodiment.When in step (2), stirring, its speed is selected 300 rev/mins.
When agitated reactor being carried out open after nature cools, obtain the liquid substance that product is does not have deposition, this explanation catalyst of the present invention remains stable through not causing inactivation after the reaction.After obtaining acetic acid through the conventional method separation, with gas chromatograph analyzer (GC-1100), select Porapak-Q stainless steel packed column for use, thermal conductivity cell detector is analyzed the product after purifying.Calculate acetic acid selectivity and acetic acid space-time yield in methanol conversion, the product then.Checking is the result see the following form.
Table 1
Table 2
Can find out that from above-mentioned checking acetic acid selectivity and acetic acid space-time yield in methanol conversion of the present invention, the product are all higher.
The road is the same as is known to the person skilled in the art; Finish in the liquid product of back gained at methanol carbonylation; Also include a certain amount of accessory substance, from the molecular structure of all reactant composition of reaction system of the present invention, can find out, its accessory substance is methyl acetate and water; Show during checking; Resulting accessory substance also has only methyl acetate and water; And both amounts are seldom---methanol conversion, acetic acid selectivity and acetic acid space-time yield in the top proof list are all higher; The productive rate that also is principal product acetic acid is higher, and can give counterevidence methyl acetate and water are all than low this analysis conclusion.In addition, methyl acetate is the organic solvent that can replace acetone, butanone, ethyl acetate, pentamethylene etc. to use, and that is to say useful a kind of accessory substance.Owing to before reaction, do not add entry, so, the water yield in the accessory substance only just bring after the reaction seldom.So the present invention has greatly reduced water gas reaction really, can be really for simplifying follow-up acetic acid and providing a great convenience separating of water.Sum up in the point that on the total production cost and say that the present invention reduces manyly than prior art really.
Claims (2)
1. the catalyst system of an acetic acid synthesis from methanol carbonylation comprises major catalyst IrCl in this catalyst system
33H
2O and co-catalyst CH
3I is characterized in that, also has the polar modifier ionic liquid in the said catalyst system, also has the transition metal halogen in the said co-catalyst; Wherein, said ionic liquid is [BMIM] Tf
2N or [Bupy] Tf
2N, said transition metal halogen is CoCl
26H
2O, NiCl
26H
2O, CuCl
22H
2O, ZnCl
2Or ZnI
2When being applied to this catalyst system in the acetic acid synthesized reaction system, with respect to this reaction system, the total mass concentration of said catalyst system accounts for below 61%, wherein, and IrCl
33H
2Mass concentration in Ir among the O is 500～1500ppm, IrCl
33H
2The mol ratio of O and said transition metal halogen is 5～10, said CH
3The mass concentration of I is 25%～35%, said ion liquid mass concentration is 25%～35%.
2. the method for an acetic acid synthesis from methanol carbonylation, it is with CH
3OH (methyl alcohol) is equipped with the synthetic method that contains catalyst system in the reaction system of primary raw material, and its step comprises:
(1) with said CH
3All components in OH and the catalyst system is all packed in the agitated reactor, and fully mixes to constitute acetic acid synthesized reaction system;
(2) the said agitated reactor of sealing and with the air in this agitated reactor of CO displacement; Adjust the pressure of CO then,, under stirring, carry out methanol carbonylation to produce acetic acid to the agitated reactor heating; It is characterized in that:
Said catalyst system is the described catalyst system of claim 1;
CH described in the step (1)
3OH is no less than 39% with respect to the mass concentration of said reaction system;
140～160 ℃ of reaction temperatures in step (2), the pressure that charges into CO remains between 2.5～3MPa, and the reaction time is no longer proceeded down degree of being with methanol carbonylation.
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| CN 201110392931 CN102366724B (en) | 2011-12-01 | 2011-12-01 | Catalyst system for synthesizing acetic acid through carbonylation of methanol and application |
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|---|---|---|---|
| CN 201110392931 CN102366724B (en) | 2011-12-01 | 2011-12-01 | Catalyst system for synthesizing acetic acid through carbonylation of methanol and application |
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| CN102366724B CN102366724B (en) | 2013-05-15 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103861643A (en) * | 2014-04-01 | 2014-06-18 | 北京众智创新科技开发有限公司 | Catalyst system for synthesizing acetic acid by carbonylating methyl alcohol carbonyl as well as application thereof |
| CN104549507A (en) * | 2014-12-15 | 2015-04-29 | 浙江大学 | Preparation method of iron-based catalyst for alkylation reaction |
| CN111320550A (en) * | 2020-03-27 | 2020-06-23 | 吉林化工学院 | Synthetic method for preparing amide compound through co-catalysis of niobium pentachloride and ionic liquid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0749948A1 (en) * | 1995-06-21 | 1996-12-27 | BP Chemicals Limited | Process for the carbonylation of alkyl alcohols and/or reactive derivatives thereof |
| CN1325374A (en) * | 1998-11-05 | 2001-12-05 | 法商亚瑟塔克斯化学公司 | Method for preparing acetic acid and/or methyl acetate in the presence of iridium and platinum |
| CN101374794A (en) * | 2006-01-30 | 2009-02-25 | 英国石油化学品有限公司 | Process for the production of acetic acid |
| CN101890369A (en) * | 2010-06-30 | 2010-11-24 | 重庆大学 | Liquid-solid phase loaded catalyst used in production of acetic acid and preparation method thereof |
-
2011
- 2011-12-01 CN CN 201110392931 patent/CN102366724B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0749948A1 (en) * | 1995-06-21 | 1996-12-27 | BP Chemicals Limited | Process for the carbonylation of alkyl alcohols and/or reactive derivatives thereof |
| CN1325374A (en) * | 1998-11-05 | 2001-12-05 | 法商亚瑟塔克斯化学公司 | Method for preparing acetic acid and/or methyl acetate in the presence of iridium and platinum |
| CN101374794A (en) * | 2006-01-30 | 2009-02-25 | 英国石油化学品有限公司 | Process for the production of acetic acid |
| CN101890369A (en) * | 2010-06-30 | 2010-11-24 | 重庆大学 | Liquid-solid phase loaded catalyst used in production of acetic acid and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 周斌等: "甲醇低压羰基法合成醋酸的催化剂体系", 《化学通报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103861643A (en) * | 2014-04-01 | 2014-06-18 | 北京众智创新科技开发有限公司 | Catalyst system for synthesizing acetic acid by carbonylating methyl alcohol carbonyl as well as application thereof |
| CN104549507A (en) * | 2014-12-15 | 2015-04-29 | 浙江大学 | Preparation method of iron-based catalyst for alkylation reaction |
| CN104549507B (en) * | 2014-12-15 | 2017-05-17 | 浙江大学 | Preparation method of iron-based catalyst for alkylation reaction |
| CN111320550A (en) * | 2020-03-27 | 2020-06-23 | 吉林化工学院 | Synthetic method for preparing amide compound through co-catalysis of niobium pentachloride and ionic liquid |
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|---|---|
| CN102366724B (en) | 2013-05-15 |
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