CN102366724B - 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 PDF

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CN102366724B
CN102366724B CN 201110392931 CN201110392931A CN102366724B CN 102366724 B CN102366724 B CN 102366724B CN 201110392931 CN201110392931 CN 201110392931 CN 201110392931 A CN201110392931 A CN 201110392931A CN 102366724 B CN102366724 B CN 102366724B
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catalyst system
acetic acid
catalyst
reaction
mass concentration
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CN102366724A (en
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杜军
胡娜
陶长元
刘作华
左赵宏
姚固
施静
肖文
范兴
孙大贵
刘仁龙
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Chongqing University
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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

A kind of catalyst system of acetic acid synthesis from methanol carbonylation and application
Technical field
The present invention relates to use 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 methanol carbonylation.The method is with methyl alcohol (CH 3OH) and carbon monoxide (CO) be raw material, produce acetic acid under the catalyst system and catalyzing effect that catalyst, promoter and/or co-catalyst consist of.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 impacts, people are constantly exploring always.for example, publication No. is CN101954295A, name is 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 reaction system ", to overcome water to the exploration of whole reaction adverse effect (as: when in 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 the product separation stage in later stage), so, the means of the water that only adds " being 4%～6% by weight percentage " have been adopted in its catalyst system in this patent application, really also obtained the beneficial effect of minimizing water gas reaction and " separating technology that is follow-up acetic acid and water provides a great convenience ".Yet, due to the water that has still added after all " being 4%～6% by weight percentage " in its catalyst system, therefore, reduce water gas reaction and described " providing a great convenience "---finally be presented as the effect that reduces costs, 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 costs---and the price of lithium iodide is more expensive, is unfavorable for reducing costs; Hydroiodic acid is relatively large to the corrosion of reactor, has increased again anticorrosion cost.Moreover the reaction minimum temperature of this reaction system is 170 ℃, although the condition calculation is gentleer, still has improved space.So the total production cost of using this catalyst system is still higher.
Summary of the invention
The first purpose of the present invention is to provide the catalyst system that can reduce the acetic acid synthesis from methanol carbonylation of total production cost when using.
The second purpose of the present invention is to provide to use and realizes the catalyst system of described the first goal of the invention, and then can reduce the acetic acid synthesized method of total production cost.
Realizing the technical scheme of described the first goal of the invention, is a kind of like this catalyst system of acetic acid synthesis from methanol carbonylation, and aspect same as the prior art is that this catalyst system comprises major catalyst IrCl 33H 2The hydrate of O(iridous chloride) and co-catalyst CH 3The I(iodomethane), its improvements are that the interior polar modifier ionic liquid in addition of described catalyst system also has the transition metal halogen in described co-catalyst; Wherein, described ionic liquid is [BMIM] Tf 2The two fluoroform sulfimide salt of N(1-butyl-3-methylimidazole) or [Bupy] Tf 2The two fluoroform sulfimide salt of N(N-butyl-pyridinium), described transition metal halogen is CoCl 26H 2The hydrate of O(cobalt chloride), NiCl 26H 2The hydrate of O(nickel chloride), CuCl 22H 2The hydrate of O(copper chloride), ZnCl 2(zinc chloride) or ZnI 2(zinc iodide); When being applied to this catalyst system in acetic acid synthesized reaction system, with respect to this reaction system, the total mass concentration of described catalyst system accounts for below 61%, wherein, and IrCl 33H 2In O take Ir(iridium) mass concentration be 500～1500ppm, IrCl 33H 2The mol ratio of O and described transition metal halogen is 5～10, described CH 3The mass concentration of I is 25%～35%, the mass concentration of described ionic liquid is 25%～35%.
Realizing the technical scheme of described the second goal of the invention, is a kind of like this method of acetic acid synthesis from methanol carbonylation, and aspect same as the prior art is, it is with CH 3OH(methyl alcohol) be equipped with in the reaction system of primary raw material the synthetic method that contains catalyst system, its step comprises:
(1) with described CH 3All components in OH and catalyst system is all packed in reactor, and fully mixes to consist of acetic acid synthesized reaction system;
(2) the described reactor of sealing and replace air in this reactor with CO; Then adjust the pressure of CO, to the reactor heating, carry out methanol carbonylation to produce acetic acid under stirring; Its improvements are:
Described caltalyst is the catalyst system of realizing described the first goal of the invention;
CH described in step (1) 3OH is no less than 39% with respect to the mass concentration of described reaction system;
140～160 ℃ of reaction temperatures in step (2), the pressure that is filled with CO remains between 2.5～3MPa, and the reaction time is no longer proceeded down as degree take methanol carbonylation.
Can find out from scheme, all do not need to add entry in catalyst system of the present invention and acetic acid synthesized reaction system, so, by in reactant just do not existed with the adverse effect of water, so just greatly reduced water gas reaction, reduced simultaneously the content of water in products, real for simplifying follow-up acetic acid and providing a great convenience separating of water.All do not use lithium iodide and hydroiodic acid in catalyst system of the present invention and reaction system, more expensive because of the former in prior art, the latter has the deficiency of relatively large corrosion also to obtain overcoming to reactor.It can also be seen that from scheme, the reaction temperature of the present invention when acetic acid synthesized is 140～160 ℃, and 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 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 total production cost and say, the present invention reduces manyly than prior art.
The present invention is further illustrated below in conjunction with the specific embodiment.
The specific embodiment
One, a kind of catalyst system of acetic acid synthesis from methanol carbonylation, this catalyst system comprises major catalyst IrCl 33H 2O and co-catalyst CH 3I in the present invention, also has the polar modifier ionic liquid in described catalyst system, also have the transition metal halogen in described co-catalyst; Wherein, described ionic liquid is [BMIM] Tf 2N or [Bupy] Tf 2N, described transition metal halogen is CoCl 26H 2O, NiCl 26H 2O, CuCl 22H 2O, ZnCl 2Or ZnI 2When being applied to this catalyst system in acetic acid synthesized reaction system, with respect to this reaction system, the total mass concentration of described catalyst system accounts for below 61%, wherein, and IrCl 33H 2In O take the mass concentration of Ir as 500～1500ppm, IrCl 33H 2The mol ratio of O and described transition metal halogen is 5～10, described CH 3The mass concentration of I is 25%～35%, the mass concentration of described ionic liquid 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 described CH 3All components in OH and catalyst system is all packed in reactor, and fully mixes to consist of acetic acid synthesized reaction system;
(2) the described reactor of sealing and replace air in this reactor with CO; Then adjust the pressure of CO, to the reactor heating, carry out methanol carbonylation to produce acetic acid under stirring;
In the present invention, above-mentioned caltalyst is the described catalyst system of this specific embodiment first;
CH described in step (1) 3OH is no less than 39% with respect to the mass concentration of described reaction system;
140～160 ℃ of reaction temperatures in step (2), the pressure that is filled with CO remains between 2.5～3MPa, and the reaction time is no longer proceeded down as degree take methanol carbonylation.
Obviously, in practice, only only have 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, therefore only do simple the disclosure.Specifically: after the reaction of step (2) stops, allowing reactor naturally cool to room temperature; Open reactor, after isolating all components and accessory substance in catalyst system with the conventional way of distillation from obtain liquid product, namely 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 stirring in step (2), its speed is selected 300 rev/mins.
When reactor being carried out open after nature cools, obtain the liquid substance that product is does not have precipitation, this explanation catalyst of the present invention remains stable through not causing inactivation after reaction.After being isolated acetic acid by conventional method, with gas chromatograph analyzer (GC-1100), select the Porapak-Q stainless stee l packed column, thermal conductivity cell detector is analyzed the product after purifying.Then calculate the selective and acetic acid space-time yield of acetic acid in methanol conversion, product.The result sees the following form.
Table 1
Figure 327236DEST_PATH_IMAGE001
Table 2
Can find out from above-mentioned checking, the acetic acid in methanol conversion of the present invention, product is selective and the acetic acid space-time yield is all higher.
The same as is known to the person skilled in the art, finish in the liquid product of rear gained at methanol carbonylation, also include a certain amount of accessory substance, can find out from the molecular structure of all reactant composition of reaction system of the present invention, its accessory substance is methyl acetate and water; Show during checking, resulting accessory substance also only has methyl acetate and water, and both amounts are seldom---methanol conversion in top proof list, acetic acid is selective and the acetic acid space-time yield is all higher, the productive rate that is also principal product acetic acid is higher, all low this analysis conclusions of methyl acetate and water of can giving counterevidence.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 not adding entry before reaction, so, the water yield in accessory substance only just bring after reaction seldom.Therefore 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 total production cost and say, the present invention reduces manyly than prior art really.

Claims (1)

1. the method for an 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 described CH 3All components in OH and catalyst system is all packed in reactor, and fully mixes to consist of acetic acid synthesized reaction system;
(2) the described reactor of sealing and replace air in this reactor with CO; Then adjust the pressure of CO, to the reactor heating, carry out methanol carbonylation to produce acetic acid under stirring; It is characterized in that:
Described catalyst system comprises major catalyst IrCl 33H 2O and co-catalyst CH 3I； Also have the polar modifier ionic liquid in described catalyst system, also have the transition metal halogen in described co-catalyst; Wherein, described ionic liquid is [BMIM] Tf 2N or [Bupy] Tf 2N, described transition metal halogen is CoCl 26H 2O, NiCl 26H 2O, CuCl 22H 2O, ZnCl 2Or ZnI 2When being applied to this catalyst system in acetic acid synthesized reaction system, with respect to this reaction system, the total mass concentration of described catalyst system accounts for below 61%, wherein, and IrCl 33H 2In O take the mass concentration of Ir as 500～1500ppm, IrCl 33H 2The mol ratio of O and described transition metal halogen is 5～10, described CH 3The mass concentration of I is 25%～35%, the mass concentration of described ionic liquid is 25%～35%;
CH described in step (1) 3OH is no less than 39% with respect to the mass concentration of described reaction system;
140～160 ℃ of reaction temperatures in step (2), the pressure that is filled with CO remains between 2.5～3MPa, and the reaction time is no longer proceeded down as degree take methanol carbonylation.
CN 201110392931 2011-12-01 2011-12-01 Catalyst system for synthesizing acetic acid through carbonylation of methanol and application Expired - Fee Related CN102366724B (en)

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CN103861643B (en) * 2014-04-01 2016-06-15 北京众智创新科技开发有限公司 A kind of catalyst system for acetic acid synthesis from methanol carbonylation and application thereof
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

Citations (4)

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Publication number Priority date Publication date Assignee Title
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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
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