CN102294265B - Catalyst for synthesis of acetic acid through carbonylation at low water concentration, preparation method and application thereof - Google Patents
Catalyst for synthesis of acetic acid through carbonylation at low water concentration, preparation method and application thereof Download PDFInfo
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- CN102294265B CN102294265B CN 201110182509 CN201110182509A CN102294265B CN 102294265 B CN102294265 B CN 102294265B CN 201110182509 CN201110182509 CN 201110182509 CN 201110182509 A CN201110182509 A CN 201110182509A CN 102294265 B CN102294265 B CN 102294265B
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Abstract
The invention discloses a catalyst for synthesis of acetic acid through carbonylation at a low water concentration, a preparation method and an application thereof. The invention belongs to the field of low pressure synthesis of acetic acid through carbonylation of methanol or/and methyl acetate, relates to a catalyst for synthesis of the acetic acid through carbonylation at the low water concentration, a preparation method for the catalyst and an application for the catalyst. According to the present invention, the catalyst adopts an alkyl phosphate-imidazole-rhodium complex as a main catalyst, and adopts methyl iodide or a mixture comprising the methyl iodide and lithium iodide as an assistant catalyst; carbon monoxide reacts with the methanol or/and the methyl acetate at a temperature of 160-200 DEG C and under pressure of 2.5-4.0 MPa to obtain the acetic acid. The catalyst has good activity and good stability under a condition of the water content of 1-6%. The alkyl phosphate-imidazole-rhodium complex is prepared through the following steps that: imidazole reacts with trialkyphosphate; rhodium, acetic acid and a hydrogen iodide solution are added; the carbon monoxide is introduced under the certain condition to obtain the alkyl phosphate-imidazole-rhodium complex, which has the following structure.
Description
Technical field:
The invention belongs to low pressure methanol or and methyl acetate carbonylation acetic acid field, relate to a kind of under low water concentration the catalyst of carbonylation acetic acid, and the preparation method and application of this catalyst.
Background technology:
The rhodium carbonyl of the solubility that the F.E.Paulik of nineteen sixty-eight U.S. Monsanto company and partner thereof etc. report-iodine catalyst system (US 3 769 329) has very high catalytic activity and selective to methanol carbonyl synthesized acetic acid, can under the reaction condition of 3.0-6.0MPa and 150-200 ℃, carry out, product has reached more than 99% with the methyl alcohol rate of collecting, selectively also brought up to 99%, main side reaction is transformationreation, propionic acid reaction and methanation reaction.The rhodium catalyst system and catalyzing is comprised of rhodium complex and iodomethane, and its active specy is diiodo-dicarbonyl rhodium ([Rh (CO)
2I
2]
-), because the relatively poor problem of its existence and stability, the water in the reaction medium need to maintain about 14% just can keep normal reaction.
For the problem that Monsanto technique exists, many researchers are devoted to the improvement of Monsanto catalyst.Research for many years mainly concentrates on these several aspects of base metal, part, carrier and auxiliary agent, and the purpose of its research is to improve the active and stable of existing catalyst, reaches the raising reaction rate, increases the purpose of acetic acid productive rate.
In the process of methanol carbonylation, in order to improve the catalytic performance of active specy centered by rhodium, can transform the structure of catalyst itself.Adopt [RhCl (CO) CPEt such as people such as J.Rankin
3]
2, with space-time yield STY (product of moles/liter. hour) by [Rh (CO)
2Cl]
25.0 bring up to 9.2 (Chem.Commun, 1997.1835), C.A.Carraz etc. select Bidentate phosphine rhodium complex, its STY reaches 13.7 (Chem.commun.2000,1277).In order to make rhodium complex catalyst that better dissolubility be arranged in reaction medium, adding some in the reaction system also is the important content of research work to the material that catalytic reaction has facilitation.This class additive is generally some metal salt compounds.In numerous additive, lithium iodide is one of maximum and the most successful example of report, and BP company adopts lithium compound as auxiliary agent, and rhodium concentration is 640ppm in the reaction medium, and during lithium concentration 5340ppm, its STY is 8 (US 6 130 355).
The industrial exemplary of significantly improving production technology by adding the inorganic salts co-catalyst is Hoechst Celanese company.The said firm has obtained to be undertaken by the Monsanto carbonylic synthesis technology license of commercial size production of acetic acid in 1978, and it has been carried out a series of improvement.Early 1980s, the said firm has developed the Processes for Producing Acetic Acid (AO Plus) of the low water content of independent intellectual property right, this technique has been improved the carbonyl synthesis acetic acid technology widely, water content in the reaction medium has significantly dropped to about 5%, unit product investment, energy consumption and supplies consumption decrease.The main feature of this technique is namely by adding inorganic salt compounded of iodine to a higher content, and (US 5001259, EP055618) with stable effect to reach the activity that improves catalyst.
Summary of the invention
The object of the invention is to select under low water content, still to have the alkylphosphonate imidazoles rhodium complex of high activity and high stability, thereby the alkylphosphonate imidazoles rhodium complex new catalyst that is used for producing acetic acid by carbonylation method is provided.The characteristics of this catalyst are in the situation that the adding lithium iodide can be produced acetic acid by carbonylation under very low water content, still have excellent activity and stability.
Another object of the present invention has provided a kind of preparation method of the alkylphosphonate imidazoles rhodium catalyst for carbonylation acetic acid.
The present invention proposes the catalyst of the low water carbonylation acetic acid of a kind of low pressure methanol or methyl acetate, it is characterized in that: this catalyst is take alkylphosphonate imidazoles rhodium complex as major catalyst, take the mixture of iodomethane or iodomethane and lithium iodide as co-catalyst.The structural formula of trialkylphosphate imidazoles rhodium complex is:
Wherein R is CH
3, C
2H
5Or C
4H
9
The preparation method of the alkylphosphonate imidazoles rhodium catalyst for carbonylation acetic acid of the present invention is: will wait mole imidazoles and trialkylphosphate to add stirred autoclave, reaction is 1-1.5 hour under 100-130 ℃ condition, then add acetic acid, acetic acid rhodium and hydrogen iodide solution, and pass into carbon monoxide 5-10 hour, obtain alkylphosphonate imidazoles rhodium complex after the reaction.
Catalyst of the present invention, it is characterized in that: alkylphosphonate imidazoles rhodium complex, methyl alcohol or methyl acetate, acetic acid, water and iodomethane are added in the reactor, and pass into carbon monoxide, the temperature of reaction is controlled at 160-200 ℃, pressure is controlled at 2.5-4.0MPa, obtains acetic acid after the reaction; The water percentage by weight is 1.5-6.0% in the described liquid reaction medium, and methyl alcohol or methyl acetate percentage by weight are 0.1-5.0%, and the iodomethane percentage by weight is 5.0-20.0%; Rhodium catalyst is take the concentration of pure rhodium as 200-1800ppm in liquid reaction medium.
The reactivity of catalyst can reduce with the reduction of water content in the reaction system, the present invention adds lithium iodide in reaction liquid, its addition is that the mol ratio of lithium and rhodium is 1-200: 1, the water percentage by weight can be controlled in the scope of 1.0-3.0% in the reaction medium, rhodium catalyst (in pure rhodium) concentration can be stablized and is controlled at 500-1800ppm, and reactivity (STY) still remains on more than 15.
Poor stability is an open defect of original carbonylation of methanol catalyst, mainly be because original catalytic active center is dicarbapentaborane diiodo-rhodium anion structure, this structure is under reaction condition, especially unstable under the flash conditions, easily generate the rhodium triiodid precipitation, cause the reduction of production capacity, even the pipeline of obstruction production equipment causes stopping production; Because adopt alkylphosphonate imidazoles rhodium catalyst, the stability of this catalyst obviously is better than Monsanto carbonylation of methanol catalyst.The Meng Shan reactivity of the used catalyst of methanol carbonylation process counts (water percentage is as about 14% in the reaction medium) about 8mol/ (Lh) take space-time yield (STY), composition and reaction condition through the control catalyst, the activity of this catalyst can reach more than the 30mol/ (Lh), through further optimizing, the potentiality on the activity provide wide space for existing expanding production of commercial plant.Methanol carbonylation itself is a reaction that selectivity ratios is higher, and side reaction mainly is that water and reaction of carbon monoxide generate hydrogen and carbon dioxide owing to containing a certain amount of water in the reactor.The hydrogen that generates is also more active, and it can participate in reaction and generate other accessory substance, such as methane, and acetaldehyde etc.This catalyst be owing to can drop to the water content in the reaction system a quite low level, thereby can greatly improve the selective of reaction.
Having of lithium iodide is beneficial to the methyl acetate that keeps higher concentration in the reaction system, can reduce like this water content in the process units, thereby greatly reduce system loading, not only saved energy consumption, and can also greatly increase the production capacity of equipment.A large amount of lithium iodide co-catalysts are that the AO Plus technology of Celanese company is with respect to the main improvement of Monsanto house journal technology (namely afterwards BP technology).The use of lithium iodide co-catalyst has improved production efficiency greatly, but the too high meeting of content of iodine brings the increase of iodine consumption in the production, increased to a certain extent production cost, the present invention adopts the alkylphosphonate imidazoles rhodium catalyst of ad hoc structure, when not adding lithium iodide or lithium acetate, water content in the reaction medium still can reach the level of AO Plus technology, when adding lithium iodide or lithium acetate, water content in the reaction medium can further reduce, and the activity of catalyst and stable still maintain very high level.
The specific embodiment
Reactor is controlled under the certain reaction temperature and pressure, carbon monoxide passes in the reactor continuously, for the carbon monoxide pressure of tension that makes the reactor upper space remains on certain level, need to be from the continuous Exhaust Gas in top of the gas-phase space of reactor, and control simultaneously the gross pressure of reactor.Utilize a liquid level in the liquid-level controller conditioned reaction device, discharge continuously liquid reacting product, and be transported in the flash vessel.The liquid phase that contains catalyst bottom the flash vessel is sent the reaction of reactor sustainable participation back to, and the gas phase at top is sent the later separation device, and further separating-purifying also obtains acetate products.Separator is separated contains the materials such as iodomethane, water, methyl acetate and sends reactor back to and further react.
The above is the basic procedure of reaction system in the continuous reaction apparatus.This flow process is suitable for the acetic acid industry process units, also can be fit to pilot-plant and mold trial device.As long as can keep the steady running of reaction system, just enough be used for the performance of evaluate catalysts.We form different catalyst system and catalyzings emphatically, and different working condition is discussed the impact of catalyst performance.In order more clearly to illustrate technology contents of the present invention, further do some description especially exemplified by several embodiment, but it should be noted that the following examples only consist of explanation of the present invention, and be not construed as limiting the invention.
Reference embodiment:
Catalyst reactor consists of rhodium carbonyl (in rhodium) 450ppm, iodomethane 15wt%, and methyl acetate 5wt%, water 6.0wt%, all the other are acetic acid; 190 ℃ of control reaction temperatures, reaction pressure 3.0MPa.The activity of carbonylation is 6.1mol/ (Lh), and finding after the reaction has a large amount of Powdered rhodium triiodid precipitations, proves the existence at the water that does not have high level or stabilizing agent, and the stability of this catalyst and activity are all very poor.
Embodiment 1
1 mole of imidazoles and 1 mole of phosphoric acid trimethyl are added in the stirred autoclave, reaction is 1 hour under 120 ℃ condition, then add acetic acid, acetic acid rhodium and hydrogen iodide solution, and passed into carbon monoxide about 5 hours, obtain alkylphosphonate imidazoles rhodium complex after the reaction.
Embodiment 2
3 moles of imidazoles and 3 mole of phosphoric acid triethyls are added in the stirred autoclave, reaction is 1.5 hours under 110 ℃ condition, then add acetic acid, acetic acid rhodium and hydrogen iodide solution, and passed into carbon monoxide about 8 hours, obtain alkylphosphonate imidazoles rhodium complex after the reaction.
Embodiment 3
5 moles of imidazoles and 5 mole of phosphoric acid tributyls are added in the stirred autoclave, reaction is 1 hour under 130 ℃ condition, then add acetic acid, acetic acid rhodium and hydrogen iodide solution, and passed into carbon monoxide about 10 hours, obtain alkylphosphonate imidazoles rhodium complex after the reaction.
Embodiment 4:
Catalyst reactor chlorooxon imidazoles rhodium complex (in rhodium) 450ppm, iodomethane 15wt%, methyl acetate 5wt%, water 5.0wt%, all the other are acetic acid; 190 ℃ of control reaction temperatures, reaction pressure 3.0MPa.The activity of carbonylation is 10.5mol/ (Lh), does not find any precipitation of rhodium catalyst after the reaction.This stability that proves this reacting middle catalyst is better.
Embodiment 5:
Catalyst reactor chlorooxon imidazoles rhodium complex (in rhodium) 450ppm, iodomethane 15wt%, methyl acetate 5wt%, water 5.0wt%, all the other are acetic acid; 190 ℃ of control reaction temperatures, reaction pressure 3.0MPa.The activity of carbonylation is 8.5mol/ (Lh), does not find any precipitation of rhodium catalyst after the reaction.This stability that proves this reacting middle catalyst is better.
Embodiment 6:
Catalyst reactor chlorooxon imidazoles rhodium complex (in rhodium) 450ppm, iodomethane 15wt%, methyl acetate 5wt%, water 3.0wt%, all the other are acetic acid; 190 ℃ of control reaction temperatures, reaction pressure 3.0MPa.The activity of carbonylation is 6.5mol/ (Lh), does not find any precipitation of rhodium catalyst after the reaction.This stability that proves this reacting middle catalyst is better.
Embodiment 7:
Catalyst reactor chlorooxon imidazoles rhodium complex (in rhodium) 700ppm, iodomethane 15wt%, methyl acetate 5wt%, water 1.5wt%, lithium iodide 10%, all the other are acetic acid; 195 ℃ of control reaction temperatures, reaction pressure 3.0MPa.The activity of carbonylation is 17.6mol/ (Lh), does not find any precipitation of rhodium catalyst after the reaction.This stability that proves this reacting middle catalyst is better.
Embodiment 8:
Catalyst reactor di(2-ethylhexyl)phosphate ethyl ester imidazoles rhodium complex (in rhodium) 1000ppm, iodomethane 15wt%, methyl acetate 5wt%, water 6%, all the other are acetic acid; 185 ℃ of control reaction temperatures, reaction pressure 3.0MPa.The activity of carbonylation is 21.1mol/ (Lh), does not find any precipitation of rhodium catalyst after the reaction.This stability that proves this reacting middle catalyst is better.
Embodiment 9:
Catalyst reactor di(2-ethylhexyl)phosphate butyl ester imidazoles rhodium complex (in rhodium) 1800ppm, iodomethane 15wt%, methyl acetate 5wt%, water 3%, all the other are acetic acid; 198 ℃ of control reaction temperatures, reaction pressure 3.0MPa.The activity of carbonylation is 38.5mol/ (Lh), does not find any precipitation of rhodium catalyst after the reaction.This stability that proves this reacting middle catalyst is better.
Embodiment 10:
Catalyst reactor di(2-ethylhexyl)phosphate butyl ester imidazoles rhodium complex (in rhodium) 1500ppm, iodomethane 15wt%, methyl acetate 5wt%, water 2.0%, lithium iodide 8%, all the other are acetic acid; 198 ℃ of control reaction temperatures, reaction pressure 3.0MPa.The activity of carbonylation is 41.5mol/ (Lh), does not find any precipitation of rhodium catalyst after the reaction.This stability that proves this reacting middle catalyst is better.
Claims (3)
1. the catalyst of a low water carbonylation acetic acid, it is characterized in that: this catalyst is take alkylphosphonate imidazoles rhodium complex as major catalyst, take the mixture of iodomethane or iodomethane and lithium iodide as co-catalyst; The structural formula of alkylphosphonate imidazoles rhodium complex is:
Wherein R is CH
3, C
2H
5Or C
4H
9
2. the preparation method of described catalyst according to claim 1, it is characterized in that: will wait mole imidazoles and trialkylphosphate to add in the stirred autoclave, reaction is 1-1.5 hour under 100-130 ℃ condition, then add acetic acid, acetic acid rhodium and hydrogen iodide solution, and pass into carbon monoxide 5-10 hour, obtain alkylphosphonate imidazoles rhodium complex.
3. the according to claim 1 application of described catalyst, it is characterized in that: alkylphosphonate imidazoles rhodium complex, methyl alcohol or methyl acetate, acetic acid, water and iodomethane are added in the reactor, the all substances summation is hereinafter referred to as liquid reaction medium in the whole reactor, and pass into carbon monoxide, the temperature of reaction is controlled at 160-200 ℃, pressure is controlled at 2.5-4.0MPa, obtains acetic acid after the reaction; The water percentage by weight is 1.5-6.0% in the liquid reaction medium, and methyl alcohol or methyl acetate percentage by weight are 0.1-5.0%, and the iodomethane percentage by weight is 5.0-20.0%; Rhodium catalyst is take the concentration of pure rhodium as 200-1800ppm in liquid reaction medium.
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| CN107141213A (en) * | 2017-05-24 | 2017-09-08 | 北京三聚环保新材料股份有限公司 | A kind of method of acetic acid synthesis from methanol carbonylation |
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| CN107011118A (en) * | 2017-05-24 | 2017-08-04 | 北京三聚环保新材料股份有限公司 | The technique that a kind of methanol prepares and refines ethanol |
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| CN101391231A (en) * | 2008-10-31 | 2009-03-25 | 中国科学院化学研究所 | Imidazole acetic-acid rhodium complexes catalyst capable of catalyzing carbonylation reaction to preparing acetic acid and acetic anhydride and preparation method and use thereof |
| CN101716527A (en) * | 2009-12-04 | 2010-06-02 | 北京化工大学 | High-stability catalyst for producing acetic acid by carbonylation method and application method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101391231A (en) * | 2008-10-31 | 2009-03-25 | 中国科学院化学研究所 | Imidazole acetic-acid rhodium complexes catalyst capable of catalyzing carbonylation reaction to preparing acetic acid and acetic anhydride and preparation method and use thereof |
| CN101716527A (en) * | 2009-12-04 | 2010-06-02 | 北京化工大学 | High-stability catalyst for producing acetic acid by carbonylation method and application method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141213A (en) * | 2017-05-24 | 2017-09-08 | 北京三聚环保新材料股份有限公司 | A kind of method of acetic acid synthesis from methanol carbonylation |
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Effective date of registration: 20201030 Address after: Building 1, 5500 Yuanjiang Road, Minhang District, Shanghai, 201109 Patentee after: Shanghai de Mou Engineering Technology Co., Ltd Address before: Room 2912, Youhao building, 158 Youhao Road, Zhongshan District, Dalian City, Liaoning Province Patentee before: Dalian Fraser Co., Ltd |