CN101716527B - High-stability catalyst for producing acetic acid by carbonylation method and application method thereof - Google Patents
High-stability catalyst for producing acetic acid by carbonylation method and application method thereof Download PDFInfo
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Abstract
The invention relates to a high-stability catalyst for producing acetic acid by low pressure carbonylation . The catalyst uses rhodium as a main catalyst, uses methyl iodide or the mixture of the methyl iodide and lithium iodide as a cocatalyst and uses an ionic liquid as a stabilizer; and the ionic liquid stabilizer is 1,3-dialkyl imidazole phosphatic dialkyl ester ([RR'im] [DRP]), wherein R and R' are alkyl groups in which the number of carbon atoms is within 1-5, and , R and R' can be both same and different. The ionic liquid is used as the efficient stabilizer, and the mixture of the acetic acid, methyl acetate and water is used as a reaction medium. The stabilizer can enable the rhodium catalyst to keep high stability under very low water content, but the stability of a traditional Monsanto catalyst can be ensured only by maintaining high water content in a reaction system. The reduction of the water content in the reaction system can enhance the space efficiency of the methanol carbonylation technology. The catalyst of the invention can also simultaneously use the lithium iodide to maintain sufficient content of iodine ions in a low water system to enhance the activity of the catalyst.
Description
Technical field
The present invention is used for catalyzer and the using method thereof that the low pressure carbonylation reaction is produced acetic acid, belongs to the catalytic reaction engineering technical field.
Background technology
Acetic acid is a kind of important Organic Chemicals, be mainly used in products such as producing Vinyl Acetate Monomer, aceticanhydride, acetates and monochloroacetic acid, it is the important source material of synthon, tackiness agent, medicine, agricultural chemicals and dyestuff, also be good organic solvent, purposes is very widely also arranged in industries such as plastics, rubber, printing.
Twentieth century end of the sixties, the rhodium carbonyl-iodine catalyst system (US 3 769 329) of the solubilities that are used for acetic acid synthesis from methanol carbonylation that the people reported such as F.E.Paulik of U.S. Monsanto company; Because methanol carbonylation there are higher catalytic activity and selectivity, and the reaction conditions gentleness, make research of carbonylation of methanol synthetic and suitability for industrialized production obtain breakthrough.Passed through the development of decades, the low pressure methanol carbonylation method has become most important synthetic method in the acetic acid industry production.
In carbonylation of methanol synthesis process route, the research of catalyzer is an important content.Purpose is to study active high, and good stability is easy to reclaim, and has the novel catalyst system of homogeneous phase and heterogeneous two class catalyzer advantages concurrently.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 existing activity of such catalysts and stability, reaches the raising speed of reaction, increases the purpose of acetic acid productive rate.
In the process of methanol carbonylation, be the catalytic performance of center active specy in order to improve with the rhodium, can transform the structure of catalyst themselves.Adopt [RhCl (CO) CPEt3] 2 as people such as J.Rankin, with space-time yield STY (product of moles/liter. hour) bring up to 9.2 (Chem.Commun by 5.0 of [Rh (CO) 2Cl] 2,1997.1835), C.A.Carraz etc. select bidentate type phosphine rhodium complex for use, its STY reaches 13.7 (Chem.commun.2000,1277).In order to make rhodium complex catalyst that better solvability be arranged in reaction medium, adding some in the reaction system also is the important content of research work to the material that catalyzed reaction has promoter action.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 rhodium catalyst less stable that Monsanto technology is used when temperature of reaction surpasses 200 ℃, just begins to decompose inactivation; When low carbon monoxide pressure of tension and low hydroiodic acid HI concentration, easily generate the rhodium triiodid precipitation, destroy the synthetic acetic acid reaction of carbonylation.Therefore in process of production except that needs are kept the dividing potential drop of high carbon monoxide, also need add excessive hydrogen iodide, so just greatly increase corrosive nature production unit to keep the stability of rhodium catalyst.
The industrial exemplary of significantly improving production technique by adding the inorganic salt promotor is a Hoechst Celanese company.The said firm has obtained to be undertaken by the Monsanto carbonylic synthesis technology permission of commercial size acetic acid production 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 of the low water content of independent intellectual property right, and this technology has been improved the production process of acetic acid widely.The principal feature of this technology is promptly by adding inorganic salt compounded of iodine to a higher content, and (US 5001259, EP055618) to reach the effect that improves activity of such catalysts and stability.
Summary of the invention
The objective of the invention is to propose a kind of catalyzer of novel producing acetic acid by carbonylation method of the Celanese of being different from technology.The characteristics of this catalyzer are not add lithium iodide or only adding under the situation of lithium iodide of lower aq, still having excellent stability and activity.
The catalyzer that the present invention proposes is the catalyzer that a kind of low pressure carbonylation of high stability is produced acetic acid, it is characterized in that: this catalyzer is Primary Catalysts with the rhodium, mixture with methyl iodide or methyl iodide and lithium iodide is a promotor, is stablizer with the ionic liquid; Ionic liquid stabilizer is 1,3-dialkylimidazolium phosphate dialkyl ester ([RR ' im] [DRP]), and R wherein, R ' is the alkyl of carbonatoms between 1-5, R and R ' are identical or different.
The using method of described catalyzer is characterized in that: produce acetic acid by the carbon monoxide carbonylation reaction; The temperature of reaction is controlled at 170-230 ℃, and pressure-controlling is at 2.0-4.0MPa; Whole reaction system is hereinafter referred to as liquid reaction medium; 1, the weight percent of 3-dialkylimidazolium phosphate dialkyl ester in liquid reaction medium is 0.1-5.0%; The water weight percent is 1.0-9.0% in the described liquid reaction medium, and the ritalin weight percent is 0.1-15.0%, and the methyl iodide weight percent is 6.0-20.0%, and the lithium iodide weight percent is 2.0-16.5%, and all the other are acetic acid; Rhodium catalyst is 200-1800ppm in the concentration of pure rhodium in liquid reaction medium.
The catalyzer that the present invention proposes is a kind of catalyzer that the low pressure carbonylation is produced acetic acid that is used for of high stability, and this rhodium complex is the active centre, is promotor with the mixture of methyl iodide or itself and lithium iodide, is stablizer efficiently with ionic liquid.Wherein ionic liquid stabilizer is 1,3-dialkylimidazolium phosphate dialkyl ester ([RR ' im] [DRP], wherein R, R ' is the alkyl of carbonatoms between 1-5, and R and R ' can be the same or different, for example, 1-butyl-3-Methylimidazole dimethyl phosphate salt, i.e. [Bmim] [DMP].The usage quantity of [RR ' im] [DRP] is the 0.1-5.0% of reaction medium gross weight, is preferably 0.5-2.5%.The rhodium carbonyl active centre of catalyzer is specially dicarbapentaborane diiodo-rhodium, and the content of rhodium carbonyl in reaction system is preferably 600-1000ppm in rhodium 200-1800ppm.The content of methyl iodide in reaction system is 6.0-20.0%, is preferably 11.0-16.0%.The content of lithium iodide in reaction system is 2.0-16.5%, is preferably 6.5-12.5%.When not adding lithium iodide, can not influence the stability of catalyzer.This catalyzer is when being used for carbonylation reaction production acetic acid, and the employing ritalin is a raw material, and medium is the mixture of acetic acid, ritalin and water.Water-content is controlled at 1.0-9.0% in the reaction system, is preferably 2.0-5.0%, and ritalin content is controlled at 0.1-15.0%, is preferably 2.5-7.5%, and the remaining reaction medium is an acetic acid.The temperature of methanol carbonylation is controlled at 170-230 ℃, is preferably 185-195 ℃.The total pressure of reactor will be controlled at 2.0-4.0MPa, is preferably about 2.5-3.5MPa.
Poor stability is an open defect of original carbonylation of methanol catalyzer, mainly be because original catalytic active center is a dicarbapentaborane diiodo-rhodium anion structure, this structure is under reaction conditions, especially unstable under the flash conditions, generate the rhodium triiodid precipitation easily, cause the reduction of throughput, even the pipeline of obstruction production unit causes stopping production; Because adopting ionic liquid is stablizer, the stability of this catalyzer obviously is better than Monsanto carbonylation of methanol catalyzer.The Meng Shan reactive behavior of the used catalyzer of methanol carbonylation process counts about 8mol/ (Lh) with space-time yield (STY), composition and reaction conditions through control catalyst, this activity of such catalysts can reach more than the 30mol/ (Lh), through further optimizing, the potentiality on the activity provide wide space for existing expanding production of full scale 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 carbonic acid gas owing to contain a certain amount of water in the reactor.The hydrogen that generates is also relatively more active, and it can participate in reaction and generate other by product, such as methane, and acetaldehyde etc.This catalyzer be owing to can drop to the water-content in the reaction system a quite low level, thereby can improve the selectivity of reaction greatly.
Having of lithium iodide is beneficial to the ritalin that keeps higher concentration in the reaction system, can reduce the water-content in the production equipment like this, thereby reduce system loading greatly, not only saved energy consumption, and can also increase the throughput of equipment greatly.A large amount of lithium iodide promotors are the main improvement with respect to Monsanto house journal technology (i.e. BP technology afterwards) of the AO Plus technology of Celanese company.The use of lithium iodide promotor has improved production efficiency greatly, but the too high meeting of iodine content brings the increase of iodine consumption in the production, increased production cost to a certain extent, the present invention adopts the ionic liquid stabilizer of ad hoc structure, can not add the consumption of lithium iodide or reduction lithium iodide.
Embodiment
Reactor is controlled at the certain reaction temperature, and under agitation, carbon monoxide is blasted reactor by distribution device in gas-fluid, for the carbon monoxide pressure of tension that makes the reactor upper space remains on certain level, need discharge gas continuously from the top of the vapour space of reactor, and the total pressure of controlling reactor simultaneously.Utilize a liquid level in the liquid-level controller conditioned reaction device, continuous expel liquid reaction product, and be transported in the flasher.Flasher comes back to reactor after methyl iodide is separated, and to keep wherein certain methyl iodide content, rest part enters the acetic acid separated purification system in downstream, obtains acetate products.Send back in the reactor after the material of flasher bottom is discharged, this strand material mainly is acetic acid and mixture of catalysts.Continue each component concentrations in the analysis reactor, and come each component in the controlling reactor to be in the concentration range of setting by the turnover logistics.
The above is the basic procedure of reactive system in the continuous reaction apparatus.This flow process is suitable for the acetic acid industry production equipment, also can be fit to pilot plant and mold trial device.As long as can keep the steady running of reactive system, just enough be used for the performance of evaluate catalysts.We form different catalyst system emphatically, and different working condition is discussed the influence 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 constitute explanation of the present invention, and be not construed as limiting the invention.
The reference example:
Catalyst reactor consists of rhodium carbonyl (in rhodium) 450ppm, methyl iodide 19wt%, and ritalin 10wt%, water 0.5wt%, all the other are acetic acid; 230 ℃ of control reaction temperature, reaction pressure 3.0MPa.The activity of carbonylation reaction is 6.5mol/ (Lh), and the reaction back finds that a large amount of Powdered rhodium triiodid precipitations is arranged.This reaction just begins to carry out up to 230 ℃.Proof is in the existence of water that does not have high level or lithium iodide, and the stability of this catalyzer and activity are all very poor.
Embodiment 1
Catalyst reactor consists of rhodium carbonyl (in rhodium) 450ppm, methyl iodide 19wt%, and ionic liquid [Bmim] [DMP] is 5wt%, ritalin 11wt%, water 0.5wt%, all the other are acetic acid; 250 ℃ of control reaction temperature, reaction pressure 3.0MPa.The activity of carbonylation reaction is 10mol/ (Lh), does not find any precipitation after the reaction.This stability that proves this reacting middle catalyst is better.
Embodiment 2
Catalyst reactor consists of rhodium carbonyl (in rhodium) 450ppm, methyl iodide 19wt%, and ionic liquid [Mmin] [DMP] is 5wt%, ritalin 10wt%, water 0.5wt%, all the other are acetic acid; 250 ℃ of control reaction temperature, reaction pressure 3.0MPa.The activity of carbonylation reaction is 10mol/ (Lh), does not find any precipitation after the reaction.This stability that proves this reacting middle catalyst is better.
Embodiment 3
Catalyst reactor consists of rhodium carbonyl (in rhodium) 800ppm, methyl iodide 15wt%, and ionic liquid [Bmim] [DBP] is 5wt%, ritalin 8wt%, water 3wt%, all the other are acetic acid; 180 ℃ of control reaction temperature, reaction pressure 2.5MPa.The activity of carbonylation reaction is 17.6mol/ (Lh), does not find any precipitation after the reaction.This stability that proves this reacting middle catalyst is with better active.
Embodiment 4
Catalyst reactor consists of rhodium carbonyl (in rhodium) 1000ppm, methyl iodide 11wt%, and ionic liquid [EEim] [DEP] is 5wt%, ritalin 2.5wt%, water 8wt%, all the other are acetic acid; 180 ℃ of control reaction temperature, reaction pressure 3.5MPa.The activity of carbonylation reaction is 25.8mol/ (Lh), does not find any precipitation after the reaction.
Embodiment 5
Catalyst reactor consists of rhodium carbonyl (in rhodium) 1000ppm, methyl iodide 8wt%, and ionic liquid [Emim] [DMP] is 2wt%, ritalin 5wt%, water 3wt%, all the other are acetic acid; 190 ℃ of control reaction temperature, reaction pressure 3.0MPa.The activity of carbonylation reaction is 23.5mol/ (Lh), does not find any precipitation after the reaction.
Embodiment 6
Catalyst reactor consists of rhodium carbonyl (in rhodium) 1000ppm, methyl iodide 8wt%, and lithium iodide 2wt%, ionic liquid [Bmim] [DMP] is 0.5wt%, ritalin 10wt%, water 4wt%, all the other are acetic acid; 185 ℃ of control reaction temperature, reaction pressure 3.0MPa.The activity of carbonylation reaction is 22.7mol/ (Lh), does not find any precipitation after the reaction.
Embodiment 7
Catalyst reactor consists of rhodium carbonyl (in rhodium) 1000ppm, methyl iodide 8wt%, and lithium iodide 16wt%, ionic liquid [Bmim] [DMP] is 1wt%, ritalin 2wt%, water 2wt%, all the other are acetic acid; 170 ℃ of control reaction temperature, reaction pressure 5.0MPa.The activity of carbonylation reaction is 20.4mol/ (Lh), does not find any precipitation after the reaction.
Embodiment 8
Catalyst reactor consists of rhodium carbonyl (in rhodium) 1800ppm, methyl iodide 8wt%, and lithium iodide 16wt%, ionic liquid [Bmim] [DMP] is 1wt%, ritalin 9wt%, water 2wt%, all the other are acetic acid; 170 ℃ of control reaction temperature, reaction pressure 3.0MPa.The activity of carbonylation reaction is 38.5mol/ (Lh), does not find any precipitation after the reaction.
Claims (1)
1. the low pressure carbonylation of a high stability is produced the using method of the catalyzer of acetic acid, and this catalyzer is Primary Catalysts with the rhodium, is promotor with the mixture of methyl iodide or methyl iodide and lithium iodide, is stablizer with the ionic liquid; Ionic liquid stabilizer is 1,3-dialkylimidazolium phosphate dialkyl ester [RR ' im] [DRP], and R wherein, R ' is the alkyl of carbonatoms between 1-5, R and R ' are identical or different;
It is characterized in that: produce acetic acid by the carbon monoxide carbonylation reaction; The temperature of reaction is controlled at 170-230 ℃, and pressure-controlling is at 2.0-4.0MPa; Whole reaction system is hereinafter referred to as liquid reaction medium; 1, the weight percent of 3-dialkylimidazolium phosphate dialkyl ester in liquid reaction medium is 0.1-5.0%; The water weight percent is 1.0-9.0% in the described liquid reaction medium, and the ritalin weight percent is 0.1-15.0%, and the methyl iodide weight percent is 6.0-20.0%, and the lithium iodide weight percent is 2.0-16.5%, and all the other are acetic acid; Rhodium catalyst is 200-1800ppm in the concentration of pure rhodium in liquid reaction medium.
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| US9598342B2 (en) | 2013-03-15 | 2017-03-21 | Celanese International Corporation | Production of acetic acid with enhanced catalyst stability |
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