CN102381956B - Method for preparation of acetic anhydride and acetic acid by means of carbonyl synthesis of methyl acetate and methanol azeotrope and method for separation - Google Patents
Method for preparation of acetic anhydride and acetic acid by means of carbonyl synthesis of methyl acetate and methanol azeotrope and method for separation Download PDFInfo
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- CN102381956B CN102381956B CN 201110262745 CN201110262745A CN102381956B CN 102381956 B CN102381956 B CN 102381956B CN 201110262745 CN201110262745 CN 201110262745 CN 201110262745 A CN201110262745 A CN 201110262745A CN 102381956 B CN102381956 B CN 102381956B
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Abstract
The invention discloses a method for preparation of acetic anhydride and acetic acid by means of carbonyl synthesis of methyl acetate and methanol azeotrope. The synthesis reaction is operated in a carbonyl synthesizing kettle (1) which is provided with a mixer, a bypass circulation device controlled by a high-pressure pump and a gas distributor (8) at the bottom. The method includes steps of adding azeotrope and catalyst from the upper portion of the kettle, and gaseous carbon monoxide is fed into the kettle from the bottom of the kettle through the gas distributor (8). The internal pressure of the kettle is 3.0-4.5MPa, and the reaction temperature is 140-220 GEG C. The catalyst includes rhodium catalyst, catalysis-supporting methyl iodide and lithium acetate, the rhodium catalyst with the concentration ranging from 200ppm to 800ppm is selected from rhodium triiodide or rhodium chloride, adding quantity of the methyl iodide is 10-30% of that of the azeotrope, and the concentration of the lithium acetate is two to three times of that of the rhodium catalyst. Reaction liquid sequentially passes through a flash evaporation kettle (2), a light component removing tower (3), an acetic acid tower (4) and an acetic anhydride tower (5) to obtain acetic anhydride with purity higher than 97% and acetic acid with purity higher than 99%. The method effectively resolves the problem of comprehensive utilization of methyl acetate and methanol azeotrope.
Description
One, technical field
The present invention relates to the preparation method of a kind of basic Organic Chemicals aceticanhydride, acetic acid, be to use exactly that by-product methyl acetate and methanol azeotrope are raw material in the polyvinyl alcohol production, oxo process generates aceticanhydride, acetic acid and separation method synchronously.
Two, background technology
It is the ketenes method of raw material that the traditional preparation process method of aceticanhydride has with acetic acid, be the oxidation style etc. of raw material with acetaldehyde, ritalin and CO direct oxo synthesis under rhodium catalyst is arranged in recent years.The traditional preparation process method of acetic acid has acetaldehyde oxidation, butane liquid phase oxidation, methyl alcohol high pressure oxo synthesis and low-pressure methanol oxo synthesis etc.
Polyvinyl alcohol is to be prepared by polyvinyl acetate resin (in methanol solvate, concentration about 50%) and caustic soda reaction (be saponification reaction, be commonly called as alcoholysis reaction).Generate a large amount of ritalins in the reaction process, and same methyl alcohol, sodium-acetate etc. are present in the saponification mother liquor.The saponification mother liquor steams ritalin and methanol azeotrope through azeotropic distillation column.Produce one ton of polyvinyl alcohol and want 1.5 tons of ritalins of by-product and methanol azeotrope, ritalin and methanol azeotrope can not be used among the polyvinyl alcohol production, and separating difficulty is big, need be hydrolyzed into acetic acid and methyl alcohol, after separating again, purifying could for the production of in, this will consume a large amount of steam, discharges a large amount of waste water simultaneously.
Three, summary of the invention
The present invention is intended to the new purposes for the by-product ritalin in the polyvinyl alcohol production and methanol azeotrope (being called for short an azeotrope down) comprehensive utilization of searching, technical problem to be solved is to be raw material with this azeotrope, generates aceticanhydride synchronously with acetic acid and realizes separating by oxo process.
By analysis, the content 75-92% of ritalin in the azeotrope, methanol content is 8-25%.
Azeotrope and the CO carbongl group synthesis reaction under catalyst action has following chemical formula:
Azeotrope and CO oxo-acetic anhydride and acetic acid are to finish in the oxo process still that band stirs, azeotrope and catalyzer add from still top, CO gas adds by gas distributor from the still bottom, temperature of reaction 140-220 ℃, still internal pressure 3.0-4.5MPa, described catalyzer comprises rhodium catalyst and promotor methyl iodide and Lithium Acetate, and described rhodium catalyst is selected from rhodium triiodid (RhI
3) or Trichlororhodium (RhCl
3), rhodium catalyst concentration 200-800ppm, methyl iodide (CH
3I) add-on is the 10-30% of azeotrope quality, and the concentration of Lithium Acetate is 2-3 times of rhodium catalyst concentration.
The preferred 160-200 of temperature of reaction ℃.
The preferred 3.2-4.2MPa of still internal pressure.
The preferred 300-700ppm of rhodium catalyst concentration, the methyl iodide add-on is 20% of azeotrope quality, the 2-3 of rhodium catalyst concentration is doubly during Lithium Acetate concentration.
Carbongl group synthesis reaction is thermopositive reaction, for keeping the temperature and pressure of setting in the still, at the bypass circuit device of still one side setting by high-pressure pump control, reaction mixture is shifted out outside the still, returns in the still after the process interchanger is removed the part heat again.
Described gas distributor places the bottom of still, and its effect is that CO gas is evenly fed in the azeotrope or in the reaction mixture on the still cross-wise direction.Gas distributor is the pipe of a circle, be communicated with the CO inlet pipe, circumference in the side that makes progress has equally distributed through hole for the effusion of CO gas, is also having several through holes on the circumference of next side, is trapped in the pipe to prevent azeotrope or reaction mixture.
Described aceticanhydride, acetic acid separated flow process are as follows: at first reaction mixture is pressed into flash distillation still 2 from the middle part of oxo process still 1, realize that aceticanhydride, acetic acid separate with the mother liquor that contains catalyzer with unreacted ritalin, methyl alcohol and CO, mother liquor returns synthesis reactor 1, and aceticanhydride, acetic acid, ritalin, methyl alcohol and CO enter lightness-removing column 3 from the top of flash distillation still 2; Realize lower boiling ritalin, methyl alcohol and CO and high boiling aceticanhydride, acetic acid separated in lightness-removing column 3, lower boiling light constituent returns synthesis reactor 1 from cat head, and aceticanhydride, acetic acid are sent into acetic acid tower 4 at the bottom of tower; Realize separating of aceticanhydride and acetic acid that in acetic acid tower 4 acetic acid directly reclaims after condensation from cat head, aceticanhydride is sent into aceticanhydride tower 5 at the bottom of tower; Realize separating of aceticanhydride and tar in aceticanhydride tower 5, aceticanhydride directly reclaims after condensation from cat head, and tar is sent into vaporizer 6 at the bottom of tower, further reclaim residual aceticanhydride in the tar vaporizer 6 in, tar discharging back burning.
The operational condition of flash distillation still 2: reaction mixture enters flash distillation still 2, flash conditions after variable valve 7 is down to 0.3-0.4MPa with pressure: pressure 0.1～0.35Mpa, 140～160 ℃ of temperature.
The operational condition of lightness-removing column 3: pressure 0.08-0.1MPa, temperature 125-135 ℃, tower top temperature 80-110 ℃.
The operational condition of acetic acid tower 4: pressure 0.03-0.08MPa, temperature 120-125 ℃, tower top temperature 100-120 ℃.
The operational condition of aceticanhydride tower 5: pressure 0.08-0.1MPa, temperature 140-145 ℃, tower top temperature 140-142 ℃.
Present method uses ritalin and methanol azeotrope to be raw material, adopts oxo synthesis synthetic aceticanhydride and acetic acid synchronously, produces product innovation; prolong and produced the industry chain, than traditional azeotrope treatment process, save a large amount of energy; reduce the discharging of pollutent, the protection environment.Solved the problem of complex utilization of ritalin and methanol azeotrope effectively.This technical process is short, the efficient height.The aceticanhydride of producing and the purity of acetic acid reach respectively more than 97% and 99%, can directly use as industrial raw material.
Four, description of drawings
Figure 1 shows that this process flow sheet synthetic and separation method, the oxo process still that 1 band stirs among the figure, 2 flash distillation stills, 3 lightness-removing columns, 4 acetic acid towers, 5 aceticanhydride towers, 6 vaporizers, 7 variable valve, 8 gas distributors, P pump, E interchanger.
Fig. 2 is the structural representation of lightness-removing column 3.
Five, embodiment
By reference to the accompanying drawings, specific implementation process is described below:
(1) preparation of rhodium catalyst
With RhI
3Or RhCl
3Put into the preparation still, add acetic acid (HAc), Rh concentration is controlled at 1000～2000ppm, feeds CO again, and the still internal pressure is controlled at 0.35MPa, and stir and be warming up to 120 ℃, insulation, pressurize was squeezed in the synthesis reactor with pump after 8 hours.
(2) oxo-acetic anhydride, acetic acid
1, the top of azeotrope from oxo process still 1 added, open stirring, add rhodium catalyst solution, add methyl iodide and Lithium Acetate simultaneously, heat up, boost, feed CO gas from the still bottom through gas distributor 8 simultaneously, the feeding amount is 5～30% (v/w) of load responsive fluid.After the reaction beginning, open the bypass circuit device by high-pressure pump control, 170-190 ℃ of temperature in the kettle of control, pressure 3.2-4.2MPa, rhodium catalyst concentration 400-600ppm, methyl iodide are 20% of azeotrope quality, and Lithium Acetate concentration is 2.5 times of rhodium catalyst concentration.React and begin half an hour to separate.Contain aceticanhydride, acetic acid and still unreacted ritalin, methyl alcohol and CO and active phodium catalyst, methyl iodide and Lithium Acetate in the reaction mixture.
(3) separation of aceticanhydride, acetic acid
2, reaction mixture is pressed into flash distillation still 2 and realizes that aceticanhydride, acetic acid, ritalin, methyl alcohol separate still internal pressure 0.1-0.35MPa, 140～160 ℃ of temperature in the kettle with the mother liquor that contains catalyzer with CO after variable valve 7 step-downs from the middle part of synthesis reactor 1.Mother liquor returns synthesis reactor 1 at the bottom of still.
3, aceticanhydride, acetic acid, ritalin, methyl alcohol and CO draw from the top of flash distillation still 2 and enter lightness-removing column 3 realization aceticanhydrides, acetic acid separates with ritalin, methyl alcohol and CO's, lightness-removing column 3 is iris type distillation towers, as shown in Figure 2, tower internal pressure 0.08-0.1Mpa, temperature 125-135 ℃, head temperature 80-110 ℃, ritalin, methyl alcohol and CO return synthesis reactor 1 from cat head.
4, aceticanhydride, acetic acid pump into acetic acid tower 4 and realize separating of aceticanhydride and acetic acid after heat exchange from lightness-removing column 3 bottoms, acetic acid tower 4 is general distillation towers, tower internal pressure 0.03-0.08MPa, temperature 120-125 ℃, head temperature 100-120 ℃, acetic acid is drawn the back condensation and is reclaimed from the top.
5, aceticanhydride pumps into the tar separation that aceticanhydride tower 5 is realized aceticanhydride and by-product from acetic acid tower 4 bottoms, aceticanhydride tower 5 also is general distillation tower, tower internal pressure 0.08-0.1MPa, interior temperature 140-145 ℃ of tower, tower top temperature 140-142 ℃, aceticanhydride is drawn the back condensation and is reclaimed from the top.
6, tar pumps into vaporizer 6 from aceticanhydride tower 5 bottoms, evaporates down in 145 ℃ and reclaims residual aceticanhydride, and burn tar discharging back.
Claims (1)
1. a ritalin and methanol azeotrope oxo-acetic anhydride, the method of acetic acid, it is characterized in that: this building-up reactions is to stir and be provided with in the oxo process still (1) that gas distributor (8) is arranged at bypass circuit device and bottom by high-pressure pump control at band to carry out, the top of azeotrope from oxo process still (1) added, open stirring, add rhodium catalyst solution, add methyl iodide and Lithium Acetate simultaneously, heat up, boost, feed CO gas from the still bottom through gas distributor (8) simultaneously, the feeding amount is 5 ~ 30%v/w of load responsive fluid, after the reaction beginning, open the bypass circuit device by high-pressure pump control, 170-190 ℃ of control temperature in the kettle, pressure 3.2-4.2MPa, rhodium catalyst concentration 400-600ppm, methyl iodide is 20% of azeotrope quality, Lithium Acetate concentration is 2.5 times of rhodium catalyst concentration, and described azeotrope is ritalin and the carbinol mixture that the saponification mother liquor that forms in the polyvinyl alcohol production steams through azeotropic distillation column, and reaction begins to separate half an hour; Reaction mixture is pressed into flash distillation still (2) and realizes that aceticanhydride, acetic acid, ritalin, methyl alcohol separate with the mother liquor that contains catalyzer with CO after variable valve (7) step-down from the middle part of synthesis reactor (1), still internal pressure 0.1-0.35MPa, 140 ~ 160 ℃ of temperature in the kettle, mother liquor return synthesis reactor (1) at the bottom of still; Aceticanhydride, acetic acid, ritalin, methyl alcohol and CO draw from the top of flash distillation still (2) and enter lightness-removing column (3) realization aceticanhydride, acetic acid separates with ritalin, methyl alcohol and CO's, lightness-removing column (3) is the iris type distillation tower, tower internal pressure 0.08-0.1MPa, temperature 125-135 ℃, head temperature 80-110 ℃, ritalin, methyl alcohol and CO return synthesis reactor (1) from cat head; Aceticanhydride, acetic acid pump into acetic acid tower (4) from lightness-removing column (3) bottom and realize separating of aceticanhydride and acetic acid after heat exchange, acetic acid tower (4) is general distillation tower, tower internal pressure 0.03-0.08MPa, temperature 120-125 ℃, head temperature 100-120 ℃, acetic acid is drawn the back condensation and is reclaimed from the top; Aceticanhydride pumps into the tar separation that aceticanhydride tower (5) is realized aceticanhydride and by-product from acetic acid tower (4) bottom, aceticanhydride tower (5) also is general distillation tower, tower internal pressure 0.08-0.1MPa, interior temperature 140-145 ℃ of tower, tower top temperature 140-142 ℃, aceticanhydride is drawn the back condensation and is reclaimed from the top; Tar pumps into vaporizer (6) from aceticanhydride tower (5) bottom, evaporates down in 145 ℃ and reclaims residual aceticanhydride, and burn tar discharging back; Described rhodium catalyst is with RhI
3Or RhCl
3Put into the preparation still, add acetic acid, Rh concentration is controlled at 1000 ~ 2000ppm, feeds CO again, and the still internal pressure is controlled at 0.35MPa, and stir and be warming up to 120 ℃, insulation, pressurize was squeezed in the synthesis reactor (1) with pump after 8 hours.
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| CN 201110262745 CN102381956B (en) | 2011-09-06 | 2011-09-06 | Method for preparation of acetic anhydride and acetic acid by means of carbonyl synthesis of methyl acetate and methanol azeotrope and method for separation |
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| CN105085132A (en) * | 2014-05-08 | 2015-11-25 | 中国石油化工股份有限公司 | Method and device for optimizing ethylene oligomerization technology |
| CN104689854B (en) * | 2015-01-07 | 2017-05-24 | 江苏索普（集团）有限公司 | Catalyst system for synthesizing acetic acid through methanol carbonylation and application of catalyst system |
| CN108518362B (en) * | 2018-03-28 | 2019-11-29 | 兖矿鲁南化工有限公司 | A kind of system and method for the pump generation cavitation preventing conveying high temperature, low boiling point working medium |
| CN109627158B (en) * | 2018-12-11 | 2021-08-13 | 中国化学工程第六建设有限公司 | Acetic anhydride joint production and separation method |
| CN110845329B (en) * | 2019-10-23 | 2022-09-20 | 中石化南京工程有限公司 | Method for synthesizing acetic anhydride and co-producing propionic acid through carbonylation |
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