CN107141213A - A kind of method of acetic acid synthesis from methanol carbonylation - Google Patents
A kind of method of acetic acid synthesis from methanol carbonylation Download PDFInfo
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- CN107141213A CN107141213A CN201710373084.7A CN201710373084A CN107141213A CN 107141213 A CN107141213 A CN 107141213A CN 201710373084 A CN201710373084 A CN 201710373084A CN 107141213 A CN107141213 A CN 107141213A
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- C07—ORGANIC CHEMISTRY
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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Abstract
The invention discloses a kind of method of acetic acid synthesis from methanol carbonylation, including, first methanol and CO are passed through in reactor and carry out carbonylation, the feeding flash column of the mixture containing acetic acid for reacting generation is flashed, isolated liquid phase component and gaseous component, gaseous component return to the reactor；Then the liquid phase component is sent into progress rectifying separation in rectifying column in the way of middle part is fed, and the position of 3 20 blocks of plates produces de- iodine gas phase above the feedboard of the rectifying column, finally, the de- iodine gas phase, which is sent into the way of middle part is fed in absorption tower, carries out de- iodine.Its technological process is simple, contains iodine compound by the way that rectifying column removing is most of, then removes remaining iodine substance by absorption tower, saves investment, improves de- iodine effect, reduce the usage amount of KOH and methanol.
Description
Technical field
The invention belongs to chemosynthesis technical field, and in particular to a kind of method of acetic acid synthesis from methanol carbonylation.
Background technology
Acetic acid is one of important Organic Chemicals, mainly for the production of vinyl acetate, aceticanhydride, cellulose acetate, vinegar
Esters of gallic acid, terephthalic acid (TPA), monoxone etc., can be widely used for the fields such as chemical industry, light industry, weaving, medicine, printing and dyeing.Production at present
The main method of acetic acid has acetaldehyde oxidation, alkene direct oxidation method and methanol carbonylation.Wherein, methanol carbonylation has
The advantages of methanol conversion is high, accessory substance is small, is increasingly becoming one of main method of production acetic acid.
In the prior art, the reaction that methanol carbonyl metaplasia production acetic acid is carried out is the acetic acid product using CO and methanol as raw material
Make solvent, noble metal Ir-Ru or Rh are major catalyst, and addition methyl acetate, iodomethane, lithium iodide and water composition homogeneous catalysis are anti-
Answer system.The step of methanol carbonyl metaplasia production acetic acid is carried out generally comprises, with homogeneous catalyst in methanol and CO feeding reactors
Solution is contacted, and the mixture of gained after contact is sent into flash column.The gas phase containing acetic acid is separated the mixture into by flash distillation
Component and the liquid phase component containing major catalyst, wherein the gaseous component containing acetic acid, which is admitted in light component rectifying column, carries out rectifying point
Acetate products are separated out, the liquid phase component containing catalyst is recycled back into reactor.
For example, Chinese patent literature CN104250208A discloses a kind of production method of Production of Acetic Acid by Methanol Carbonylation, should
Gas phase portion at the top of reactor is directly sent into flash column by method, is flashed after obtained gaseous component elder generation through light, heavy constituent essence
Evaporate isolated product acetic acid.The process employs two rectifying columns, removing light component and heavy constituent are respectively intended to, wherein being used for
Its size of the rectifying column of removing heavy constituent is far longer than lightness-removing column, and the reboiler and condenser of rectifying tower configuration are taken off again in addition, from
And make it that the energy consumption in the overall investment cost height and production process of enterprise is also of a relatively high.In addition, methanol carbonylation
The presence that iodine is also had in iodomethane, lithium iodide and its catalyst used is added with homogeneous catalytic reaction system, so that
Inevitably contain iodine impurity in the product acetic acid that must be obtained, and when producing downstream product using acetic acid as raw material, iodate
Thing often results in many catalyst poisoning inactivations, thus the control of iodine is necessary again, in summary, is entered from the source of acetic synthesis
Row control, while enterprise's production cost is reduced, can effectively control the content of iodine in the acetate products of synthesis, for improving again
The economic benefit of enterprise has far-reaching influence.
Due to acetic acid hydrogenation can measure than production water, dewatering unit be subsequently must through process, and hydrogenation after for carry out
Purifying ethanol, also needs additionally to add water as extractant, thus acetic acid as hydrogenation be prepared as ethanol raw material when, containing a certain amount of
Water is smaller for follow-up hydrogenation energy consumption, but can significantly save the energy consumption of methanol acetic acid workshop section.
The content of the invention
Therefore, the technical problem to be solved in the present invention is to overcome the vinegar produced in the prior art for being hydrogenated with production ethanol
Sour process units investment is big, the defect of high energy consumption, so as to propose that one kind can either meet hydrogenation production ethanol demand, device is made again
The scheme that investment, energy consumption are greatly reduced so that the acetic acid fuel economy for meeting hydrogenation production ethanol is more obvious.
Therefore, the technical scheme that the application takes is,
The invention provides a kind of method of acetic acid synthesis from methanol carbonylation, including,
(1) in the presence of a catalyst, methanol and CO are passed through in reactor and carry out carbonylation, containing for generation will be reacted
The mixture feeding flash column for having acetic acid is flashed, and isolated liquid phase component and gaseous component, gaseous component return described
Reactor；
(2) liquid phase component isolated in step (1) is sent into the way of middle part is fed and rectifying is carried out in rectifying column
Separation, respectively obtains overhead fraction, tower bottom distillate and de- iodine gas phase, wherein feedboard of the de- iodine gas phase by the rectifying column
The position extraction of top 3-20 block plates, the rectifying column tower top temperature is 100-130 DEG C；
(3) the de- iodine gas phase in step (2) is sent into the way of middle part is fed in absorption tower and carries out de- iodine, obtain acetic acid
Product and tower reactor liquid phase ingredient, acetate products are by the overhead extraction on the absorption tower, and tower reactor liquid phase ingredient returns to rectifying column and carry
Section is evaporated, wherein the KOH aqueous solution is added at the absorption tower tower top 2-5 block towers is used as de- iodine absorbing liquid.
Preferably, in the method for above-mentioned acetic acid synthesis from methanol carbonylation, in the step (2), the de- iodine gas phase is adopted
Go out temperature for 100-140 DEG C.
Preferably, in the method for above-mentioned acetic acid synthesis from methanol carbonylation, in the step (2), the rectifying tower bottom
Temperature is that the pressure in 140-165 DEG C, tower is 0.05-0.4MPa.
Preferably, in the method for above-mentioned acetic acid synthesis from methanol carbonylation, in the step (1), the temperature of carbonylation
For 170-190 DEG C, pressure 2.0-3.5MPa；The condition of flash distillation is 50-160 DEG C of temperature, pressure 0.1-1.5MPa.
Preferably, in the method for above-mentioned acetic acid synthesis from methanol carbonylation, in the step (2), in addition to by overhead fraction
The step of reactor being returned to tower bottom distillate.
Preferably, in the method for above-mentioned acetic acid synthesis from methanol carbonylation, in the step (3), in addition to it is described absorb
The step of methanol is as de- iodine absorbing liquid is added in tower, the mouth that adds of wherein methanol is located under KOH aqueous solution addition mouth
The top of square and described absorption tower charging aperture.
Preferably, in the method for above-mentioned acetic acid synthesis from methanol carbonylation, in the step (3), the KOH of addition is water-soluble
The mass ratio of methanol of the liquid with adding is (10-40):(60-90).
Preferably, in the method for above-mentioned acetic acid synthesis from methanol carbonylation, in the step (3), the matter of the KOH aqueous solution
Amount concentration is 1-50wt%.
Preferably, in the method for above-mentioned acetic acid synthesis from methanol carbonylation, in the step (3), institute in the KOH aqueous solution
It is (80-120) that KOH amount, which is stated, with the mol ratio of content of iodine in the de- iodine gas phase:100.
Preferably, in the method for above-mentioned acetic acid synthesis from methanol carbonylation, in the step (3), absorbing tower pressure is 0.05-
0.4MPa, tower top temperature is 100-130 DEG C, and bottom temperature is 102-138 DEG C.
Preferably, in the method for above-mentioned acetic acid synthesis from methanol carbonylation, in the step (2), overhead fraction is returned into institute
State and condensed before reactor, condensation temperature is 40-55 DEG C.
Preferably, in the method for above-mentioned acetic acid synthesis from methanol carbonylation, in the step (2), in addition to from rectifying column again
The step of boiling device bottom discharge reboiler residue.
The solvent and catalyst and methanol of carbonylation use and rubbing for CO are carried out in the present invention, in the step (1)
You can be selected than there is no particular limitation according to the production method of Production of Acetic Acid by Methanol Carbonylation conventional in the art
Select, can also be selected according to the requirement of the target product of acquisition.Carry out in carbonylation processes, can adjust both
Inventory, so that the stable working condition of each device processing.
Carbonylation will be carried out in methanol and CO feeding reactors, the wherein liquid phase of reactor bottom is sent from reactor bottom
Enter the gas phase at the top of flash column, reactor after pressure regulation, the liquid phase for being incorporated to reactor bottom is sent into flash column and flashed together,
Flash conditions are controlled, to obtain required liquid phase component and gaseous component, obtained gaseous component is flashed and returns to reactor, preferably
Returned after direct weighting, or liquid phase returns to reactor after deep cooling is condensed, gas phase point two parts a, part speeds to put to absorption
Tower, reactor, -20~15 DEG C of described deep cooling condensation temperature are returned after remainder pressurization.
The gaseous component includes but is not limited to CH3I, CO etc., flashes obtained liquid phase component and is sent into from the bottom of flash column
Rectifying separation is carried out in rectifying column, the liquid phase component includes but is not limited to water, acetic acid, CH3I, HI etc..
In the step (2), flash obtained liquid phase component and progress essence in rectifying column is sent into the way of middle part is fed
Cut from, respectively obtain overhead fraction, tower bottom distillate and de- iodine gas phase, overhead fraction include but is not limited to water, methyl acetate and
CH3I etc., it is preferred that reactor is returned again to after can the overhead fraction be condensed, the condenser fixed gas of generation is after processing
Outer row, tower bottom distillate includes but is not limited to acetic acid and a small amount of water, includes from the reboiler residue of rectifying column reboiler bottom discharge
But liquid phase high-boiling components and salt are not limited to, its reboiler residue regular discharge.Reflux ratio does not have during above-mentioned distillation operation
It is special to limit, it is preferable that the application control is 0.5-5.
In the step (3), de- iodine gas phase, which is sent into the way of middle part is fed in absorption tower, carries out de- iodine, obtains acetic acid
Product and tower reactor liquid phase ingredient, acetate products are by the overhead extraction on the absorption tower, and tower reactor liquid phase ingredient returns to rectifying column and carry
Section is evaporated, the tower reactor liquid phase ingredient includes but is not limited to acetic acid, water and KI.
Technical solution of the present invention, has the following advantages that：
1. the present invention provide it is a kind of be used for produce can direct hydrogenation thick acetic acid raw material method, simplify technological process,
Taken off by the way that the reactant in reactor is sent directly into flash column, and the liquid phase in flash column is sent directly into rectifying column
Light processing, is iodinated by controlling the tower top temperature of rectifying column and in specific position extraction gas phase take off, that is, passes through rectifying
Tower removing is most of to contain iodine compound, then removes remaining iodine substance by absorption tower, saves investment, reduce KOH with
The usage amount of methanol.
2. the method for the acetic acid synthesis from methanol carbonylation that the present invention is provided, using rectifying column plus the structure on absorption tower, this Shen
Please in absorption tower for absorbing reaction tower be not rectifying column, therefore and reboiler and condenser need not be configured so that more former system
The cost of investment reduction by 50% of standby essence acetic acid, energy consumption reduction by 40%, so that more obvious from methanol ethanol economy.
3. the method for the acetic acid synthesis from methanol carbonylation that the present invention is provided, thick production of acetic acid energy consumption is low, and is totally used for first
Alcohol is prepared for ethanol overall process, in the case of based on same acetic acid hydrogenation technique, is hydrogenated with relative to refined acetic acid, under energy consumption
Depreciation reaches that 60-90kg marks oil/ton alcohol product.
Brief description of the drawings
, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical scheme of the prior art
The accompanying drawing used required in embodiment or description of the prior art is briefly described, it should be apparent that, in describing below
Accompanying drawing is some embodiments of the present invention, for those of ordinary skill in the art, before creative work is not paid
Put, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is the technological process of a specific example of the method for acetic acid synthesis from methanol carbonylation in the embodiment of the present invention 1
Figure；
Embodiment
Carbonylation in the application is the ordinary skill in the art, and its raw material dosage, reaction condition is this area
Conventional selection, preferably 170-190 DEG C of reaction temperature, pressure 2.0-3.5MPa, for ease of contrast, carbonyl in following embodiments
Change reaction to carry out by general condition, methanol and CO mol ratio are 1:1.1, the temperature of carbonylation is 190 DEG C, reaction pressure
For 3.0MPa, catalyst can be any carbonylating catalyst, the described low water catalyst as disclosed in CN102294265B.
For ease of comparing, the catalyst that the following embodiments of the application are prepared using embodiment 1 in CN102294265B.
Embodiment 1
As shown in figure 1, the technological process of the alcohol carbonylation acetic acid of the present embodiment is,
(1) in the presence of a catalyst, methanol and CO are passed through in reactor and carry out carbonylation, containing for generation will be reacted
The mixture feeding flash column for having acetic acid is flashed, and the temperature of flash distillation is 140 DEG C in flash column, and the pressure of flash distillation is
1.2MPa, flash distillation obtains liquid phase component and gaseous component, and gas phase group returns to the reactor, liquid phase component bag comprising CH3I and CO
Aqueous, sour, CH3I and HI enter next step.
(2) liquid phase component isolated in step (1) is sent into the way of middle part is fed and rectifying is carried out in rectifying column
Separation, respectively obtains overhead fraction, tower bottom distillate and de- iodine gas phase, rectifying column has 60 blocks of column plates, feedboard wherein in this step
For the 30th block of column plate of number from top to bottom, de- iodine gas phase position of the 12nd block of plate above the feedboard of the rectifying column is adopted
Go out, it is 125 DEG C that it, which produces temperature, the rectifying column tower top temperature is 110 DEG C, the temperature of bottom of towe is 150 DEG C, and the pressure in tower is
0.1MPa, reflux ratio 1.2；Overhead fraction includes water, methyl acetate and CH3I, and reactor is returned after being condensed at 40 DEG C, produces
Raw condenser fixed gas passes through deep cooling, and liquid phase returns to reaction Fu, and gas phase is discharged after washing process, and tower bottom distillate includes vinegar
Sour and a small amount of water, wherein 80% returns to reactor, 20% returns to flash column, and specific return method for example can be, in rectifying column
The liquid-phase collection disk of tower reactor arrangement above one, liquid phase is produced from described liquid-phase collection disk, adopts and described sudden strain of a muscle is returned after pumping up
Steam tower and reaction Fu.Also include process periodically from rectifying column reboiler bottom discharge liquid phase high-boiling components and salt.
(3) the de- iodine gas phase in step (2) is sent into the way of middle part is fed in absorption tower and carries out de- iodine, obtain acetic acid
Product and tower reactor liquid phase ingredient, acetate products are by the overhead extraction on the absorption tower, and tower reactor liquid phase ingredient returns to rectifying column and carry
Section is evaporated, absorption tower is that plate column has 40 blocks of column plates wherein in this step, and feedboard is the 20th block of column plate of number from top to bottom, is absorbed
Tower tower pressure is 0.3MPa, and tower top temperature is 110 DEG C, and bottom temperature is 125 DEG C, wherein adding at described 2 blocks of plates of absorption tower tower top
Enter the KOH aqueous solution as de- iodine absorbing liquid, the mass concentration of the KOH aqueous solution is 25wt%, described in the KOH aqueous solution
The mol ratio of content of iodine is 80 in KOH amount and the de- iodine gas phase:100, it is additionally added at described 10 blocks of plates of absorption tower tower top
Methanol is as the second de- iodine absorbing liquid, and the mass ratio of methanol of the KOH aqueous solution of addition with adding is 10:60.
In the present embodiment the acetometer that hydrogenation produces ethanol, 0.10kg/ tons of vinegar of KOH consumptions are can be directly used for produce one ton
Acid, equipment investment cost reduction by 30%, the content of iodine in acetate products is 2ppm after measured.
Embodiment 2
As shown in figure 1, the technological process of the alcohol carbonylation acetic acid of the present embodiment is,
(1) in the presence of a catalyst, methanol and CO are passed through in reactor and carry out carbonylation, containing for generation will be reacted
The mixture feeding flash column for having acetic acid is flashed, and the temperature of flash distillation is 160 DEG C in flash column, and the pressure of flash distillation is
0.5MPa, flash distillation obtains liquid phase component and gaseous component, and gas phase group returns to the reactor, liquid phase component bag comprising CH3I and CO
Aqueous, sour, CH3I and HI enter next step.
(2) liquid phase component isolated in step (1) is sent into the way of middle part is fed and rectifying is carried out in rectifying column
Separation, respectively obtains overhead fraction, tower bottom distillate and de- iodine gas phase, rectifying column has 80 blocks of column plates, feedboard wherein in this step
For the 40th block of column plate of number from top to bottom, de- iodine gas phase position of the 20th block of plate above the feedboard of the rectifying column is adopted
Go out, it is 140 DEG C that it, which produces temperature, the rectifying column tower top temperature is 130 DEG C, the temperature of bottom of towe is 165 DEG C, and the pressure in tower is
0.3MPa, reflux ratio 2；Overhead fraction includes water, methyl acetate and CH3I, and reactor is returned after being condensed at 40 DEG C, produces
Condenser fixed gas pass through deep cooling, liquid phase returns to reaction Fu, and gas phase discharge after washing process, and tower bottom distillate includes acetic acid
With a small amount of water, wherein 60% returns to reactor, 40% returns to flash column, in addition to periodically from rectifying column reboiler bottom discharge liquid
The process of phase high-boiling components and salt.
(3) the de- iodine gas phase in step (2) is sent into the way of middle part is fed in absorption tower and carries out de- iodine, obtain acetic acid
Product and tower reactor liquid phase ingredient, acetate products are by the overhead extraction on the absorption tower, and tower reactor liquid phase ingredient returns to rectifying column and carry
Section is evaporated, absorption tower is that plate column has 30 blocks of column plates wherein in this step, and feedboard is the 15th block of column plate of number from top to bottom, is absorbed
Tower tower pressure is 0.4MPa, and tower top temperature is 100 DEG C, and bottom temperature is 102 DEG C, wherein adding at described 5 blocks of plates of absorption tower tower top
Enter the KOH aqueous solution as de- iodine absorbing liquid, the mass concentration of the KOH aqueous solution is 50wt%, described in the KOH aqueous solution
The mol ratio of content of iodine is 120 in KOH amount and the de- iodine gas phase:100, it is additionally added at described 8 blocks of plates of absorption tower tower top
Methanol is as the second de- iodine absorbing liquid, and the mass ratio of methanol of the KOH aqueous solution of addition with adding is 40:90.
In the present embodiment the acetometer that hydrogenation produces ethanol, 0.15kg/ tons of vinegar of KOH consumptions are can be directly used for produce one ton
Acid, equipment investment cost reduction by 35%, the content of iodine in acetate products is 3ppm after measured.
Embodiment 3
As shown in figure 1, the technological process of the alcohol carbonylation acetic acid of the present embodiment is,
(1) in the presence of a catalyst, methanol and CO are passed through in reactor and carry out carbonylation, containing for generation will be reacted
The mixture feeding flash column for having acetic acid is flashed, and the temperature of flash distillation is 100 DEG C in flash column, and the pressure of flash distillation is
1.5MPa, flash distillation obtains liquid phase component and gaseous component, and gas phase group returns to the reactor, liquid phase component bag comprising CH3I and CO
Aqueous, sour, CH3I and HI enter next step.
(2) liquid phase component isolated in step (1) is sent into the way of middle part is fed and rectifying is carried out in rectifying column
Separation, respectively obtains overhead fraction, tower bottom distillate and de- iodine gas phase, rectifying column has 60 blocks of column plates, feedboard wherein in this step
For the 30th block of column plate of number from top to bottom, the position of the de- iodine gas phase the 3rd block of plate above the feedboard of the rectifying column is produced,
It is 100 DEG C that it, which produces temperature, and the rectifying column tower top temperature is 100 DEG C, and the temperature of bottom of towe is 140 DEG C, and the pressure in tower is
0.4MPa, reflux ratio 3；Overhead fraction includes water, methyl acetate and CH3I, and reactor is returned after being condensed at 40 DEG C, produces
Condenser fixed gas pass through deep cooling, liquid phase returns to reaction Fu, and gas phase discharge after washing process, and tower bottom distillate includes acetic acid
Reactor is all returned with a small amount of water.Also include mistake periodically from rectifying column reboiler bottom discharge liquid phase high-boiling components and salt
Journey.
(3) the de- iodine gas phase in step (2) is sent into the way of middle part is fed in absorption tower and carries out de- iodine, obtain acetic acid
Product and tower reactor liquid phase ingredient, acetate products are by the overhead extraction on the absorption tower, and tower reactor liquid phase ingredient returns to rectifying column and carry
Section is evaporated, absorption tower is that plate column has 50 blocks of column plates wherein in this step, and feedboard is the 25th block of column plate of number from top to bottom, is absorbed
Tower tower pressure is 0.1MPa, and tower top temperature is 130 DEG C, and bottom temperature is 138 DEG C, wherein adding at described 4 blocks of plates of absorption tower tower top
Enter the KOH aqueous solution as de- iodine absorbing liquid, the mass concentration of the KOH aqueous solution is 30wt%, described in the KOH aqueous solution
The mol ratio of content of iodine is 1 in KOH amount and the de- iodine gas phase:1, it is additionally added methanol at described 10 blocks of plates of absorption tower tower top
As the second de- iodine absorbing liquid, the mass ratio of methanol of the KOH aqueous solution of addition with adding is 30:70.
In the present embodiment the acetometer that hydrogenation produces ethanol, 0.13kg/ tons of vinegar of KOH consumptions are can be directly used for produce one ton
Acid, equipment investment cost reduction by 40%, the content of iodine in acetate products is 2ppm after measured.
Embodiment 4
As shown in figure 1, the technological process of the alcohol carbonylation acetic acid of the present embodiment is,
(1) in the presence of a catalyst, methanol and CO are passed through in reactor and carry out carbonylation, containing for generation will be reacted
The mixture feeding flash column for having acetic acid is flashed, and the temperature of flash distillation is 80 DEG C in flash column, and the pressure of flash distillation is 1.5MPa,
Flash distillation obtains liquid phase component and gaseous component, and gas phase group returns to the reactor comprising CH3I and CO, liquid phase component comprising water,
Acid, CH3I and HI enter next step.
(2) liquid phase component isolated in step (1) is sent into the way of middle part is fed and rectifying is carried out in rectifying column
Separation, respectively obtains overhead fraction, tower bottom distillate and de- iodine gas phase, rectifying column has 70 blocks of column plates, feedboard wherein in this step
For the 35th block of column plate of number from top to bottom, the position of the de- iodine gas phase the 8th block of plate above the feedboard of the rectifying column is produced,
It is 110 DEG C that it, which produces temperature, and the rectifying column tower top temperature is 120 DEG C, and the temperature of bottom of towe is 160 DEG C, and the pressure in tower is
0.2MPa, reflux ratio 4；Overhead fraction includes water, methyl acetate and CH3I, and reactor is returned after being condensed at 40 DEG C, produces
Condenser fixed gas pass through deep cooling, liquid phase returns to reaction Fu, and gas phase discharge after washing process, and tower bottom distillate includes acetic acid
With a small amount of water, wherein 85% returns to reactor, 15% returns to flash column, and specific return method for example can be, in rectifying tower
The liquid-phase collection disk of kettle arrangement above one, liquid phase is produced from described liquid-phase collection disk, adopts and described flash distillation is returned after pumping up
Tower and reaction Fu.Also include process periodically from rectifying column reboiler bottom discharge liquid phase high-boiling components and salt.
(3) the de- iodine gas phase in step (2) is sent into the way of middle part is fed in absorption tower and carries out de- iodine, obtain acetic acid
Product and tower reactor liquid phase ingredient, acetate products are by the overhead extraction on the absorption tower, and tower reactor liquid phase ingredient returns to rectifying column and carry
Section is evaporated, absorption tower is that plate column has 50 blocks of column plates wherein in this step, and feedboard is the 25th block of column plate of number from top to bottom, is absorbed
Tower tower pressure is 0.2MPa, and tower top temperature is 120 DEG C, and bottom temperature is 130 DEG C, wherein adding at described 3 blocks of plates of absorption tower tower top
Enter the KOH aqueous solution as de- iodine absorbing liquid, the mass concentration of the KOH aqueous solution is 10wt%, described in the KOH aqueous solution
The mol ratio of content of iodine is 1.2 in KOH amount and the de- iodine gas phase:1, it is additionally added first at described 7 blocks of plates of absorption tower tower top
Alcohol is as the second de- iodine absorbing liquid, and the mass ratio of methanol of the KOH aqueous solution of addition with adding is 10:60.
In the present embodiment the acetometer that hydrogenation produces ethanol, 0.15kg/ tons of vinegar of KOH consumptions are can be directly used for produce one ton
Acid, equipment investment cost reduction by 50%, the content of iodine in acetate products is 3ppm after measured.
Embodiment 5
As shown in figure 1, the technological process of the alcohol carbonylation acetic acid of the present embodiment is,
(1) in the presence of a catalyst, methanol and CO are passed through in reactor and carry out carbonylation, containing for generation will be reacted
The mixture feeding flash column for having acetic acid is flashed, and the temperature of flash distillation is 120 DEG C in flash column, and the pressure of flash distillation is
1.3MPa, flash distillation obtains liquid phase component and gaseous component, and gas phase group returns to the reactor, liquid phase component bag comprising CH3I and CO
Aqueous, sour, CH3I and HI enter next step.
(2) liquid phase component isolated in step (1) is sent into the way of middle part is fed and rectifying is carried out in rectifying column
Separation, respectively obtains overhead fraction, tower bottom distillate and de- iodine gas phase, rectifying column has 60 blocks of column plates, feedboard wherein in this step
For the 30th block of column plate of number from top to bottom, the position of the de- iodine gas phase the 6th block of plate above the feedboard of the rectifying column is produced,
It is 125 DEG C that it, which produces temperature, and the rectifying column tower top temperature is 105 DEG C, and the temperature of bottom of towe is 140 DEG C, and the pressure in tower is
0.2MPa, reflux ratio 4；Overhead fraction includes water, methyl acetate and CH3I, and reactor is returned after being condensed at 40 DEG C, produces
Condenser fixed gas pass through deep cooling, liquid phase returns to reaction Fu, and gas phase discharge after washing process, and tower bottom distillate includes acetic acid
With a small amount of water, wherein 90% returns to reactor, 10% returns to flash column, and specific return method for example can be, in rectifying tower
The liquid-phase collection disk of kettle arrangement above one, liquid phase is produced from described liquid-phase collection disk, adopts and described flash distillation is returned after pumping up
Tower and reaction Fu.Also include process periodically from rectifying column reboiler bottom discharge liquid phase high-boiling components and salt.
(3) the de- iodine gas phase in step (2) is sent into the way of middle part is fed in absorption tower and carries out de- iodine, obtain acetic acid
Product and tower reactor liquid phase ingredient, acetate products are by the overhead extraction on the absorption tower, and tower reactor liquid phase ingredient returns to rectifying column and carry
Section is evaporated, absorption tower is that plate column has 46 blocks of column plates wherein in this step, and feedboard is the 23rd block of column plate of number from top to bottom, is absorbed
Tower tower pressure is 0.05MPa, and tower top temperature is 110 DEG C, and bottom temperature is 125 DEG C, wherein adding at described 2 blocks of plates of absorption tower tower top
Enter the KOH aqueous solution as de- iodine absorbing liquid, the mass concentration of the KOH aqueous solution is 1wt%, described in the KOH aqueous solution
The mol ratio of content of iodine is 80 in KOH amount and the de- iodine gas phase:100, it is additionally added at described 10 blocks of plates of absorption tower tower top
Methanol is as the second de- iodine absorbing liquid, and the mass ratio of methanol of the KOH aqueous solution of addition with adding is 10:90.
In the present embodiment the acetometer that hydrogenation produces ethanol, 0.12kg/ tons of vinegar of KOH consumptions are can be directly used for produce one ton
Acid, equipment investment cost reduction by 50%, the content of iodine in acetate products is 4ppm after measured.
Comparative example 1
The method and Chinese patent literature CN104250208A embodiments 1 that this comparative example methanol carbonyl prepares acetic acid are basic
Identical, it is different that it differs only in carbonylation, all conditions of the carbonylation of this comparative example, raw material, catalyst,
Solvent, reaction condition etc. are same as Example 1.
To produce one ton of acetometer in the present embodiment, thick acetic acid (conversion is butt) energy consumption is the 105kg mark pure vinegar of oil/ton
Acid, the content of iodine in acetate products is 90ppm after measured.
Comparative example 2
The method that this comparative example methanol carbonyl prepares acetic acid is substantially the same manner as Example 1, and it is differed only in, and takes off iodine
The extraction position of gas phase is the 25th block of plate above feedboard, and it is 105 DEG C that it, which produces temperature,.Can be straight to produce one ton in the present embodiment
The acetometer for being hydrogenated with production ethanol is connect, the methanol and 25wt%KOH amount of aqueous solution used of the program increase compared with embodiment 1
35%, the content of iodine in acetate products is 8ppm after measured.
Obviously, above-described embodiment is only intended to clearly illustrate example, and the not restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (12)
1. a kind of method of acetic acid synthesis from methanol carbonylation, including,
(1) in the presence of a catalyst, methanol and CO are passed through in reactor and carry out carbonylation, reaction generation is contained into vinegar
The mixture feeding flash column of acid is flashed, and isolated liquid phase component and gaseous component, gaseous component return to the reaction
Kettle；
(2) liquid phase component isolated in step (1) is sent into progress rectifying separation in rectifying column in the way of middle part is fed,
Overhead fraction, tower bottom distillate and de- iodine gas phase are respectively obtained, wherein the de- iodine gas phase is above the feedboard of the rectifying column
The position extraction of 3-20 block plates, the rectifying column tower top temperature is 100-130 DEG C；
(3) the de- iodine gas phase in step (2) is sent into the way of middle part is fed in absorption tower and carries out de- iodine, obtain acetate products
With tower reactor liquid phase ingredient, acetate products by the absorption tower overhead extraction, tower reactor liquid phase ingredient return rectifying column stripping section,
The KOH aqueous solution is added wherein at the absorption tower tower top 2-5 block towers and is used as de- iodine absorbing liquid.
2. the method for acetic acid synthesis from methanol carbonylation according to claim 1, it is characterised in that in the step (2), institute
The extraction temperature for stating de- iodine gas phase is 100-140 DEG C.
3. the method for acetic acid synthesis from methanol carbonylation according to claim 1 or 2, it is characterised in that the step (2)
In, the temperature at the rectifying tower bottom is that the pressure in 140-165 DEG C, tower is 0.05-0.4MPa.
4. according to the method for any described acetic acid synthesis from methanol carbonylation of claim 1-3, it is characterised in that the step
(1) in, the temperature of carbonylation is 170-190 DEG C, pressure 2.0-3.5MPa；The condition of flash distillation is 50-160 DEG C of temperature, pressure
Power 0.1-1.5MPa.
5. according to the method for any described acetic acid synthesis from methanol carbonylation of claim 1-4, it is characterised in that
In the step (2), in addition to the step of overhead fraction and tower bottom distillate are returned into the reactor.
6. according to the method for any described acetic acid synthesis from methanol carbonylation of claim 1-5, it is characterised in that the step
(3) in, in addition to the step of methanol is as de- iodine absorbing liquid is added into the absorption tower, the wherein addition mouthful of methanol is located at institute
State the KOH aqueous solution and add the lower section of mouth and the top of the absorption tower charging aperture.
7. the method for acetic acid synthesis from methanol carbonylation according to claim 6, it is characterised in that in the step (3), plus
The mass ratio of methanol of the KOH aqueous solution entered with adding is (10-40):(60-90).
8. according to the method for any described acetic acid synthesis from methanol carbonylation of claim 1-7, it is characterised in that the step
(3) in, the mass concentration of the KOH aqueous solution is 1-50wt%.
9. according to the method for any described acetic acid synthesis from methanol carbonylation of claim 1-8, it is characterised in that the step
(3) in, the mol ratio of KOH amount described in the KOH aqueous solution and content of iodine in the de- iodine gas phase is (80-120):100.
10. according to the method for any described acetic acid synthesis from methanol carbonylation of claim 1-9, it is characterised in that the step
(3) in, absorbing tower pressure is 0.05-0.4MPa, and tower top temperature is 100-130 DEG C, and bottom temperature is 102-138 DEG C.
11. the method for acetic acid synthesis from methanol carbonylation according to claim 5, it is characterised in that
In the step (2), condensed before overhead fraction is returned into the reactor, condensation temperature is 40-55 DEG C.
12. according to the method for any described acetic acid synthesis from methanol carbonylation of claim 1-11, it is characterised in that the step
(2) in, in addition to from rectifying column reboiler bottom discharge reboiler residue the step of.
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| CN111762920A (en) * | 2020-07-21 | 2020-10-13 | 河南城建学院 | Method for reducing concentration of potassium ions in acetic acid waste liquid |
| CN111847716A (en) * | 2020-07-21 | 2020-10-30 | 河南城建学院 | Purification device for acetic acid waste liquid |
| WO2021047056A1 (en) * | 2019-09-12 | 2021-03-18 | 南京延长反应技术研究院有限公司 | Enhanced reaction system and process for preparing acetic acid by means of carbonylation methanol |
| CN116099455A (en) * | 2023-04-12 | 2023-05-12 | 西南化工研究设计院有限公司 | Carbonylation reaction system and method based on multi-kettle serial connection |
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