CN1865215A - Purification method for acetic acid synthesized by low pressure methanol carbonylation - Google Patents
Purification method for acetic acid synthesized by low pressure methanol carbonylation Download PDFInfo
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Abstract
This invention relates to a method for purifying methanol carbonyl synthesized acetic acid at low pressure, comprising: flash distill the reaction solution containing catalyst in the flash evaporator to produce the gas-phase crude acetic acid with impurities, produce wet acetic acid with impurities by lightness-removing column distillation, then send the wet acetic acid to the dehydration column for further dehydration and impurities removing, use the current method to further purify the dehydrated and impurities removed acetic acid to be acceptable high-grade product, wherein the gas phase is cooled at the top of the dehydration column and sent to a second distillation decanter, which separates the liquid to be a low-density phase mainly comprising of water and acetic acid and a high-density phase mainly comprising of methyliodide and methyl acetate; the gas phase is cooled at the top of the said lightness-removing column and then sent to the first distillation decanter which separates the liquid to be a low-density phase mainly comprising of water and acetic acid and a high-density phase mainly comprising of methyliodide and methyl acetate, decant the high-density phase produced by the second distillation decanter to the first distillation decanter.This method is characterized of simplified method and purification energy consumption decreasing.
Description
Technical field
The present invention relates to a kind of method of acetic acid synthesized by low pressure methanol carbonylation, this acetic acid is by methyl alcohol being carried out the carbonylation preparation in the presence of the catalyzer that contains the 8th family's metal, more specifically, the present invention relates to prepare the method for purification of high purity acetic acid, wherein in preparation process by catalytic carbonylation reaction generation acetic acid by rhodium, reduce the ritalin and the methyl iodide impurity that contain in the product, significantly reduced the needed energy consumption of purifying acetic acid simultaneously.
Background technology
Acetic acid is important chemical intermediate and chemical reaction solvent.Maximum purposes is the Vinyl Acetate Monomer (VAM) that accounts for its turnout 40%, and VAM can be in order to make protective coating, tackiness agent and plastics.Produce pure terephthalic acid (PTA) and be acetic acid second largest with fastest-rising purposes, it accounts for aggregate consumption 19%.The annual growth of acetic acid demand in 2003 is 3%, and demand reaches 692.5 ten thousand tons.Global acetic acid consumption will reach about 9,100,000 tons by 2006.By 2010, the annual growth of West Europe, the U.S. and Japanese demand was expected to be 1%～3%, and the annual growth of the Asian-Pacific area (not comprising Japan) demand is 6.6%.
With carbon monoxide and methyl alcohol is raw material, and producing acetic acid with oxo synthesis is way commonly used usually at present.The methanol carbonyl synthesis method has high-pressure process and two kinds of technology of low-pressure process.The former is high owing to investing, the energy consumption height, and oneself is replaced by the latter.Developed the production technique of acetic acid synthesized by low pressure methanol carbonylation since U.S. Monsanto Company after, the acetic acid synthesized by low pressure methanol carbonylation technology becomes the main method of producing acetic acid in the world at present.
Traditional Meng Shandou/BP technology needs a large amount of water to keep the stability and the speed of reaction of catalyzer in reactive system, because the concentration of water is up to 14%～15% in the reactor, therefore water being separated from acetic acid is the operation of high energy consumption, and has limited the throughput of device.Develop the technology of energy compensate for catalyst stability decreases, reduce the concentration of water, then can reduce process cost and investment cost significantly.
The technological process of production of known low-pressure methanol carbonyl synthesized acetic acid is seen Fig. 1 (draw from " chemical encyclopedia ", 4 editions second volumes were 719 pages in 1991).Add reactor 1 bottom with carbon monoxide, lighting end and the water-containing acetic acid that catalyzer mother liquor, refining system return that contain that return after the methyl alcohol preheating, 175 ~ 200 ℃ of temperature, under stagnation pressure 3MPa (28.5atm), the carbon monoxide pressure of tension 1～1.5MPa, reaction solution is drawn in the top of reactor 1 side line in the reaction back, flash distillation is decompressed to about 200kPa, reaction product is separated, latter's Returning reactor 1 (reactor 1 expellant gas contains carbon monoxide, methyl iodide, hydrogen, methane sends into scrubbing tower 6) with the mother liquor that contains catalyzer.The reaction mixture that contains thick acetic acid, lighting end enters first tower-lightness-removing column 2 of refining system with gas phase, deviates from lighting end, and the gas of cat head (containing methyl iodide, ritalin, small amount of methanol) enters scrubbing tower through 7 of distillation tower condensation liquid baths.The still liquid of lightness-removing column 2 is moisture thick acetic acid, is sent second tower-dehydration tower 3, the dry crude acetic acid of dehydration tower 3 bottoms to be admitted to the 3rd Ta-Tuo heavy ends column 4 again.Draw finished acid from taking off heavy ends column 4 top side lines, this tower bottoms contains propionic acid 40% and other high carboxylic acids; Taking off acetic acid in heavy ends column 4 bottom fraction, to be sent to the 4th tower at last be spent acid distillation tower 5, to recycle.Discharging the heavy spent acid at the bottom of the tower is output 0.2%, can burn or reclaim.Consist of CO 40～80% after three towers and reactor 1 expellant gas gather, all the other 20～60% are H
2, CO
2, N
2, O
2And acetic acid, the methyl iodide of trace, behind scrubbing tower 6 usefulness cold methanol washing and recycling iodine, burn emptying together.In order to guarantee that iodine content is qualified in the finished product, in dehydration tower 3, to add small amount of methanol and make HI be converted into CH
3I; Add a small amount of KOH iodide ion is shifted out at the bottom of still with the form of KI taking off heavy ends column 4 imports, can obtain containing the pure acetic acid of iodine 5～40ppb.”
In this technology, adopting the halogenide of rhodium is that catalyzer, methyl iodide are promotor, has realized methyl alcohol and carbon monoxide carbonyl synthesis acetic acid under 2.8-3.0MPa and 175-185 ℃.Because active ingredient rhodium complex [Rh (CO) in the reaction system
2I
2]
-Unstable, make and from reaction solution, to take out method based on the thick product of acetic acid, selected for use the recycle stock that is multiple times than methyl alcohol to carry out flash distillation, but its iodine consumes, the energy consumption height.
Celanese Corp. releases AO Plus method (sour optimized method) technical patent, has improved all technology of Meng Shan greatly.AO Plus technology is by adding high density inorganic iodine (mainly being lithium iodide) to improve the stability of rhodium catalyst, after adding lithium iodide and methyl iodide, water concentration is reduced to 4% ~ 5% in the reactor, but carbonylation rate still keeps high level, thereby has greatly reduced the separation costs of device.BP company released the Cativa technical patent in 1996, the Cativa process using is based on the new catalyst system of iridium, and use multiple new auxiliary agent, as rhenium, ruthenium, osmium etc., the iridium catalyst systems activity is higher than rhodium catalyst, and by product is few, and can operate under lower at water concentration (less than 5%) situation, can improve traditional methanol carbohylation process greatly, cut down productive expense, reduce development cost 50% up to 30%.In addition, because of water concentration reduces, the CO utilising efficiency improves, and steam consumption reduces.
Along with the variation that catalyzer in this reaction solution is formed, the purification of Dichlorodiphenyl Acetate also has requirement to change.The purification schemes of BP, contest road Dichlorodiphenyl Acetate has been done research, has carried out the improvement of purifying technique, and BP has explained the change that the technology that adopts single rectification zone is come catalyzer in the adaptive response liquid in patent CN93108283; And the contest road is controlled the stratified temperature of decanting vessel and add water transformation acetic acid purification schemes in material at first distillation tower in patent CN96190401.
But notice also that under study for action along with the composition of catalyzer changes: water content in catalyzer reduces on the one hand; Ritalin and methyl iodide content in catalyzer increases on the other hand.Moreover the inorganic iodine salt stabilizing agent suppresses evaporation of water in flash vaporization process, promotes the evaporation of acetic acid, ritalin and methyl iodide.The effect of two aspects makes that into the content of lightness-removing column (2) ritalin and methyl iodide obviously increases, ritalin content is at 5 ~ 6% (wt), methyl iodide content is at 35 ~ 50% (wt), make that ritalin and methyl iodide concentration improve in the inner gas phase of this tower, ritalin and methyl iodide also obviously increase in the fluid of trim the top of column, cause the head product acetic acid of extracting out from lightness-removing column (2), though moisture reduction but the amount of ritalin and methyl iodide obviously increase, caused containing ritalin in the discharging of dehydration tower (3) and the feed stream and methyl iodide increases, especially ritalin and methyl iodide content increase in the trim the top of column thing, caused this tower product to be polluted by ritalin and methyl iodide, so under the prerequisite that catalyzer changes, the technology of purification acetic acid also needs new improvement.About catalyst system changes the phenomenon that the content of the head product acetic acid ritalin cause the content of lightness-removing column (2) ritalin and methyl iodide into obviously to increase and to extract out from lightness-removing column (2) and methyl iodide obviously increases, can from the result of comparison example examples of implementation 1 of the present invention and other examples of implementation, it is evident that.
Summary of the invention
The technical problem that will solve of the present invention provides a kind of method of purification of acetic acid synthesized by low pressure methanol carbonylation, and this method has reduced the concentration of ritalin and methyl iodide impurity effectively when simplifying its purification process and reducing the purifying energy consumption.Prepare the caused shortcoming of the prior art of acetic acid to overcome continuous production equipment.
Technical problem to be solved by this invention can be achieved through the following technical solutions:
A kind of method of purification of acetic acid synthesized by low pressure methanol carbonylation, it comprises the reaction solution impure gas-phase crude acetic acid that flash distillation produces in flasher that contains catalyzer, goes out impure wet acetic acid by lightness-removing column rectifying.Then wet acetic acid is sent into dehydration tower and further deviate from water and impurity, through the acetic acid of dehydration and impurity, further purifying with existing way is qualified quality products; It is characterized in that, behind the vapor condensation of dehydration tower top, deliver to a rectifying decanting vessel for the second time, the decanting vessel of rectifying for the second time with liquid be divided into moisture and acetic acid be main low density mutually with contain methyl iodide and ritalin be the high-density led mutually; Behind the vapor condensation of described lightness-removing column top, deliver to rectifying decanting vessel for the first time, the decanting vessel of rectifying for the first time with liquid be divided into moisture and acetic acid be main low density mutually with contain methyl iodide and ritalin be the high-density led mutually; The high-density that the decanting vessel of rectifying for the second time produces imports the decanting vessel of rectifying for the first time mutually.
In method of purification of the present invention, the high-density that the decanting vessel of rectifying for the second time produces imports the flow of rectifying first time decanting vessel mutually by the control of the decanting vessel of rectifying for the second time high-density phase liquid level.
Described liquid level control can be continuous derivation, also can be intermittently to derive.
In method of purification of the present invention, add entry at rectifying second time decanting vessel and/or at rectifying first time decanting vessel.
The total amount that the described total amount that adds water equals the water yield taken away according to the water yield, product and by product that side reaction in the reactor is used deducts the water yield that raw material is brought into.
Temperature in the decanting vessel of rectifying for the second time is controlled at 10～45 ℃.Temperature in the decanting vessel of rectifying for the first time is controlled at 23～40 ℃.
For lightness-removing column, dehydration tower, can realize with any type of rectifying tower, comprise various forms of packing towers and tray column, but must guarantee its isolating theoretical stage.In general the theoretical stage of lightness-removing column is at 3 ~ 10 grades, and the theoretical stage of dehydration tower needs only rectifying tower in the requirement of these scopes at 20～30 grades, and rectifying can obtain high-quality product.The pressure of distillation operation carries out under the condition of normal pressure or pressurization, and the control of pressure is by the pressure decision of waste gas washing, and experimentation keeps system pressure in 0～200kpa (gauge pressure).
Above-mentioned method of purification can the higher-quality acetate products of output under the acting in conjunction of following catalytic machine.
It is catalyzer that this catalyzer adopts the halogenide of rhodium, ritalin, methyl iodide are promotor, inorganic salt compounded of iodine is a stablizer, this catalyst system liquid reaction medium specifically comprises: mass concentration is 0.03-0.12wt% rhodium catalyst (in a rhodium metal), 0.3-1.0wt% alkalimetal ion, 3-15wt% iodide ion, 1-4wt% ritalin, 10-21wt% methyl iodide, 0.1-0.5wt%VIIIB family and group vib metallic element, water 4-15wt%, remainder is an acetic acid.
Description of drawings
Further specify the present invention below in conjunction with the drawings and specific embodiments.
Fig. 1 is the schematic flow sheet of Monsanto method low pressure carbonylation system acetic acid.Among the figure: 1 is reactive system; 2 is lightness-removing column; 3 is dehydration tower; 4 is weight-removing column; 5 is waste acid column; 6 is air-washing system; 7 is distillation tower condensation liquid bath.
Fig. 2 is the schematic flow sheet of low pressure carbonylation system acetic acid of the present invention.Among the figure: 1 is reactive system; 2 is lightness-removing column; 3 is dehydration tower; 4 is weight-removing column; 5 is waste acid column; 6 is air-washing system; 7 is distillation tower condensation liquid bath; 8 is the decanting vessel of rectifying for the first time; 9 is the decanting vessel of rectifying for the second time; 39 is condenser; 40 is condenser.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, below in conjunction with embodiment, further set forth the present invention.
Keeping catalyzer to contain mass concentration is under 0.03 ~ 0.1wt% rhodium catalyst condition (in rhodium metal); Keep the alkalimetal ion of mass concentration at 0.3wt% ~ 0.8wt%; Keep mass concentration at the I of 8wt% ~ 15wt% ion; Keep the ritalin of mass concentration at 2wt ~ 4wt%; Keep the methyl-iodide of mass concentration at 10 ~ 21wt%; Keep water any one concentration at mass concentration 4wt% ~ 15wt%; Keep containing mass concentration at the VIIIB of 0.1 ~ 0.4wt% family and group vib metallic element; This VIIIB family element mainly comprises Fe, Ni, and this group vib element mainly comprises Cr, Mo, also can comprise other elements of this two family, and the tungsten of the iridium of VIIIB family, ruthenium, osmium and group vib for example, these elements form carbonylcomplex with CO in catalyzer; Remainder is an acetic acid.Alkalimetal ion is the mixture that has comprised potassium, lithium etc.
With the composition of above-mentioned catalyzer, in reactor, CO and methyl alcohol are under the catalyzer condition, and carbonylation reaction generates acetic acid, and reactor will contain the reaction solution derivation of catalyzer and acetic acid, carry out vacuum flashing in flasher.Become gas phase and liquid phase by flash separation, contain catalyzer in the liquid phase, be recycled reactor.The gas phase that flash distillation is produced enters lightness-removing column 2, and wet acetic acid is extracted out from the side of this tower in this tower, sends into dehydration tower 3, and main component is acetic acid and water in this wet acetic acid, and remainder also contains a spot of ritalin and methyl iodide.Be divided into two liquid phases behind the cat head vapor condensation of lightness-removing column 2 in rectifying second time decanting vessel, except the backflow of lightness-removing column 2 manipulation requires, this two-phase is all returned reactor.Send into the wet acetic acid of dehydration tower 3 and deviate from water in this tower, exsiccant acetic acid is sent into weight-removing column 4 at the bottom of the tower, and the aqueous acetic acid of cat head is condensed into Returning reactor after the liquid phase.Exsiccant acetic acid is sent into weight-removing column 4, sloughs heavy constituent such as propionic acid, the product that output is qualified.
Catalyst system of the present invention contain can stablize the Primary Catalysts rhodium stablizer, this stablizer is characterised in that the mixing solutions that can be dissolved in water and acetic acid, and enough I can be provided
-Ion, therefore, all can be dissolved in the inorganic salt compounded of iodine of acetic acid and water, all can be used as stablizer uses, what the present invention studied is multiple basic metal salt compounded of iodine blended stablizer, and preferred KI and LiI, and its principle is to require metal salt compounded of iodine solubleness in acetic acid and/or water to want big, this atoms metal amount is little, the I that provides like this
-Ion is just sufficient.Experimental results show that K
+And Li
+Concentration maintains 0.3%wt ~ 0.8wt% in containing the reaction solution of catalyzer, and the ratio of these two kinds of alkalimetal ions has solubleness decision separately, and not limited by other.
In the catalyzer of acetic acid synthesis from methanol carbonylation, add the basic metal salt compounded of iodine,, can keep containing in the catalyzer I of mass concentration at 8wt% ~ 15wt% as stablizer
-Ion can make to keep containing 0.03 ~ 0.1wt% rhodium catalyst (in rhodium metal) in the catalyzer.
The present invention obtains the I of some amount after adding stablizer
-Ionic concn can make in the catalyzer to keep: mass concentration is in the ritalin concentration of 2 ~ 4wt%; Mass concentration is in the concentrationofmethyiodide iodide of 10 ~ 21wt%; Water is in any one concentration of mass concentration 4wt% ~ 15wt%, when especially quality concentration is reduced in 4wt% ~ 8wt%; Remainder is an acetic acid.Under this condition, Primary Catalysts is still stable.
Contain mass concentration in the catalyzer at the VIIIB of 0.1 ~ 0.4wt% family and group vib metallic element; This VIIIB family element mainly comprises Fe, Ni, and this group vib element mainly comprises Cr, Mo, also can comprise other elements of this two family, and the tungsten of the iridium of VIIIB family, ruthenium, osmium and group vib for example, these elements form carbonylcomplex with CO in catalyzer.
Behind dehydration tower 3 cat head vapor condensations, be provided with the decanting vessel of rectifying for the second time 9, make this liquid that contains water, acetic acid and ritalin, methyl iodide be divided into two liquid phases.By rectifying second time decanting vessel 9 effect, upper phase be contain acetic acid and water be low density main and that contain little acetic acid methyl esters and methyl iodide mutually, lower floor's liquid be contain methyl iodide and ritalin be high-density main and that contain little acetic acid and water mutually.
The present invention imports the high-density in the dehydration tower 3 cats head rectifying for the second time decanting vessel 9 in the rectifying first time decanting vessel 8 at lightness-removing column 2 tops mutually, promote low density in the rectifying decanting vessel 8 for the first time mutually and the separating of high-density phase, reduce the time of stratified liquid, improve stratified effect.
The present invention adds water simultaneously in rectifying second time decanting vessel 9 and the decanting vessel of rectifying for the first time 8; Secondly, these two summations that add the amount of water are fixed; Again secondly, this amount that adds water total amount of equaling the water yield taken away according to the water yield, product and by product that side reaction in the reactor is used deducts the water yield that raw material is brought into; At last, the present invention in rectifying first time decanting vessel 8 and the decanting vessel of rectifying for the second time 9 add water according to reaction solution in moisture content and the flash distillation gas phase water-content adjust, can only add water at rectifying first time decanting vessel 8, also can only add water at rectifying second time decanting vessel 9, can certainly add water simultaneously in rectifying first time decanting vessel 8 and the decanting vessel of rectifying for the second time 9, this is adjustable.The water yield that the present invention adds no longer needs to deviate from from device.
The present invention controls with the material that imports the decanting vessel of rectifying for the first time 8 discharge of rectifying second time decanting vessel 9 middle-high density phases.Discharging of liquid level switch formula or liquid level stepless control discharging are adopted in control.For the second time the high-density in the rectifying decanting vessel 9 adopt mutually the switched attenuator switched-mode discharging still derive continuously with reaction solution in methyl iodide content relevant with ritalin content.
Contain ritalin and surpass 2wt%, methyl iodide greater than 10wt% in reaction solution, especially at methyl iodide during greater than 13wt%, the decanting vessel of rectifying for the second time 9 middle-high densities obviously increase mutually, and stratified phenomenon is very obvious.
The present invention also finds, when ritalin content in reaction solution is higher than certain concentration, the non-constant of layered effect of the decanting vessel of rectifying for the first time 8, the high-density phase density that is embodied in the decanting vessel of rectifying for the second time 8 descends rapidly, and experiment finds that ritalin this adverse influence when 4wt% is above is just apparent in view.Analyze reason, think that the density of ritalin is lower than water and acetic acid, ritalin solubleness in water is very little and solubleness in methyl iodide is very big, after its concentration in rectifying first time decanting vessel 8 improves, be dissolved in during layering contain a large amount of methyl iodide high-density mutually in, make the density of high-density phase reduce rapidly, and cause layered effect poor.
When methyl iodide content in reaction solution is higher than certain concentration, the layered effect of the decanting vessel of rectifying for the first time 8 improves, the high-density phase density that is embodied in the decanting vessel of rectifying for the first time 8 improves, the layered effect of the decanting vessel of rectifying for the second time 9 improves, the middle mutually methyl iodide concentration of high-density that is embodied in the decanting vessel of rectifying for the second time 9 improves, and water and acetate concentration reduce.Experiment finds that this methyl iodide is favourable when concentration is higher than 10wt% in reaction solution, and when methyl iodide when concentration is higher than 13wt% in reaction solution, this favourable effect is more obvious.
Temperature in the decanting vessel of rectifying for the first time 8 reduces wherein the phase-splitting and the layering of liquid are favourable, but when temperature is reduced to a fixed point, this effect is just not obvious, this phase-splitting and stratified effect are embodied in the variation of the decanting vessel of rectifying for the first time 8 high-density phase densities, effective, the density height, weak effect density is low.Find in the experiment that the temperature in decanting vessel is lower than 40 ℃, especially be lower than below 36 ℃ that this favourable effect is good, this favourable effect is not clearly when temperature is lower than 25 ℃.This refrigerative temperature can be obtained by the control of condenser 39.
For the second time the temperature in the rectifying decanting vessel 9 is low more is favourable to the wherein phase-splitting and the layering of liquid, this variation be embodied in the decanting vessel of rectifying for the second time 9 middle-high densities mutually in methyl iodide content increase.Experiment is found, this temperature is being lower than below 45 ℃, it is exactly tangible changing, because the amount of the high-density phase in this decanting vessel of rectifying for the second time 9 is less, therefore the end, help phase-splitting and layering to temperature more more, but this temperature can not be low excessively, causes the curing of liquid in the decanting vessel 9 of rectifying for the second time.This refrigerative temperature can be obtained by the control of condenser 40.
When methyl iodide content in reaction solution is higher than certain concentration, the instability of catalyst rhodium in the liquid that can induce reaction.The concentration that methyl iodide in reaction solution is found in experiment near or surpass this adverse influence of 18wt% and begin to have significantly and manifest, when the concentration of methyl iodide in the reaction solution during near 21wt%, this disadvantageous effect is more obvious.
When the raising of inorganic iodine salt concn, when iodide ion concentration improved, the stability of catalyst rhodium improved in the reaction solution, makes rhodium under the concentration atmosphere of higher ritalin and methyl iodide, can be stabilized in a high concentration.
For lightness-removing column 2, dehydration tower 3, weight-removing column 4, can realize with any type of rectifying tower, comprise various forms of packing towers and tray column, but must guarantee its isolating theoretical stage.In general the theoretical stage of lightness-removing column (2) is at 3 ~ 10 grades, and best at 5 ~ 7 grades, in general the theoretical stage of dehydration tower 3 is at 20 ~ 30 grades, and best at 23 ~ 28 grades, in general the theoretical stage of weight-removing column 4 is at 30 ~ 40 grades, and the best is at 30 ~ 35 grades.As long as rectifying tower is in the requirement of these scopes, rectifying can obtain high-quality product.The pressure of distillation operation carries out under the condition of normal pressure or pressurization, and the control of pressure is by the pressure decision of waste gas washing, and experimentation keeps system pressure in 0 ~ 200kpa (gauge pressure).
When concrete reaction is purified, at first dispose catalyzer as required and add acetic acid in reactor, prepare suitable reaction solution, then with the reactor increasing temperature and pressure, successive feeds methyl alcohol 36 and CO 37 in reactor when condition meets.The temperature of reaction is at 190-195 ℃, the pressure of reaction is about 28-30atm, then reaction solution is shifted out the acetic acid 10 of moisture, ritalin, methyl iodide and some other impurity by flash distillation, the about wt 50% of acetic acid content, and remove the part heat, rely on the pump circulation cooling system of reactor to remove remaining reaction heat simultaneously.Here it is reactive system 1 is consistent in the patent 2003101082903 of the embodiment of this system and applicant's application.Be not described in detail at this.
The acetic acid 10 that contains a large amount of impurity enters lightness-removing column 2 and carries out lightness-removing column 2, and lightness-removing column 2 is to have the theoretical rectifying tower that separates progression of 5-7 level.Carry dense acetic acid 12 from 2 times tower extraction of lightness-removing column, acetate concentration is about 90% (wt), and all the other are water, ritalin, methyl iodide and some trace impurities.Keep sub-fraction to carry 16 times reactive systems 1 of dense acetic acid liquid in lightness-removing column 2 bottoms.Contain the light constituent gaseous stream 17 of low boilers in lightness-removing column 2 top extraction, contain water, ritalin, methyl iodide, acetic acid and some impurity in the logistics 17.The temperature that logistics 17 condensation and being cooled in condenser 39 needs, condensator outlet logistics 11 contains the gas-liquid two-phase, logistics 11 is isolated gas phase earlier in rectifying first time decanting vessel 8, be separated into two liquid phases then, it is two-layer up and down that liquid phase relies on the difference of density to be separated into, 13 times reaction solution systems 1 of high-density logistics, and low density logistics 13 is divided into two-way, one logistics 14 is as the backflow of tower, 44 times reactive systems of another burst logistics.
Introduce two bursts of logistics in rectifying first time decanting vessel 8 simultaneously: one is a water 42, and another strand is the high-density logistics 21 from rectifying second time decanting vessel 9.The adding of water 42 can promote the generation of low density phase in the decanting vessel 8, can promote the generation of decanting vessel 8 high-density phases from the adding of the high-density logistics 21 of decanting vessel 9.These two bursts of logistics add according to control mode separately.
Logistics 12 contains 10wt% water, ritalin, methyl iodide and some trace impurities, enters dehydration tower 3.Dehydration tower 3 is to have the theoretical rectifying tower that separates progression of 23-28 level.Carry dense acetic acid 18 from dehydration tower 2 bottom extraction, acetate concentration is about 99wt%, and all the other are water, propionic acid and some trace impurities.Contain the light constituent gaseous stream 19 of low boilers in dehydration tower 3 top extraction, mainly contain water, acetic acid in the logistics 19, ritalin, methyl iodide and some impurity.Logistics 19 condensation and be cooled to temperature below 45 ℃ in condenser 40, condensator outlet logistics 20 contains the gas-liquid two-phase, logistics 20 is isolated gas phase earlier in rectifying second time decanting vessel 9, be separated into two liquid phases then, it is two-layer up and down that liquid phase relies on the difference of density to be separated into, and high-density logistics 21 enters the decanting vessel of rectifying for the first time 8 by control, and low density logistics 22 is divided into two-way, one logistics 23 is as the backflow of tower, 24 times reactive systems of another burst logistics.
In rectifying second time decanting vessel 9, introduce water 43 simultaneously.
The logistics of introducing water 42 and 43 in rectifying first time decanting vessel 8, the decanting vessel of rectifying for the second time 9 simultaneously is in check.The total amount of logistics 42 and logistics 43 is logistics 41, and logistics 41 is a fixed value when constant at acetate yield and catalyzer (reaction solution), reaction conditions (temperature, pressure): the total amount that it equals the water yield that side reaction is used in the reactor the water yield, product and by product take away deducts the water yield that raw material is brought into.Therefore, the total amount of logistics 42 and logistics 43 is subjected to the levels of catalysts of processing condition and acetic acid synthesis from methanol carbonylation and determines, the variation of any one material in two strands of materials can cause the variation of another strand material.The variation range of per share material all changes between " 0 " and maximum, and this maximum is exactly that the total amount of the water yield taken away of side reaction is used in the reactor the water yield, product and by product deducts the water yield that raw material is brought into.
For the second time rectifying decanting vessel 9 discharge high-density logistics 21 control according to be the liquid level of high-density logistics in rectifying second time decanting vessel 9, adopt bang-bang control according to liquid level, open during high liquid level, close during low liquid level, adopt discontinuous to discharge.When only methyl iodide had reduction trend in reactor, logistics 21 derived continuously.
Logistics 18 enters weight-removing column 4, and rectification and purification goes out product 25 then, gives off the spent acid 30 that contains propionic acid.
Logistics 41 requires to be pure water that described water 42 and water 43 are provided by logistics 41.
In implementation process, all examples of implementation write down the input of raw material and the extraction of product and by product in the set time, as the examination to the catalyzer ability.Simultaneously, be that the yield that benchmark calculates is weighed catalyzer transformation efficiency and optionally examination with raw material CO and methyl alcohol.
Embodiment 1
Reaction solution consists of: acetic acid 70.5wt%, ritalin 1wt%, methyl iodide 12wt%, water 14wt%, Fe0.0025wt%, Ni0.0024wt%, Cr0.0050wt%, Mo0.0100wt%, I
-2.5wt%, Rh0.04wt%.
Experimentize according to embodiment, and temperature are about 40 ℃ in the maintenance decanting vessel 8 that keeping decanting vessel 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 100kg/h, and keeping logistics 42 flows is 100kg/h.Experiment is to catalyzer composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of the composition of logistics 25, logistics 30 detects.And obtain product 25127kg, spent acid 300.2kg.What table 1 write down is logistics capacity and the processing condition of embodiment 1.
Embodiment 1 is as a kind of contrast of the present invention, and decanting vessel (9) is not done decanting vessel and used.
Table 1
| Title | Numerical value | Unit |
| Logistics (41) flow | 100 | kg/h |
| Logistics (42) flow | 100 | kg/h |
| Logistics (43) flow | 0 | kg/h |
| Logistics (15) density | 1835 | kg/m 3 |
| The temperature of decanting vessel (8) | 34 | ℃ |
| The temperature of decanting vessel (9) | / | ℃ |
| The input amount of methyl alcohol | 71.0 | kg(100％) |
| The input amount of CO | 68.62 | kg(100％) |
| Product (25) amount of obtaining | 127 | kg |
| Spent acid (30) amount of obtaining | 0.20 | kg |
| Calculate yield with CO | 0.86 | ％ |
| Calculate yield with methyl alcohol | 0.95 | ％ |
Embodiment 2:
Reaction solution consists of: acetic acid 59.8wt%, ritalin 1.94wt%, methyl iodide 10.37wt%, water 7.17wt%, K
+0.5000wt%, Li
+0.3700wt%, Fe 0.1357wt%, Ni 0.0798wt%, Cr 0.0916wt%, I
-10.83wt%, Rh 0.0650wt%.
Experimentize according to embodiment, and temperature are about 36 ℃ in the maintenance decanting vessel 8 that keeping decanting vessel 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 100kg/h, and keeping logistics 42 flows is 75kg/h.Experiment is to catalyzer composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of the composition of logistics 25, logistics 30 detects.And obtain product 25 179.5kg, spent acid 30 0.23kg.What table 2 write down is logistics capacity and the processing condition of embodiment 2.
Table 2
| Title | Numerical value | Unit |
| Logistics (41) flow | 100 | kg/h |
| Logistics (42) flow | 75 | kg/h |
| Logistics (43) flow | 25 | kg/h |
| Logistics (15) density | 1810 | kg/m 3 |
| The temperature of decanting vessel (8) | 38.9 | ℃ |
| The temperature of decanting vessel (9) | 42.7 | ℃ |
| The input amount of methyl alcohol | 98.8 | kg(100％) |
| The input amount of CO | 93.7 | kg(100％) |
| Product (25) amount of obtaining | 179.5 | kg |
| Spent acid (30) amount of obtaining | 0.23 | kg |
| Calculate yield with CO | 0.89 | |
| Calculate yield with methyl alcohol | 0.97 |
Embodiment 3:
Reaction solution consists of: acetic acid 64.9wt%, ritalin 3.0wt%, methyl iodide 14.0wt%, water 8.4wt%, propionic acid 0.0341wt%, K
+0.4000wt%, Li
+0.3600wt%, Fe 0.1551wt%, Ni 0.1027wt%, Cr 0.1085wt%, Mo 0.0708wt%, I
-9.5wt%, Rh 0.0740wt%.
Experimentize according to embodiment, and temperature are about 32 ℃ in the maintenance decanting vessel 8 that keeping decanting vessel 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 90kg/h, and keeping logistics 42 flows is 50kg/h.Experiment is to catalyzer composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of the composition of logistics 25, logistics 30 detects.And obtain product 25 225.8kg, spent acid 30 0.25kg.What table 3 write down is logistics capacity and the processing condition of embodiment 3.
Table 3
| Title | Numerical value | Unit |
| Logistics (41) flow | 90 | kg/h |
| Logistics (42) flow | 50 | kg/h |
| Logistics (43) flow | 40 | kg/h |
| Logistics (15) density | 1822 | kg/m 3 |
| The temperature of decanting vessel (8) | 32.2 | ℃ |
| The temperature of decanting vessel (9) | 42.7 | ℃ |
| The input amount of methyl alcohol | 123 | kg(100％) |
| The input amount of C0 | 113.6 | kg(100％) |
| Product (25) amount of obtaining | 225.8 | kg |
| Spent acid (30) amount of obtaining | 0.25 | kg |
| Calculate yield with CO | 0.93 | ％ |
| Calculate yield with methyl alcohol | 0.98 | ％ |
Embodiment 4:
Reaction solution consists of: acetic acid 64.4wt%, ritalin 2.50wt%, methyl iodide 13.0wt%, water 7.8wt%, K
+0.4000wt%, Li
+0.3600wt%, Fe 0.1503wt%, Ni 0.1083wt%, Cr 0.1019wt%, Mo 0.0687wt%, I
-10.0wt%, Rh 0.0780wt%.
Experimentize according to embodiment, and temperature are about 28 ℃ in the maintenance decanting vessel 8 that keeping decanting vessel 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 110kg/h, and keeping logistics 42 flows is 40kg/h.Experiment is to catalyzer composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of the composition of logistics 25, logistics 30 detects.And obtain product 25 231.3kg, spent acid 30 0.25kg.What table 4 write down is logistics capacity and the processing condition of embodiment 4.
Table 4
| Title | Numerical value | Unit |
| Logistics (41) flow | 110 | kg/h |
| Logistics (42) flow | 40 | kg/h |
| Logistics (43) flow | 70 | kg/h |
| Logistics (15) density | 1831 | kg/m 3 |
| The temperature of decanting vessel (8) | 28.7 | ℃ |
| The temperature of decanting vessel (9) | 35 | ℃ |
| The input amount of methyl alcohol | 125.5 | kg(100％) |
| The input amount of CO | 117.5 | kg(100％) |
| Product (25) amount of obtaining | 231.3 | kg |
| Spent acid (30) amount of obtaining | 0.25 | kg |
| Calculate yield with CO | 0.92 | ％ |
| Calculate yield with methyl alcohol | 0.98 | ％ |
Embodiment 5:
Reaction solution consists of: acetic acid 66.0wt%, ritalin 2.9wt%, methyl iodide 13.9wt%, water 6.8wt%, propionic acid 0.0481wt%, K
+0.3800wt%, Li
+0.3600wt%, Fe 0.1627wt%, Ni 0.0798wt%, Cr 0.1231wt%, Mo 0.0737wt%, I
-10.1wt%, Rh 0.0800wt%.
Experimentize according to embodiment, and temperature are about 25 ℃ in the maintenance decanting vessel 8 that keeping decanting vessel 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 100kg/h, and keeping logistics 42 flows is 25kg/h.Experiment is to catalyzer composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of the composition of logistics 25, logistics 30 detects.And obtain product 25 251kg, spent acid 30 0.25kg.What table 5 write down is logistics capacity and the processing condition of embodiment 5.
Table 5
| Title | Numerical value | Unit |
| Logistics (41) flow | 100 | kg/h |
| Logistics (42) flow | 25 | kg/h |
| Logistics (43) flow | 75 | kg/h |
| Logistics (15) density | 1837 | kg/m 3 |
| The temperature of decanting vessel (8) | 25 | ℃ |
| The temperature of decanting vessel (9) | 40 | ℃ |
| The input amount of methyl alcohol | 135.0 | kg(100％) |
| The input amount of CO | 126.8 | kg(100％) |
| Product (25) amount of obtaining | 251.0 | kg |
| Spent acid (30) amount of obtaining | 0.25 | kg |
| Calculate yield with CO | 0.92 | ％ |
| Calculate yield with methyl alcohol | 0.99 | ％ |
Embodiment 6:
Reaction solution consists of: acetic acid 59.0wt%, ritalin 2.1wt%, methyl iodide 14.7wt%, water 5.5wt%, K
+0.2600wt%, Li
+0.4500wt%, Fe 0.1545wt%, Ni 0.0755wt%, Cr 0.0176wt%, Mo 0.0169wt%, I
-12.2wt%, Rh 0.100wt%.
Experimentize according to embodiment, and temperature are about 23 ℃ in the maintenance decanting vessel 8 that keeping decanting vessel 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 100kg/h, and keeping logistics 42 flows is 0kg/h.Experiment is to catalyzer composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of the composition of logistics 25, logistics 30 detects.And obtain product 25 255kg, spent acid 30 0.35kg.What table 6 write down is logistics capacity and the processing condition of embodiment 6.
Table 6
| Title | Numerical value | Unit |
| Logistics (41) flow | 100 | kg/h |
| Logistics (42) flow | 0 | kg/h |
| Logistics (43) flow | 100 | kg/h |
| Logistics (15) density | 1840 | kg/m 3 |
| The temperature of decanting vessel (8) | 23.3 | ℃ |
| The temperature of decanting vessel (9) | 40 | ℃ |
| The input amount of methyl alcohol | 138.0 | kg(100％) |
| The input amount of CO | 129.0 | kg(100％) |
| Product (25) amount of obtaining | 255 | kg |
| Spent acid (30) amount of obtaining | 0.35 | kg |
| Calculate yield with CO | 0.92 | ％ |
| Calculate yield with methyl alcohol | 0.99 | ％ |
Embodiment 7:
Reaction solution consists of: acetic acid 60.7wt%, ritalin 2.3wt%, methyl iodide 15.2wt%, water 5.0wt%, K
+0.2500wt%, Li
+0.4100wt%, Fe 0.1537wt%, Ni 0.0684wt%, Cr 0.023wt%, Mo 0.0217wt%, I
-11.6wt%, Rh0.0780wt%.
Experimentize according to embodiment, and temperature are about 23 ℃ in the maintenance decanting vessel 8 that keeping decanting vessel 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 120kg/h, and keeping logistics 42 flows is 90kg/h.Experiment is to catalyzer composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of the composition of logistics 25, logistics 30 detects.And obtain product 25 263kg, spent acid 30 0.25kg.What table 7 write down is logistics capacity and the processing condition of embodiment 7.
Table 7
| Title | Numerical value | Unit |
| Logistics (41) flow | 120 | kg/h |
| Logistics (42) flow | 90 | kg/h |
| Logistics (43) flow | 30 | kg/h |
| Logistics (15) density | 1830 | kg/m 3 |
| The temperature of decanting vessel (8) | 30 | ℃ |
| The temperature of decanting vessel (9) | 40 | ℃ |
| The input amount of methyl alcohol | 143.0 | kg(100％) |
| The input amount of CO | 134.0 | kg(100％) |
| Product (25) amount of obtaining | 263 | kg |
| Spent acid (30) amount of obtaining | 0.25 | kg |
| Calculate yield with CO | 0.92 | ％ |
| Calculate yield with methyl alcohol | 0.98 | ％ |
Embodiment 8:
Reaction solution consists of: acetic acid 58.7wt%, ritalin 2.70wt%, methyl iodide 16.4wt%, water 4.4wt%, propionic acid 1.0774wt%, K
+0.2100wt%, Li
+0.5000wt%, Fe 0.1537wt%, Ni 0.0684wt%, Cr 0.0230wt%, Mo 0.0217wt%, I
-12.2wt%, Rh 0.0900wt%.
Experimentize according to embodiment, and temperature are about 30 ℃ in the maintenance decanting vessel 8 that keeping decanting vessel 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 75kg/h, and keeping logistics 42 flows is 60kg/h.Experiment is to catalyzer composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of the composition of logistics 25, logistics 30 detects.And obtain product 25 255kg, spent acid 30 0.35kg.What table 8 write down is logistics capacity and the processing condition of embodiment 8.
Table 8
| Title | Numerical value | Unit |
| Logistics (41) flow | 75 | kg/h |
| Logistics (42) flow | 60 | kg/h |
| Logistics (43) flow | 15 | kg/h |
| Logistics (15) density | 1831 | kg/m 3 |
| The temperature of decanting vessel (8) | 30 | ℃ |
| The temperature of decanting vessel (9) | 40 | ℃ |
| The input amount of methyl alcohol | 143.5 | kg(100％) |
| The input amount of CO | 134.0 | kg(100％) |
| Product (25) amount of obtaining | 263 | kg |
| Spent acid (30) amount of obtaining | 0.25 | kg |
| Calculate yield with CO | 0.92 | ％ |
| Calculate yield with methyl alcohol | 0.98 | ％ |
Embodiment 9:
Reaction solution consists of: acetic acid 58.7wt%, ritalin 3.80wt%, methyl iodide 18.8wt%, water 7.0wt%, K
+0.1700wt%, Li
+0.5500wt%, Fe 0.0537wt%, Ni 0.0284wt%, I
-10.1wt%, Rh 0.0640wt%.
Experimentize according to embodiment, and temperature are about 30 ℃ in the maintenance decanting vessel 8 that keeping decanting vessel 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 75kg/h, and keeping logistics 42 flows is 60kg/h.Experiment is to catalyzer composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of the composition of logistics 25, logistics 30 detects.And obtain product 25 251kg, spent acid 30 0.25kg.What table 9 write down is logistics capacity and the processing condition of embodiment 9.
Table 9
| Title | Numerical value | Unit |
| Logistics (41) flow | 75 | kg/h |
| Logistics (42) flow | 60 | kg/h |
| Logistics (43) flow | 15 | kg/h |
| Logistics (15) density | 1851 | kg/m 3 |
| The temperature of decanting vessel (8) | 30 | ℃ |
| The temperature of decanting vessel (9) | 40 | ℃ |
| The input amount of methyl alcohol | 135.2 | kg(100％) |
| The input amount of CO | 126.7 | kg(100％) |
| Product (25) amount of obtaining | 251.0 | kg |
| Spent acid (30) amount of obtaining | 0.25 | kg |
| Calculate yield with CO | 0.99 | ％ |
| Calculate yield with methyl alcohol | 0.92 | ％ |
Embodiment 10:
Reaction solution consists of: acetic acid 59.7wt%, ritalin 3.8wt%, methyl iodide 21.2wt%, water 7.3wt%, K
+0.1600wt%, Li
+0.4300wt%, Fe 0.0637wt%, Ni 0.0284wt% I
-8.9wt%, Rh0.055wt%.
Experimentize according to embodiment, and temperature are about 30 ℃ in the maintenance decanting vessel 8 that keeping decanting vessel 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 65kg/h, and keeping logistics 42 flows is 65kg/h.Experiment is to catalyzer composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of logistics (25), the composition of logistics 30 detect.And obtain product 25 225kg, spent acid 30 0.25kg.What table 10 write down is logistics capacity and the processing condition of embodiment 10.
Table 10
| Title | Numerical value | Unit |
| Logistics (41) flow | 75 | kg/h |
| Logistics (42) flow | 60 | kg/h |
| Logistics (43) flow | 15 | kg/h |
| Logistics (15) density | 1881 | kg/m 3 |
| The temperature of decanting vessel (8) | 30 | ℃ |
| The temperature of decanting vessel (9) | 40 | ℃ |
| The input amount of methyl alcohol | 124 | kg(100％) |
| The input amount of CO | 113 | kg(100％) |
| Product (25) amount of obtaining | 225 | kg |
| Spent acid (30) amount of obtaining | 0.25 | kg |
| Calculate yield with CO | 0.97 | ％ |
| Calculate yield with methyl alcohol | 0.93 | ％ |
Embodiment 11:
Reaction solution consists of: acetic acid 63.4wt%, ritalin 2.7wt%, methyl iodide 14.2wt%, water 5.6wt%, K
+0.1700wt%, Li
+0.6300wt%, Fe 0.1537wt%, Ni 0.0684wt%, Cr 0.0230wt%, Mo 0.0217wt%, I
-13.8wt%, Rh 0.085wt%.
Experimentize according to embodiment, and temperature are about 30 ℃ in the maintenance decanting vessel 8 that keeping decanting vessel 9 temperature is less than 45 ℃.Keeping logistics 41 flows is 70kg/h, and keeping logistics 42 flows is 50kg/h.Experiment is to catalyzer composition, logistics 12 compositions, the density of logistics 15, the concentration of logistics 21, and the composition of the composition of logistics 25, logistics 30 detects.And obtain product 25 260kg, spent acid 30 0.25kg.What table 11 write down is logistics capacity and the processing condition of embodiment 11.
Table 11
| Title | Numerical value | Unit |
| Logistics (41) flow | 70 | kg/h |
| Logistics (42) flow | 50 | kg/h |
| Logistics (43) flow | 20 | kg/h |
| Logistics (15) density | 1811 | kg/m 3 |
| The temperature of decanting vessel (8) | 30 | ℃ |
| The temperature of decanting vessel (9) | 40 | ℃ |
| The input amount of methyl alcohol | 140.1 | kg(100％) |
| The input amount of CO | 134.1 | kg(100％) |
| Product (25) amount of obtaining | 260 | kg |
| Spent acid (30) amount of obtaining | 0.25 | kg |
| Calculate yield with CO | 0.99 | ％ |
| Calculate yield with methyl alcohol | 0.90 | ％ |
Embodiment 12
Present embodiment takes out part separately with 9 inlet stream 20 of the decanting vessel of rectifying for the second time among the embodiment 8, is further cooling off, and carries out the decant layering under differing temps.Low density after the layering is taken out mutually with high-density mutually, and component is wherein analyzed, observe the change in concentration of low density phase and high-density phase component under the temperature variation, it the results are shown in Table I.Experiment shows that temperature is low more, and ritalin and methyl iodide are high more in the concentration of high-density in mutually, and is low more in the concentration of low density in mutually, to the methyl iodide obvious effect.
Table I
| Temperature ℃ | Logistics | Density kg/m 3 | Acetic acid %wt | Ritalin %wt | Methyl iodide %wt | Water %wt | |
| 45 | 20 | 35.8 | 13.70 | 16.20 | 34.2 | ||
| 45 | After the cooling layering | The low density phase | 1076 | 36.28 | 13.722 | 15.22 | 34.77 |
| The high-density phase | 1719 | 7.49 | 13.14 | 78.90 | 0.3895 | ||
| 30 | After the cooling layering | The low density phase | 1080 | 37.01 | 13.73 | 13.62 | 35.63 |
| The high-density phase | 1754 | 7.35 | 13.34 | 78.98 | 0.325 | ||
| 20 | After the cooling layering | The low density phase | 1083 | 37.47 | 13.73 | 12.62 | 36.18 |
| The high-density phase | 1776 | 7.25 | 13.45 | 79.00 | 0.2859 | ||
| 10 | After the cooling layering | The low density phase | 1085 | 37.92 | 13.72 | 11.65 | 36.70 |
| The high-density phase | 1799 | 7.144 | 13.725 | 79.04 | 0.2497 | ||
Embodiment 13
Present embodiment takes out part separately with 9 inlet stream 20 of the decanting vessel of rectifying for the second time among the embodiment 8, and cooling temperature carries out the decant layering at 30 ℃ under different amount of water.Low density after the layering is taken out mutually with high-density mutually, and component is wherein analyzed, the change in concentration of observation component, it the results are shown in Table II.Experiment shows that it is many more to add water, and ritalin and methyl iodide are high more in the concentration of high-density in mutually, and is low more in the concentration of low density in mutually.Logistics (20) amount of getting is 17.9kg.
Table II
| Amount of water kg | Logistics | Density kg/m 3 | Acetic acid %wt | Ritalin %wt | Methyl iodide %wt | Water %wt | |
| 1.5 | After the layering | The low density phase | 1074 | 33.99 | 12.61 | 12.68 | 40.66 |
| The high-density phase | 1837 | 5.915 | 1210 | 81.77 | 0.2699 | ||
| 1.0 | After the layering | The low density phase | 1077 | 34.95 | 13.055 | 12.95 | 39.09 |
| The high-density phase | 1821 | 6.331 | 12.49 | 80.90 | 0.2854 | ||
| 0.5 | After the layering | The low density phase | 1083 | 35.96 | 13.36 | 13.27 | 37.42 |
| The high-density phase | 1772 | 6.806 | 12.90 | 79.99 | 0.303 | ||
More than show and described ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in the foregoing description and the specification sheets just illustrates principle of the present invention; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (16)
1, a kind of method of purification of acetic acid synthesized by low pressure methanol carbonylation, it comprises the reaction solution impure gas-phase crude acetic acid that flash distillation produces in flasher that contains catalyzer, goes out impure wet acetic acid by lightness-removing column rectifying.Then wet acetic acid is sent into dehydration tower and further deviate from water and impurity, through the acetic acid of dehydration and impurity, further purifying with existing way is qualified quality products; Wherein behind the vapor condensation of dehydration tower top, deliver to a rectifying decanting vessel for the second time, the decanting vessel of rectifying for the second time with liquid be divided into moisture and acetic acid be main low density mutually with contain methyl iodide and ritalin be the high-density led mutually; Behind the vapor condensation of described lightness-removing column top, deliver to rectifying decanting vessel for the first time, the decanting vessel of rectifying for the first time with liquid be divided into moisture and acetic acid be main low density mutually with contain methyl iodide and ritalin be the high-density led mutually; The high-density that the decanting vessel of rectifying for the second time produces imports the decanting vessel of rectifying for the first time mutually.
2, method of purification according to claim 1, wherein the high-density of the decanting vessel of rectifying for the second time generation imports the flow of the decanting vessel of rectifying for the first time mutually by the control of the decanting vessel of rectifying for the second time high-density phase liquid level.
3, method of purification according to claim 2, wherein said liquid level control is continuous derivation.
4, method of purification according to claim 2, wherein said liquid level control is intermittently to derive.
5, method of purification according to claim 1 wherein adds entry at rectifying second time decanting vessel with at rectifying first time decanting vessel.
6, method of purification according to claim 1 wherein adds entry at rectifying second time decanting vessel or at rectifying first time decanting vessel.
7, according to claim 5 or 6 described methods of purification, the total amount that the wherein said total amount that adds water equals the water yield taken away according to the water yield, product and by product that side reaction in the reactor is used deducts the water yield that raw material is brought into.
8, method of purification according to claim 1, wherein the temperature in the decanting vessel of rectifying for the second time is controlled at 10-45 ℃.
9, method of purification according to claim 1, wherein the temperature in the decanting vessel of rectifying for the second time is controlled at 20-45 ℃.
10, method of purification according to claim 1, wherein the temperature in the decanting vessel of rectifying for the first time is controlled at 23-40 ℃.
11, method of purification according to claim 1, wherein the temperature in the decanting vessel of rectifying for the first time is controlled at 26-36 ℃.
12, method of purification according to claim 1, wherein lightness-removing column has 3-10 theoretical stage.
13, method of purification according to claim 1, wherein lightness-removing column has 5-7 theoretical stage.
14, method of purification according to claim 1, wherein dehydration tower has 20-30 theoretical stage.
15, method of purification according to claim 1, wherein dehydration tower has 23-27 theoretical stage.
16, method of purification according to claim 1, wherein the pressure of distillation operation carries out under the condition of normal pressure or pressurization, and the control of pressure is by the pressure decision of waste gas washing, and experimentation keeps system pressure at gauge pressure 0-200kpa.
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| CN104805290A (en) * | 2015-03-27 | 2015-07-29 | 中国昆仑工程公司 | Method for recovering acetic acid, cobalt and manganese from discharged residues of PTA (purified terephthalic acid) film evaporator |
| CN112010746A (en) * | 2020-08-18 | 2020-12-01 | 南京延长反应技术研究院有限公司 | External micro-interface strengthening system and method for preparing acetic acid through methanol carbonylation |
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| DE69609796T2 (en) * | 1995-04-27 | 2000-12-28 | Daicel Chem | METHOD FOR PRODUCING ACETIC ACID |
| US6103934A (en) * | 1998-12-18 | 2000-08-15 | Millennium Petrochemicals, Inc. | Manufacturing and process control methods |
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| CN104805290A (en) * | 2015-03-27 | 2015-07-29 | 中国昆仑工程公司 | Method for recovering acetic acid, cobalt and manganese from discharged residues of PTA (purified terephthalic acid) film evaporator |
| CN112010746A (en) * | 2020-08-18 | 2020-12-01 | 南京延长反应技术研究院有限公司 | External micro-interface strengthening system and method for preparing acetic acid through methanol carbonylation |
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Effective date of registration: 20150119 Address after: 200241 Minhang District, Wu Long Road, No. 4280, Shanghai Patentee after: Shanghai Hua Yi derived energy chemical Co., Ltd Address before: 200241 No. 4600 Wu Long Road, Shanghai Patentee before: Wujing Chemical Co., Ltd., Shanghai |