CN101391946A - Control method of acetaldehyde content during acetic acid synthesis from methanol carbonylation - Google Patents
Control method of acetaldehyde content during acetic acid synthesis from methanol carbonylation Download PDFInfo
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- CN101391946A CN101391946A CNA2008102349204A CN200810234920A CN101391946A CN 101391946 A CN101391946 A CN 101391946A CN A2008102349204 A CNA2008102349204 A CN A2008102349204A CN 200810234920 A CN200810234920 A CN 200810234920A CN 101391946 A CN101391946 A CN 101391946A
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Abstract
The invention provides a method for controlling the content of acetaldehyde in the synthesizing process of acetic acid by methanol carbonylation. The method comprises the steps: after flash evaporation of carbonylation materials, volatile phases are formed after the separation of a light component tower and condensed and separated to form 'light phases' and 'heavy phases', wherein, the 'light phases' are completely or partly led into a distillation tower for distillation, tower top distillates containing acetaldehyde and methyl iodide are obtained from the top of the tower, and tower bottom reflux substances containing methyl iodide, acetic acid and water are obtained form the bottom of the tower; and after condensation of the tower top distillates through a condenser, extraction is carried out by water, the extraction liquid containing acetaldehyde is discharged outside for independent treatment, and the faffinate and the tower bottom reflux substances are put back to a main reaction system to complete the procedures of follow-up processing with the left 'light phases'. The method can effectively control the content of acetaldehyde in the synthesizing process of the acetic acid by methanol carbonylation, reduce or remove compounds (PRC S) which deacidize hypermanganate, and reduce the loss of cocatalysts of methyl iodide and the like.
Description
Technical field
The present invention relates to the production technique of acetic acid synthesis from methanol carbonylation, relate in particular in the acetic acid synthesis from methanol carbonylation process, the control method of main permanganate-reducing compound " acetaldehyde " content belongs to the organic synthesis chemical technology field.
Background technology
At present in the method for suitability for industrialized production acetic acid, the most effective is to authorize United States Patent (USP) 3,769, the 329 described methyl alcohol of Paulik etc. and the carbonylation of CO on October 30th, 1973.The United States Patent (USP) of issuing on March 19th, 1,991 5,001,259, issued on June 25th, 1991 5, issued on September 1st, 026,908,1992 5,144, the European patent EP 0,161 that on July 1st, 068 and 1992 announced is among the 874B2, disclose in the presence of rhodium catalyst, pure carbonylation has been made carbonatoms Duo one the Technology of carboxylic acid than pure.
Pointed out in these patents reaction system for low water concentration 4% weight or lower (general industry water is 14～15% weight) condition under catalyst stability and speed of reaction remain on higher level, promptly catalyzer does not precipitate under lower water concentration, its catalyzer mainly exists with the carbonylation form, and in catalyst system, contain considerable simple iodide, be preferably lithium iodide.Make acetate under so low water concentration, increased the trace impurity that is present in the acetic acid product, as permanganate-reducing compound, propionic acid etc., the compound that reduces the acetic acid permanganate-reducing time is mainly carbonyl compound and beta-unsaturated carbonyl compounds.
Minimizing that the present invention relates to or removal permanganate-reducing compound (PRC ' S), the acetaldehyde that it at first is mainly side reaction and is produced, and further react the saturated and undersaturated aldehyde ketone of generation and many carbon alkyl iodide etc. by acetaldehyde, the existence of these compounds can limit the industrial use of acetate products, can make acetic acid make poisoning of catalyst when making vinyl acetate as the existence of methyl-iodide.United States Patent (USP) 5,783,731 usefulness amine compound are handled organic streams, amine and acetaldehyde reaction form oxime, carry out fractionation by distillation purifying acetic acid then, this has increased the technology cost and can introduce new impurity, and distillation simultaneously is difficult to remove some and the acetate boiling point impurity of approaching permanganate-reducing time.Therefore, in the feasible way, United States Patent (USP) 5,756,836 disclose and a kind ofly have been lower than the method that 1500ppm makes high-purity acetic acid by the acetaldehyde concentration in the reaction soln is regulated, and the concentration that generates by control acetaldehyde suppresses the generation of impurity, obtains the high-purity acetic acid product by distillation again.
April 12 nineteen ninety-five European patent EP 0,487,284 disclose the impurity that exists in the acetic acid product is gathered in the overhead product of lighting end cat head usually, therefore handle overhead product and generate 9 oxime derivate with amine compound, 9 oxime derivate can separate with remaining overhead product by distillation, thereby can improve the quality of acetate products.European patent EP 0,687,662A2 and United States Patent (USP) 5,625,095 propose to use single-stage or multistage distillation to remove acetaldehyde, thus the acetaldehyde concentration below reactor maintenance 400ppm.EP0,687,662 and United States Patent (USP) 5,625, thus 095 the generation of control reaction conditions control acetaldehyde is proposed, but generate more propionic acid by product.
Summary of the invention
The present invention be directed to the deficiency that prior art exists, the control method of acetaldehyde in a kind of acetic acid synthesis from methanol carbonylation process is provided, to reduce or to remove the compound (PRC`S) of the permanganate-reducing that forms in the process of used for preparing acetic acid through carbonylation reaction product, improve the quality of acetic acid synthesis from methanol carbonylation finished product.
For realizing purpose of the present invention, the control method of acetaldehyde in the acetic acid synthesis from methanol carbonylation process, with VIII family metal as carbonylating catalyst, carry out carbonylation reaction by methyl alcohol and CO and generate acetic acid, it is characterized in that: in the main reaction system, after the flash distillation of carbonylation material, separate the volatile phase of formation through lights column, this is volatile through condensation separation formation " light phase " and " heavy phase ", wherein " light phase " all or part of distillation tower that is introduced into distills, obtain to comprise the overhead product of acetaldehyde and methyl-iodide from cat head, at the bottom of tower, obtain to comprise methyl-iodide, reflux at the bottom of the tower of acetic acid and water; Described overhead product is through after the condenser condenses, water extracts, the extraction liquid that contains acetaldehyde effluxes and manages elsewhere, and raffinate then returns the main reaction system with reflux at the bottom of the described tower, continues to finish each operation process of subsequent disposal with remaining " gently mutually ".
Further, the control method of acetaldehyde in the above-mentioned acetic acid synthesis from methanol carbonylation process, wherein: when extraction, water and material temperature are 0～15 ℃, and extracting pressure is 50～200KPa.
Further, the control method of acetaldehyde in the above-mentioned acetic acid synthesis from methanol carbonylation process, wherein: the feeding rate of the operating parameters of described distillation tower and the water of extraction process, it is permanganate-reducing compound concentrations by rapid chemical assaying reaction district, and finally determine by the permanganate-reducing time of acetic acid finished product, to reduce the loss of promotors such as methyl-iodide.
Technological merit of the present invention---especially compare with the patent of U.S. Celanese Int Corp, mainly contain following some:
Though 1 all is gently to separate acetaldehyde component mutually by what fractionation by distillation was just divided tower, the process of control purpose and control is completely different, and Celanese Corp. separates acetaldehyde by knockout tower and just removes acetaldehyde as much as possible; Come the red-tape operati condition and the application is variation according to the content of reducing substances in reactor and the finished product, as far as possible other promotor in the material is turned back in the system.
2, the material density that distills out by mensuration of Celanese Corp. is estimated the acetaldehyde in the material; The application accurately controls acetaldehyde in the material by the rapid chemical analytical method.
3, Celanese Corp. controls gathering of acetaldehyde in the distillation tower by the feed back that adds certain acetic acid and water at the top of separating the acetaldehyde tower; The application controls the generation that acetaldehyde gathers by the content of the moisture in the control material and the working pressure of tower.
4, Celanese Int Corp has only considered the influence of dme to extract acetaldehyde when water is handled overhead product and separated other promotor except that acetaldehyde of acetaldehyde recovery; The application has considered the content according to reducing substances in the system, decides the moisture add-on of extraction, controls the partition ratio of promotor by controlling extraction temperature and extracting pressure, has reduced the loss of useful matter to greatest extent.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
The present invention is by the concentration of acetaldehyde in the controlling reactor, and the fraction overhead overhead product gently separates acetaldehyde in mutually, water extract acetaldehyde under certain conditions, thereby the compound of the permanganate-reducing in the control acetic acid finished product on the lenient side.In order to improve chemical reaction rate, make that it is particularly important that the present invention seems when reactor content was in low water concentration (0.1～4% weight ratio).
Particularly, methyl alcohol and CO are in the presence of VIII family oxo catalyst, in acetic acid synthesized, the side reaction of acetaldehyde takes place to generate, and constantly in process stream, change into other permanganate-reducing compound, but the overwhelming majority still exists with acetaldehyde ground form in reactive system, its by flash separation after, be gathered into the weight two-phase at light constituent distillation cat head, and the content (5～20 times) of content acetaldehyde in the heavy phase of acetaldehyde in the light constituent.
According to technical solution of the present invention, as shown in Figure 1, light phase materials a is sent into distillation tower A distill, obtain to comprise the overhead product of acetaldehyde and methyl-iodide from cat head, reflux at the bottom of the tower that obtains to comprise methyl-iodide, acetic acid and water at the bottom of the tower.After the described overhead product process condenser B condensation, a part refluxes and enters distillation tower A, another part enters extraction tower C and carries out extracting and separating, extraction agent b adopts water, the extraction liquid c that forms mainly is an acetaldehyde solution, it is effluxed and reason elsewhere, and raffinate then merges with reflux at the bottom of the tower of distillation tower A, constitute the material d of low acetaldehyde content, return the main reaction system.
Light phase materials is sent in the distillation tower still-process, the control tower operating parameters, feeding rate, pressure tower, tower still temperature, tower top temperature, reflux ratio etc., its objective is concentration according to acetaldehyde in the reactor, then accelerate the speed that removes of acetaldehyde as excessive concentration, normal as the concentration of acetaldehyde, then adjust the operating parameters of tower, thereby as much as possible promotors such as methyl-iodide are retained in the tower still, are circulated back to reactive system.
The present invention uses the method that detects acetaldehyde to be chemical fast detection method, and having overcome patent publication No. is CN1, and 926, the measurement material density that 088A announces is difficult to accurately to measure the drawback of the content of the acetaldehyde in the material.The method of chemistry rapid detection acetaldehyde is: take by weighing a certain amount of material, add excessive oxammonium hydrochloride, get final product with the alkali standard solution titration, method quick and precisely.
Moisture content 30～70% (weight ratio) and tower working pressure in the strict control of the present invention light constituent are 50～200KPa, make that the interior acetaldehyde of distillation tower can be as United States Patent (USP) 6,339,171 is disclosed such, acetaldehyde easy polymerization in the presence of methyl-iodide generates the polymkeric substance of higher molecular weight in distillation tower, these polymericular weights are higher than 1000, and easily adhere on the distillation tower inwall, extremely difficult removing, the working pressure by moisture in the control tower charging and tower can address the above problem well.
In order to reclaim promotor such as methyl-iodide as far as possible, the acetaldehyde that the distillation cat head steams by the water extraction to reclaim promotor such as methyl-iodide.Under the normal extraction conditions, the partition ratio of methyl-iodide in the extraction two-phase is bigger, be difficult to reach processing requirement, be 1.8% weight ratio generally speaking, although as U.S. Patent Publication No. CN1,926,088A is described, the adding dme can reduce methyl-iodide and be allocated in water, but still reaches about 0.8% weight ratio.The present application people finds under 0～10 ℃ of cold condition, and is forced into 100～1000KPa and extracts, and can greatly reduce methyl iodide because of the extraction loss.
Another characteristics of the present invention are to detect the decreasing ratio of the time control acetaldehyde of the permanganate-reducing compound in the finished product by control, thereby control the loss of promotors such as methyl-iodide.
The present invention proposes the process control of from the process stream of carbonyl synthesis acetic acid, removing the permanganate-reducing compound.Procedure is as follows: from the primary separation top of tower overhead product of carbonyl synthesis acetic acid gently mutually fractionation by distillation acetaldehyde, water extracting and separating acetaldehyde, thus remove the compound of permanganate-reducing, reduce the loss of promotors such as methyl-iodide simultaneously as much as possible.
With specific examples technical solution of the present invention is described further below, they are prominent example only, and the scope of the present invention is not constituted any limitation.
Embodiment 1
Delivering to the distillatory " light constituent " that distillation tower carries out consists of:
| Component | Methyl alcohol | Methyl iodide | Ritalin | Acetaldehyde | Acetic acid | Water |
| Content % | 1～5 | 2～8 | 1～6 | 0.5～3 | 30～60 | 40～70 |
40 meters of distillation tower heights are the structured packing of stainless steel ripple in 1 meter of the tower diameter, tower, and the light constituent feed rate is 60L/h, and tower still temperature is 100 ℃, 30 ℃ of tower top temperatures, and tower top pressure is 100KPa, reflux ratio 1: 1.The feed separation situation is as follows:
Cooling temperature of charge to 5 ℃ adds water coolant with 1: 1 ratio in material, control extraction tower pressure 150KPa, and material is composed as follows after the extracting and separating:
Embodiment 2
Delivering to the distillatory " light constituent " that distillation tower carries out consists of:
| Component | Methyl alcohol | Methyl iodide | Ritalin | Acetaldehyde | Acetic acid | Water |
| Content % | 1～5 | 2～8 | 1～6 | 0.5～3 | 30～60 | 40～70 |
40 meters of distillation tower heights are the structured packing of stainless steel ripple in 1 meter of the tower diameter, tower, and the light constituent feed rate is that 30L/h tower still temperature is 95 ℃, 25 ℃ of tower top temperatures, and tower top pressure is 50KPa, reflux ratio 3: 1.The feed separation situation is as follows:
Cooling temperature of charge to 0 ℃ adds water coolant with 1: 1 ratio in material, material is composed as follows after the control extraction tower pressure 300KPa extracting and separating:
The The above results contrast shows, technical solution of the present invention can control effectively to the acetaldehyde in the acetic acid synthesis from methanol carbonylation process, and can reduce the loss of promotors such as methyl-iodide, thereby reduce or remove the compound (PRC`S) of the permanganate-reducing that forms in the process of used for preparing acetic acid through carbonylation reaction product the most economically, improve the quality of acetic acid synthesis from methanol carbonylation finished product.
Claims (3)
1, the control method of acetaldehyde in the acetic acid synthesis from methanol carbonylation process, with VIII family metal as carbonylating catalyst, carry out carbonylation reaction by methyl alcohol and CO and generate acetic acid, it is characterized in that: in the main reaction system, after the flash distillation of carbonylation material, separate the volatile phase of formation through lights column, this is volatile through condensation separation formation " light phase " and " heavy phase ", wherein " light phase " all or part of distillation tower that is introduced into distills, obtain to comprise the overhead product of acetaldehyde and methyl-iodide from cat head, at the bottom of tower, obtain to comprise methyl-iodide, reflux at the bottom of the tower of acetic acid and water; Described overhead product is through after the condenser condenses, water extracts, the extraction liquid that contains acetaldehyde effluxes and manages elsewhere, and raffinate then returns the main reaction system with reflux at the bottom of the described tower, continues to finish each operation process of subsequent disposal with remaining " gently mutually ".
2, according to the control method of acetaldehyde in the acetic acid synthesis from methanol carbonylation process of claim 1, it is characterized in that: when extraction, water and material temperature are 0～15 ℃, and extracting pressure is 50～200KPa.
3, according to the control method of acetaldehyde in the acetic acid synthesis from methanol carbonylation process of claim 1 or 2, it is characterized in that: the feeding rate of the operating parameters of described distillation tower and the water of extraction process, be permanganate-reducing compound concentrations, and finally determine by the permanganate-reducing time of acetic acid finished product by rapid chemical assaying reaction district.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928212A (en) * | 2010-08-27 | 2010-12-29 | 南京扬池工业气体有限公司 | Method for intermittently recycling and separating light component waste in production of acetic acid |
| CN101935271A (en) * | 2010-08-27 | 2011-01-05 | 南京扬池工业气体有限公司 | Continuous recovery and separation method of light-component wastes in acetic acid production |
| US8889904B2 (en) | 2010-05-18 | 2014-11-18 | Celanese International Corporation | Processes for producing acetic acid |
| CN107986953A (en) * | 2017-12-06 | 2018-05-04 | 江苏索普（集团）有限公司 | The process units and production technology of a kind of synthesizing acetic acid by methanol low-pressure carbonylation |
| CN109232223A (en) * | 2018-11-02 | 2019-01-18 | 江苏索普（集团）有限公司 | A kind of technique synthesizing acetic acid |
| CN109415291A (en) * | 2016-07-07 | 2019-03-01 | 株式会社大赛璐 | Acetic acid manufacturing process |
| CN113600109A (en) * | 2021-08-17 | 2021-11-05 | 江苏索普工程科技有限公司 | Micro-interface reaction system and method for preparing acetic acid through methanol carbonylation |
-
2008
- 2008-11-04 CN CNA2008102349204A patent/CN101391946A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8889904B2 (en) | 2010-05-18 | 2014-11-18 | Celanese International Corporation | Processes for producing acetic acid |
| US9409848B2 (en) | 2010-05-18 | 2016-08-09 | Celanese International Corporation | Processes for producing acetic acid |
| US9149735B2 (en) | 2010-05-18 | 2015-10-06 | Celanese International Corporation | Processes for producing acetic acid |
| CN101928212B (en) * | 2010-08-27 | 2012-11-21 | 南京扬池工业气体有限公司 | Method for intermittently recycling and separating light component waste in production of acetic acid |
| CN101928212A (en) * | 2010-08-27 | 2010-12-29 | 南京扬池工业气体有限公司 | Method for intermittently recycling and separating light component waste in production of acetic acid |
| CN101935271B (en) * | 2010-08-27 | 2012-07-04 | 南京扬池工业气体有限公司 | Continuous recovery and separation method of light-component wastes in acetic acid production |
| CN101935271A (en) * | 2010-08-27 | 2011-01-05 | 南京扬池工业气体有限公司 | Continuous recovery and separation method of light-component wastes in acetic acid production |
| CN109415291A (en) * | 2016-07-07 | 2019-03-01 | 株式会社大赛璐 | Acetic acid manufacturing process |
| CN109415291B (en) * | 2016-07-07 | 2022-01-04 | 株式会社大赛璐 | Acetic acid manufacturing process |
| CN107986953A (en) * | 2017-12-06 | 2018-05-04 | 江苏索普（集团）有限公司 | The process units and production technology of a kind of synthesizing acetic acid by methanol low-pressure carbonylation |
| CN107986953B (en) * | 2017-12-06 | 2021-07-23 | 江苏索普化工股份有限公司 | Production device and production process for synthesizing acetic acid by methanol low-pressure carbonyl |
| CN109232223A (en) * | 2018-11-02 | 2019-01-18 | 江苏索普（集团）有限公司 | A kind of technique synthesizing acetic acid |
| CN113600109A (en) * | 2021-08-17 | 2021-11-05 | 江苏索普工程科技有限公司 | Micro-interface reaction system and method for preparing acetic acid through methanol carbonylation |
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Application publication date: 20090325 |