Distillation: processes – separatory – With measuring – testing or inspecting – Of concentration
Reexamination Certificate
2001-03-20
2003-08-12
Manoharan, Virginia (Department: 1764)
Distillation: processes, separatory
With measuring, testing or inspecting
Of concentration
C203S018000, C203S078000, C203S079000, C203S080000, C203S099000, C203SDIG001, C568S868000, C568S916000
Reexamination Certificate
active
06605192
ABSTRACT:
This invention relates to a process for producing high purity monoethylene glycol. Monoethylene glycol is industrially produced by hydrolysis of ethylene oxide, dewatering and purifying distillation. To improve the selectivity of the ethylene oxide (hereinafter abbreviated to EO) hydrolysis, the hydrolysis reactor is operated using a large excess of water (water:EO weight ratio=4:1 to 15:1). This makes it possible to suppress the fraction of higher glycols, especially diethylene glycol, triethylene glycol, etc. The hydrolysis reactor is customarily operated at temperatures of 120 to 250° C. and pressures of 30-40 bar. The hydrolysis product is initially dewatered, to a residual water content of 100-200 ppm, and then separated into the various glycols in pure form.
The dewatering is generally carried out in a battery of pressure-graduated columns, with decreasing pressure. For heat integration reasons, generally only the bottoms reboiler of the first pressure column is heated with external steam, whereas all the other pressure columns are heated with the vapors from the preceding column. The feed enters each column at a point below the first plate, since no stripping section is required to separate water and glycols. Depending on the water content of the hydrolysis reactor effluent and on the pressure/temperature level of the external steam used in the first column's bottoms reboiler, the pressure dewatering battery comprises from 2 to 7 columns. The pressure dewatering stage is followed by a vacuum dewatering stage, which generally takes place in a column equipped with a stripping section. The water obtained from the dewatering is returned to a point upstream of the hydrolysis reactor. The dewatered glycol mixture is separated into the pure materials in a plurality of columns. Monoethylene glycol, diethylene glycol and triethylene glycol are each withdrawn as top-of-column product, while all other higher glycols are obtained in the form of a mixture known as polyethylene glycols as the bottom product of the last column.
Conventional glycol plants, in addition to the product streams, customarily have only a further single outlet, the acetaldehyde purge at the bottoms reboiler of the second pressure dewatering column. There, the uncondensed fraction of the first column's vapors used for heating is removed from the system. Thus, secondary components, either carried into the glycol plant by the water/EO stream or formed in the glycol plant as a consequence of secondary reactions, can only be removed from the system via the acetaldehyde purge or via the product streams. The latter impairs product quality and so is undesirable.
Hitherto, glycol plants were optimized only with regard to their principal functions, especially with regard to energy and capital costs reduction for the dewatering and purifying distillation. Of late, increasingly tougher requirements are being placed on the product quality of monoethylene glycol, especially with regard to the level of secondary components. There are two monoethylene glycol product qualities: technical grade (antifreeze grade) with lower purity requirements, for use as coolant, and fiber grade, with strict requirements, for use in fiber manufacture, for example. The exact specification of fiber grade varies with the customer, but for free aldehydes, reckoned as acetaldehyde, spectrophotometrically assayed as blue MBTH complex, it generally envisages the range from 7 to 20 ppm and for the minimum UV transmission it generally envisages 76%-80% at 220 nm and 90%-95% at 275 nm. The contributors to the free aldehydes measurement are in particular formaldehyde, acetaldehyde and glycolaldehyde. The UV-active substances, known as UV spoilers, are largely unknown, but are specification-destructive even in concentrations of less than 1 ppm. Examples are acrolein and crotonaldehyde.
JP-A-60,089,439 describes a process for purifying glycol by vacuum distillation with a supply of inert gas. The nitrogen stream strips out a portion of the secondary components to leave a high purity glycol which is suitable for fiber manufacture. However, the process has the disadvantage that large amounts of nitrogen are needed for effective removal of secondary components. This leads to undesirable product losses in the exit gas and to an excessively large fluid-dynamic stress on the distillation column.
DE-A-1 942 094 describes a process for purifying monoethylene glycols by steam distillation in a stripping column, the steam increasing the volatility of the impurities with regard to monoethylene glycol.
CA-C-1330350 describes a process for purifying monoethylene glycol by addition of bisulfite ions and subsequent treatment with anion exchange resins.
There are also purification processes for monoethylene glycol where the formation of secondary components is said to be reduced by special measures in the area of apparatus construction and the materials of construction used for the apparatus. DE-A-19 602 116 describes a purification process for monoethylene glycol in an apparatus whose surface has been treated with reducing phosphorus compounds.
However, the abovementioned processes have the disadvantage of requiring additives or additional equipment-based measures to recover high purity monoethylene glycol.
It is an object of the present invention to provide a simple distillative process for recovering high purity monoethylene glycol, without the use of additives or of specific materials of construction. Specification-destructive secondary components are to be removed from the system in predominantly aqueous waste streams having glycol contents of not more than 1% by weight and the secondary components in the waste streams are to be concentrated by a factor of 10-100, since too much wastewater is produced otherwise.
We have found that this object is achieved by a process for the distillative recovery of high purity monoethylene glycol from the hydrolysis product of ethylene oxide by pressure dewatering, preferably in a battery, vacuum dewatering and subsequent purifying distillation, which comprises withdrawing during the vacuum dewatering an aqueous stream which contains monoethylene glycol in a concentration below 1% by weight, preferably below 0.1% by weight, medium boilers and low boilers and which, optionally after further workup, is removed from the system.
Particular preference is given to a process in which, in addition to the abovementioned solution, the pressure dewatering takes place in a dewatering column having a stripping section with at least one separating stage, preferably with from 2 to 10 separating stages, particularly preferably with from 3 to 6 stages, and in which a portion of the overhead stream of the dewatering column(s) having a stripping section is removed from the system.
It was determined that removal of specification-destructive secondary components is particularly effective at certain locations in the process. Identifying these locations in the process is not a trivial matter, since the complex phase equilibria have hitherto made it impossible to arrive at a sufficiently confident assessment of the behavior of the secondary components. For this reason, conventional large industrial processes have only a very coarse outlet for extremely low boiling secondary components, the acetaldehyde purge at the bottoms reboiler of the second pressure dewatering column. This outlet is not optimized, since the behavior of the secondary components was largely unknown and was not taken into account at the process design stage.
The components are herein subdivided into three classes with regard to their boiling range:
1. low boilers, having a volatility greater than that of water (especially acetaldehyde, formaldehyde in pure water, acrolein),
2. medium boilers, having a volatility between that of water and monoethylene glycol (especially formaldehyde in glycol-containing aqueous solutions, formaldehyde in anhydrous monoethylene glycol, glycolaldehyde, crotonaldehyde), and
3. high boilers, having a lower volatility than monoethylene glyco
Adrian Till
Bessling Bernd
Hasse Hans
Theis Gerhard
Vansant Frans
BASF - Aktiengesellschaft
Keil & Weinkauf
Manoharan Virginia
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