Method of purifying glyoxylic esters and distillation equipment for purifying glyoxylic esters

A method for purifying glyoxylates includes (1) a coarse distillation process in which a crude glyoxylate in which water coexists is, in a film form, continuously subjected to coarse distillation, and (2) an azeotropic dehydration process in which the crude glyoxylate purified through the coarse distillation process is subjected to azeotropic dehydration in the presence of an azeotropic agent such as propyl acetate. By this method, high-purity glyoxylates can be efficiently and easily obtained at lower costs.

TECHNICAL FIELD 
The present invention relates to a method for purifying glyoxylates and a 
distiller for purification of glyoxylates. 
BACKGROUND ART 
Glyoxylates are chemical intermediates, for example, monomers suitably used 
as material for synthesizing sodium polyglyoxylate which is an effective 
builder component of a surface active agent. 
In the case where the glyoxylates to be used as material for forming 
polymers contain impurities, particularly protic compounds such as water, 
alcohols, or carboxylic acids, a molecular weight of the resultant polymer 
tends to decrease. Therefore, when such glyoxylates are used as material 
for copolymers, the impurities have to be removed from the glyoxylates. 
However, since the glyoxylates reversibly combine with water or alcohols in 
particular thereby forming hydrate, hemiacetal, or the like, to purify the 
glyoxylates is not easy. 
The following purifying methods applicable to the glyoxylates have been 
proposed: 
(1) executing distillation, with phosphoric anhydride added to a material 
containing glyoxylates; 
(2) adding a higher alcohol with a boiling point of not lower than 
180.degree. to a material containing glyoxylates, and executing 
distillation at a pressure not exceeding 800 mmHg (107 kPa) (the Japanese 
Publication for Laid-Open Patent Application No.62-178541/1987 (Tokukaisho 
62-178541)); 
(3) distilling a mixture containing glyoxylates, glycolates, water, 
alcohols, and the like under a reduced pressure so that a content of water 
and alcohols decreases to less than 1 weight percent (wt. %), then, 
distilling it by adjusting so that a molar ratio of glycolate to 
glyoxylates becomes 1 to 1.4 (the Japanese Examined Patent Publication 
No.5-28694/1993 (Tokukohei 5-28694), the Japanese Publication for 
Laid-Open Patent Application No.60-97936/1985 (Tokukaisho 60-97936)); 
(4) when glyoxylates are produced from corresponding glycolates by 
oxidative dehydrogenation in a gaseous phase, adding an azeotropic agent 
such as methylene chloride, chloroform, n-pentane, cyclohexane, nonane, 
di-isopropyle ether, methyl ethyl ketone, benzene, toluene, or the like to 
a gaseous reaction mixture resulting on the oxidative dehydrogenation, and 
introducing the same to a distillation column (the Japanese Publication 
for Laid-Open Patent Application No.60-23345/1985 (Tokukaisho 60-23345)); 
(5) esterifying glyoxylic acid by reacting 1 mol of glyoxylic acid with 0.5 
to 2 mol of lower alcohol in the presence of an azeotropic agent such as 
benzene or dichloroethane, and distilling the same after a concentration 
of water and alcohol in the reactive solution becomes not more than 10 wt. 
% each with respect to the resultant glyoxylates (the Japanese Publication 
for Laid-Open Patent Application No.61-50941/1985 (Tokukaisho 61-50941), 
the Japanese Examined Patent Publication No.4-66856/1992 (Tokukohei 
4-66856)); and 
(6) processing a reaction product obtained by oxidative dehydrogenation 
with respect to glycolates under a reduced pressure, then, supplying the 
reaction product thus processed to a multi-stage distillation column which 
holds a dense azeotropic agent such as methylene-dichloride, 
1,1,1-trichloroethane, or benzene in the vicinity of its top, so that 
glyoxylates are taken from an intermediate point between the supplying 
part and the top part of the distillation column (the Japanese Examined 
Patent Publication No.7-42252/1995 (Tokukohei 7-42252), the Japanese 
Publication for Laid-Open Patent Application No.2-73040/1990 (Tokukaihei 
2-73040), the Japanese Examined Patent Publication No.7-45435/1995 
(Tokukohei 7-45435), the Japanese Publication for Laid-Open Patent 
Application No.1-254643/1989 (Tokukaihei 1-254643), the Japanese Examined 
Patent Publication No.5-28694/1993 (Tokukohei 5-28694)). 
However, the method (1) is not preferable from an economic viewpoint, since 
phosphoric anhydride is consumed reacting with water or alcohols and hence 
it is hardly recovered. The method (2) has a drawback in that side 
reactions such as ester interexchange and the like may possibly occur. 
Moreover, since the method (3) requires excessive glycolates, the method 
(3) has a drawback in that productivity lowers due to the presence of the 
excessive glycolates. For these reasons, it is impossible to efficiently 
produce high-purity glyoxylates by the above methods (1) through (3). 
Furthermore, as a result of various examinations by the inventors of the 
present application, the azeotropic agents used in the methods (4) and (5) 
exhibit insufficient performances, and high-purity glyoxylates are hardly 
obtained at a high yield with the use of the above azeotropic agents. 
Besides, in the case where a chemical compound such as benzene or 
trichloroethane is used as an azeotropic agent as in the case of the 
method (6), such a compound is toxic and it is difficult to deal with it. 
In the aforementioned conventional methods, prior to a purification process 
whereby water is removed by azeotropy, coarse distillation for 
preliminarily concentrating glyoxylates in crude glyoxylates is carried 
out so that the purification is efficiently conducted, by utilizing a 
distillation column. 
However, by the above conventional methods, the glyoxylates in the crude 
glyoxylates are, during coarse distillation, subjected to heating for a 
long period of time thereby becoming hydrolyzed. This causes a yield of 
the glyoxylates obtained through the purification process to decrease, 
thereby disenabling efficient production of high-purity glyoxylates. 
Moreover, by the conventional methods, the glyoxylic acid produced through 
hydrolyzation is further resolved by a subsequent distillation process, 
thereby producing side products. Therefore, a content of the glyoxylates 
to be obtained lowers, leading to a drawback in that a purification 
efficiency of the glyoxylates deteriorates. 
DISCLOSURE OF THE INVENTION 
The object of the invention is to provide a method for purifying 
glyoxylates and a distiller for purifying glyoxylates, whereby the 
high-purity glyoxylates can be efficiently and conveniently obtained at 
lower costs. 
As a result of the inventors' eager study in order to achieve the above 
object, it was found that by continuously conducting coarse distillation 
with respect to a crude glyoxylate in a film form in which water coexists, 
and/or distilling the same with the use of aliphatic ester as azeotropic 
agent, high-purity glyoxylate can be efficiently and conveniently obtained 
at lower costs. The present invention was completed based on this finding. 
It should be noted that it has not yet been known that in the purification 
of the glyoxylates, an excellent dehydrating effect can be achieved by 
using aliphatic esters as azeotropic agents, and as a result high-purity 
glyoxylates can be obtained. 
Specifically, to achieve the above object, the method of the present 
invention for purifying the glyoxylates is characterized in comprising an 
azeotropic dehydration step of conducting azeotropic dehydration with 
respect to a crude glyoxylate in which water coexists, in the presence of 
an aliphatic ester as an azeotropic agent. 
By the foregoing method, removal of water from the crude glyoxylate can be 
efficiently carried out by using the aliphatic ester as the azeotropic 
agent. This ensures that a high-purity glyoxylate suitable as a polymer 
material can be efficiently and easily obtained at lower costs. Moreover, 
the purifying method of the present invention is superior in safety and 
handling, since, unlike the conventional methods, a toxic chemical 
compound is not used as an azeotropic agent. 
Furthermore, to achieve the aforementioned object, another method of the 
present invention for purifying the glyoxylates is characterized in 
comprising a coarse distillation step of continuously conducting coarse 
distillation with respect to a crude glyoxylate in a film form in which at 
least water coexists, and a main distillation step of further distilling a 
crude purified liquid obtained by the coarse distillation step, the liquid 
containing glyoxylate. 
According to the foregoing method, low-boiling-point components such as 
water which have lower boiling points than that of the glyoxylate are 
decreased in the crude glyoxylate by coarse distillation process, and 
subsequently, the coarsely purified liquid is purified by the main 
distillation process. As a result, a high-purity glyoxylate is obtained. 
Besides, in the above method, by continuously conducting the coarse 
distillation with respect to the glyoxylate in a film form, a heating time 
in the coarse distillation with respect to the crude glyoxylate is 
decreased as compared with cases where conventional distillation columns 
are used. Therefore, hydrolization of the glyoxylate in the coarse 
distillation is suppressed, allowing a high-purity glyoxylate to be 
obtained at a high yield. 
Furthermore, by making the main distillation process include the 
aforementioned azeotropic dehydration process using the azeotropic agent, 
it is possible to obtain high-purity glyoxylates at further higher yield. 
For a fuller understanding of the nature and advantages of the invention, 
reference should be made to the ensuing detailed description taken in 
conjunction with the accompanying drawings.

BEST MODE FOR CARRYING OUT THE INVENTION 
The following description will explain an embodiment of the present 
invention in detail. 
A method of the present invention for purifying glyoxylates is a method 
wherein coarse distillation is continuously conducted with respect to a 
crude glyoxylate in a film form, in which water coexists, and/or the crude 
glyoxylate is distilled with the use of an aliphatic ester as an 
azeotropic agent. Example of such a glyoxylate to be processed are 
compounds which are expressed by the following formula (1): 
##STR1## 
where R.sub.3 represents an organic residual group. 
In the formula (1), a substituent represented by R.sub.3 is not 
particularly limited as long as it is an organic residual group. Examples 
of the substituent include hydrocarbon groups such as a methyl group, an 
ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 
sec-butyl group, and a tert-butyl group. 
In other words, no specific glyoxylates are preferred, but concretely 
speaking, examples of the glyoxylates include methyl glyoxylate, ethyl 
glyoxylate, n-propyl glyoxylate, isopropyl glyoxylate, n-butyl glyoxylate, 
sec-butyl glyoxylate, and tert-butyl glyoxylate. The purifying method of 
the present invention is effectively applied to methyl glyoxylate in 
particular among the glyoxylates. 
The glyoxylates processed by the method of the present invention are 
compounds which are preferably used as chemical intermediates, such as 
monomers for synthesizing sodium polyglyoxylate which is an effective 
builder component such as a surface active agent. No specific method for 
producing the glyoxylates is particularly preferable, and various methods 
which have conventionally been known can be used. For example, oxidization 
in a gas phase is conducted with respect to (1) glyoxal and/or glycol 
aldehyde, plus (2) alcohol or olefin, in the presence of oxygen and a 
catalyst. By doing so, desired crude glyoxylates can be easily obtained. 
Besides, production conditions of the glyoxylates, that is, reaction 
conditions such as a reaction temperature and a reaction time are not 
particularly limited. They may be appropriately set so that the reaction 
is completed. 
The glyoxylates resulting on the reaction, that is, the crude glyoxylates 
not yet purified, contain, as side products of the reaction, a plurality 
of impurities such as components having lower boiling points than those of 
the glyoxylates. The crude glyoxylates may be used as they are, but in the 
case where they are used as polymer materials, contents of the impurities, 
particularly protic compounds such as water, alcohols, and carboxylic 
acids have to be sufficiently small. 
However, the glyoxylates reversibly react with water or alcohols in 
particular among the impurities, thereby forming hydrates, hemiacetal, or 
the like, and hence to purify the glyoxylates is not easy. 
The following description will explain, referring to FIG. 1, an example of 
a concrete purifying method of the present invention applied to the 
glyoxylates, that is, a sequence of distillation processes including the 
azeotropic dehydration. 
The sequence of distillation processes of the present invention including 
the azeotropic dehydration can be carried out by performing the following 
two steps in this order: (i) a coarse distillation step for obtaining 
crude purified liquid by removing a majority of low-boiling-point 
components from a treated liquid which is a crude glyoxylate containing 
the low-boiling-point components; and (ii) a main distillation step for 
further purifying the crude purified liquid by distillation. In the coarse 
distillation step, from a liquid of the crude glyoxylates containing 
low-boiling-point components such as water, a majority of the 
low-boiling-point components are removed, so that the crude purified 
liquid is obtained. 
The main distillation step includes an azeotropic dehydration step whereby 
an azeotropically purified liquid is obtained by removing residual water 
from the crude purified liquid by azeotropic dehydration, and a 
fractionating step whereby the glyoxylates of high purity (not less than 
95 percent) are obtained from the azeotropically purified liquid by 
fractionating. 
In each step, any scheme of a batch distillation type or a continuous 
distillation type can be applicable by the use of various conventional 
distillation devices. The following description will explain the sequence 
of processes composed of the coarse distillation step, the azeotropic 
dehydration step, and the fractionating step, taking as an example a case 
where the continuous distillation scheme is applied to each step. 
It is preferable to start the process sequence with continuous coarse 
distillation with respect to a crude glyoxylate in a film form. The crude 
glyoxylate is a material mixture containing a glyoxylate, and 
low-boiling-point components including water. In the above step, to 
perform the coarse distillation as described above, it is preferable to 
remove from the crude glyoxylate a majority of low-boiling-point 
components including water which are contained in the crude glyoxylate, by 
utilizing a thin film evaporator (a liquid-film-type distillation device, 
a low-boiling-point component distillation device) 1. 
It should be noted that operational conditions such as a temperature, a 
pressure, and a rate of supply of the material may be appropriately set, 
in accordance with a composition of the material mixture, but it is 
desirable that the operation is carried out at as low a pressure as 
possible so that a temperature of a bottom product becomes low, with view 
to lowering the heat history. On the other hand, if the operation is 
carried out at an extremely low pressure, an excessive performance is 
required of a condenser for recovering distillate vapor, thereby leading 
to economic disadvantages. A preferable pressure range is 30 mmHg to 760 
mmHg (4kPa to 101 kPa), and a more preferable range is 200 mmHg to 500 
mmHg (27 kPa to 67 kPa). 
Furthermore, from a viewpoint of suppressing the heat history during the 
operation, a residence time of the crude glyoxylate in the coarse 
distillation step is preferably as short as possible in a range such that 
as uniform a film as possible is formed. On the other hand, from a 
viewpoint of improving the purification efficiency in the coarse 
distillation step, the residence time is preferably long. Therefore, in 
practice, the residence time is preferably set in a range of 0.1 to 20 
minutes, and more preferably in a range of 0.1 to 10 minutes. 
The liquid film in the coarse distillation step preferably has a small 
thickness in a range such that the film is uniformly formed. Concretely, a 
preferable range of the thickness is 0.1 to 3 mm, and a more preferable 
range is 0.1 to 2 mm. Furthermore, a range of 0.1 to 1 mm is particularly 
preferable. 
The bottom product, that is, for example, the bottom product from the 
column bottom of the thin-film evaporator 1 is used as a material 
subjected to the subsequent azeotropic dehydration step. A predetermined 
quantity of an azeotropic agent, for example, 0.5 to 4 times a volume of 
the bottom product, is added to the bottom product resulting on the 
foregoing coarse distillation operation (step), and it is used as the 
material in the azeotropic dehydration step. 
The material is continuously supplied to a material supply stage which is 
provided between the column top and the column bottom of an azeotropic 
dehydration column (distillation column) 2, through a material supply tube 
(not shown). Note that a position of the material supply tube in the 
azeotropic dehydration column 2, that is, a position of the material 
supply stage, is not particularly limited. Besides, the processed liquid 
through the azeotropic dehydration is continuously taken out of the 
processing system, that is, the azeotropic dehydration column 2, as a 
bottom product and a distillate, through a bottom product discharging tube 
and a distillate discharging tube which are not shown. 
Here, the bottom product discharging tube may be set, for example, at the 
bottom (the lowest stage) of the azeotropic dehydration column 2, while 
the distillate discharging tube may be set at the top (the highest stage) 
of the azeotropic dehydration column 2, but there is no particular 
limitation on their positions. By doing so, a distillate composed of an 
aliphatic ester as the azeotropic agent, water, and other 
low-boiling-point components is obtained from the distillate discharging 
tube (column top) of the azeotropic dehydration column 2, while a bottom 
product composed of (i) a glyoxylate, (ii) hemiacetal resulting on 
reaction between a glyoxylate and alcohols including glycolates, ethylene 
glycol, and the like, and (iii) other higher-boiling-point impurities is 
obtained from the bottom product discharging tube (column bottom). 
Processing conditions in the azeotropic dehydration step, i.e., the number 
of stages of the azeotropic dehydration column 2, a temperature, a 
pressure, and an material supply amount (supply rate), and others are not 
particularly limited, but are appropriately determined by experiments or 
computations depending on a composition of the material. However, the 
operation is preferably executed so that water and the azeotropic agent 
remaining in the bottom product account for not more than 0.2 wt. % and 
not more than 0.5 wt. %, respectively. Besides, such an azeotropic 
dehydration process may be repeated a plurality of times if necessary, to 
achieve a higher dehydrating effect. For example, in the case where the 
azeotropic dehydration process is conducted twice, the first operation may 
be carried out in conditions such that the azeotropic agent is distributed 
to the column bottom so that the crude glyoxylate and the azeotropic agent 
are brought into full contact with each other in the column, and the 
second operation may be carried out in operational conditions such that 
the azeotropic agent does not reach the column bottom so that the 
azeotropic agent would not remain in the bottom product. 
The bottom product is used as a material subjected to the subsequent 
fractionating process. From an economic viewpoint, however, it is 
preferable that the aliphatic esters in the distillate are separated from 
water by gravity separation and are purified and re-used. 
Subsequently, in the fractionating process, the bottom product obtained 
through the previous azeotropic dehydration operation (process) is 
continuously supplied to a supply stage provided between a column top and 
a column bottom of a fractionating distillation column (distillation 
column) 3, so as to be used as a material subjected to the fractionating 
process. By doing so, a high-purity glyoxylate is obtained as distillate 
from, for example, the column top of the fractionating distillation column 
3, while a bottom product composed of a residual glyoxylate, hemiacetals 
of the glyoxylate and alcohols, and other high-boiling-point impurities is 
obtained from, for example, the column bottom of the fractionating 
distillation column 3. 
Furthermore, from an economic viewpoint, it is preferable that the bottom 
product of the fractionating distillation column 3 is supplied to another 
distillation column so that high-boiling-point residues are separated 
therefrom, and the glyoxylate and hemiacetals of the glyoxylates which are 
left may be returned to the azeotropic dehydration process. 
An aliphatic ester is preferable as an azeotropic agent applied to the 
azeotropic dehydration process. The glyoxylates are purified easily and 
safely by azeotropic dehydration with the use of such aliphatic ester. 
The exact reason why the aliphatic esters are effective as the azeotropic 
agents is still unknown, but it is presumed that it may be related to 
properties of the aliphatic esters, namely, sufficient affinity with the 
glyoxylates and a small compatibility with water. 
The aliphatic esters used as the azeotropic agents in the present invention 
are not particularly limited, but to be more concrete, compounds expressed 
by the following formula (2) are given as examples of the same: 
EQU R.sub.1 COOR.sub.2 (2) 
where R.sub.1 represents hydrogen, a methyl group, or an ethyl group, while 
R.sub.2 represents an alkyl group with 1 to 4 carbons. Among these 
aliphatic esters, n-propyl acetate and isopropyl acetate are particularly 
preferable. 
Any one of the aliphatic esters forms a low-boiling azeotropic mixture with 
water. The low-boiling azeotropic mixtures have azeotropic points, 
respectively, which are sufficiently lower than those of the glyoxylates. 
Moreover, the compatibility thereof with water is low, and hence they are 
easily separated from water by gravity separation. Therefore, if 
particularly necessary, it is possible to purify them for re-use. 
A quantity of an aliphatic ester to be added to a crude glyoxylate is not 
particularly limited, and processing conditions such as a temperature, a 
pressure, and a processing time (the number of distillation column stages) 
of the process system are not particularly limited, either. However, the 
temperature in the system is preferably high within a range such that a 
side reaction does not occur, so that separation and removal of water 
which exists chemically combined with the glyoxylate is promoted. 
A method for adding the aliphatic esters is not particularly limited, and 
various conventional methods are applicable. Among them, the following 
method is preferable: a desired set amount of an aliphatic ester is added 
to, and mixed with, a crude glyoxylate in advance, and the resultant 
mixture is continuously supplied to, for example, a middle stage of the 
distillation column. More preferable is the following method: the 
glyoxylates are supplied to the distillation column in advance, and after 
a majority of low-boiling-point components such as water is removed from 
the same by the coarse distillation operation, a desired set amount of the 
aliphatic ester is added to and mixed with the remnant (residue), and 
thereafter, the mixture is continuously supplied to, for example, a middle 
stage of the distillation column. 
According to the present invention, by the use of the aliphatic esters as 
the azeotropic agents, water is easily removed from the crude glyoxylates 
due to the azeotropic dehydration. By doing so, high-purity glyoxylates 
which are preferably used as polymer materials are efficiently and easily 
obtained at lower costs. 
Moreover, the purifying method of the present invention is superior in 
safety and handling, since, unlike the conventional methods, a toxic 
chemical compound is not used as an azeotropic agent. On top of that, the 
glyoxylates purified by the aforementioned purifying method have high 
quality, and are suitably applied to the aforementioned purposes. 
As a thin-film evaporator (liquid-film-type distillation device) 1 applied 
to the coarse distillation process, various public known liquid-film-type 
evaporators are applicable. The liquid-film-type evaporators are 
evaporators wherein treated liquid is formed in a thin film form and is 
brought into contact with a heated surface. Such evaporators are 
classified into the categories such as an ascending film type, a falling 
film type, and a forced agitation type. Among them, either the falling 
film type or the forced agitation type is preferable for the present 
invention. 
As the thin film evaporator 1 of the forced-agitation liquid-film type, one 
shown in FIGS. 2 through 4 is taken as example, which is equipped with a 
rotary vane for agitating the treated liquid while controlling a thickness 
of the liquid film. 
The thin film evaporator 1 is equipped with, from the top, a driving unit 
11 for driving a motor and the like, an evaporating-condensing unit 12 in 
a cylindrical form beneath the driving unit 11, and a liquid receiving 
unit 13 in a cylindrical form with a bottom, which is connected with the 
evaporating-condensing unit 12. 
Inside the evaporating-condensing unit 12, a rotor 14 driven by the driving 
unit 11 is rotatably provided so as to be coaxial with the 
evaporating-condensing unit 12. Therefore, a circumferential surface of 
the rotor 14 is at a substantially uniform distance from an evaporating 
surface as an inner surface of the evaporating-condensing unit 12, that 
is, a heating surface 12a. The evaporating-condensing unit 12 is equipped 
with a jacket 12b for controlling a temperature of the heating surface 12a 
by passage of heated water or the like so that the jacket 12b covers an 
outer surface of the wall having the heating surface 12a inside. 
On the circumferential surface of the rotor 14, there are installed wipers 
15 for rubbing an inner surface of the evaporating-condensing unit 12. The 
wipers 15 are formed in a rectangular blade shape each, so that their 
lengthwise direction conforms an axial direction of the rotor 14, and they 
can be extruded in radial directions of the rotor 14. Therefore, on the 
circumferential surface of the rotor 14, there are provided wiper holding 
members 16, which are formed in a groove form each for holding the wipers 
15 so that the wipers 15 are freely extruded therefrom and accommodated 
therein. A plurality of the wiper holding members 16 are provided thereon 
at regular intervals in a circumferential direction of the rotor 14. 
Furthermore, on a rubbing surface of each wiper 15, a plurality of grooves 
15a are provided (1) so as to be oblique with respect to a rubbing 
direction, with their head ends being on an upstream side of the falling 
treated liquid, while their rear ends being on a downstream side of the 
treated liquid, and (2) so as to be parallel with each other. 
On a top of the rotor 14, there is provided a liquid distributing disk 17 
in a disk form which rotates in an interlocked manner with the rotor 14. 
The liquid distributing disk 17 has a plurality notched nozzles (not 
shown) on its circumferential surface. The notched nozzles are to evenly 
distribute the treated liquid over the inner surface of the heating 
surface 12a by using the centrifugal force, the treated liquid being to 
become the crude glyoxylates through the process and being supplied into 
the evaporating-condensing unit 12 through a material inlet 11a. 
The aforementioned driving unit 11 is adjusted depending on the size and 
other factors of the evaporating-condensing unit 12 so that the rotor 14 
has an appropriate number of rotations corresponding to a circumferential 
speed of about 4 to 5 m/s. Besides, shaft seal parts (not shown) of the 
driving unit 11 are provided with mechanical seals, whereby sealing is 
enabled in high vacuum at a level of 10.sup.-4 Torr (0.013 Pa). 
The liquid receiving unit 13 is equipped with a condensed liquid 
discharging outlet 13a through which the remnant is taken out as a bottom 
product (crude purified liquid). There may be provided a scraper (not 
shown) in a bottom part of the rotor 14, so that the scraper pushes out 
the remnant that now has a high viscosity, through a lower part of the 
heating surface 12a to the liquid receiving unit 13. 
Furthermore, mist separators (not shown) for separating mist of the treated 
liquid from vapor and returning it to the treated liquid may be provided 
between neighboring wipers 15. 
In addition, a recovering column 18 with a necessary minimum number of 
distillation stages for recovering the glyoxylate contained in vapor 
discharged from the column top may be provided to a vapor outlet lib of 
the thin film evaporator 1. The number of the distillation stages and a 
height of packing section are appropriately determined depending on a 
distillate composition, operational conditions, a type of a column 
packing, and the like. A condenser 19 for recovering toxic components 
contained in the vapor discharged from the column top of the recovering 
column 18, such as an organic solvent, may be connected with the 
recovering column 18. The thin film evaporator 1 is vacuumed through the 
condenser 19, and by doing so, the pressure-reduced state in the thin film 
evaporator 1 is maintained. 
The following description will explain operations of the thin film 
evaporator. First, the treated liquid supplied through the material inlet 
11a is distributed through each notched nozzle of the liquid distributing 
disk 17 by the centrifugal force evenly over the heating surface 12a. The 
heating surface 12a to which the treated liquid is thus evenly applied is 
rubbed by the wipers 15, which are pressed against the heating surface 12a 
by the centrifugal force due to the rotation of the rotor 14. Therefore, 
each wiper 15 contributes to form a thin film of the treated liquid with a 
uniform thickness (0.1 to 3 mm) on the heating surface 12a, while renewing 
a surface portion of the treated liquid film. 
Each groove 15a of the wipers 15 prevents scatter of the treated liquid 
which may be caused by the wipers 15, and, since each groove 15a is formed 
obliquely with respect to the rubbing direction, it deliberately causes 
the treated liquid to go down in the liquid falling direction. 
Here, vapor of the treated liquid (crude glyoxylate) flowing down on the 
heating surface 12a is taken out from the thin film evaporator 1 through 
the vapor outlet 11b provided on the column top thereof, by sucking. On 
the other hand, a heat medium (heated water or pressurized steam) is sent 
in through a heat medium inlet 12d in a lower portion of the jacket 12b, 
while the heat medium is taken out through a heat medium outlet 12c in an 
upper portion of the jacket 12b. 
By supplying the heat medium in such a direction, the jacket 12b for 
controlling the temperature of the heating surface 12a is caused to have 
such a temperature gradient as causes a temperature of the heating surface 
12a gradually to lower in a direction reverse to a moving direction of the 
treated liquid on the heating surface 12a. This vapor sucking direction 
and this heat medium supplying direction makes the coarse distillation of 
the treated liquid (crude glyoxylate) efficient. 
Thus, by the above method, low-boiling-point components including water is 
continuously removed from the treated liquid by distillation, by keeping 
the treated liquid in a film form with a uniform thickness while allowing 
it to flow down, preferably at a reduced pressure realized by discharging 
vapor through the vapor outlet 11b. 
Thus, by the above method wherein the treated liquid, in a film form, is 
continuously processed, the heat conduction efficiency with respect to the 
treated liquid is enhanced, thereby enabling quick removal of the 
low-boiling-point components in the treated liquid. Therefore, a time 
while the treated liquid stays on the heating surface 12a, that is, a 
heating time, can be reduced, as compared with a case where a conventional 
distillation column is used. 
Thus, the above method has the following advantages: (1) hydrolization of 
the glyoxylate in the treated liquid which tends to occur in the 
distilling process when the heating time increases is avoided, thereby 
efficiently increasing the content of the glyoxylates in the crude 
glyoxylates obtained through the coarse distillation process; and (2) 
production of glyoxylic acids which are impurities generated in the 
hydrolization is avoided. 
Therefore, by the aforementioned method, the efficient purification of the 
glyoxylate is enabled with simple operations. Besides, by the 
aforementioned method, a composition of the vapor discharged is kept 
substantially uniform by continuously processing the treated liquid in a 
film form. Therefore, in the case where the recovering column is provided 
at the vapor outlet, even if recovering conditions are kept constant, 
degradation of the recovery efficiency is avoidable in the aforementioned 
method. As a result, the purification of the glyoxylates is simplified 
while the high yield is ensured. 
It should be noted that a case where the thin film evaporator of the 
falling film type is used in the coarse distillation process is taken as 
example to explain the above method, but it is possible to use a thin film 
evaporator of the liquid film ascending type. 
In such a liquid-film-ascending-type evaporator, by boiling the treated 
liquid in a vertical long tube, the remnant of the treated liquid ascends 
accompanying the rise of generated vapor. As the remnant rises upwards, it 
comes to boil, and a quantity of the vapor gradually increases in an upper 
part of the long tube. Therefore, bubbles in the long tube grow, and in a 
further upper part of the tube, vapor rapidly rises therethrough, causing 
the remnant to rise in a film form along the tube wall. Thus, from the 
remnant which ascends in the film form, the low-boiling-point components 
are efficiently removed. 
Furthermore, in the above description on the aforementioned method, (1) a 
case where the thin film evaporator 1 is used in the coarse distillation 
process, and (2) a case where one of the aliphatic esters is used as an 
azeotropic agent in the azeotropic dehydration process, are separately 
explained, but combination of these may be applicable. By such 
combination, the efficiency in purification of the glyoxylates is 
heightened. 
The following description will more concretely explain the present 
invention, by showing examples and comparative examples, but the present 
invention is not limited by these examples. 
[EXAMPLE 1] 
(1) Coarse distillation Process 
To start with, methanol accounting for 53.0 wt. %, water accounting for 
22.0 wt. %, formaldehyde accounting for 3.0 wt. %, methyl glyoxylate which 
is a glyoxylate, accounting for 20.0 wt. %, and methyl glycolate which is 
a glycolate, accounting for 2.0 wt. %, were supplied as starting material 
(crude glyoxylate) to a low-boiling-point component distillation device, 
and light-boiling-point components including water were removed by coarse 
distillation in predetermined conditions. By doing so, a bottom product 
composed of 20.9 wt. % of methanol, 15.0 wt. % of water, 2.1 wt. % of 
formaldehyde, 56.1 wt. % of methyl glyoxylate, and 5.9 wt. % of methyl 
glycolate was obtained. Here, a mass balance of the glyoxylate in the 
whole system was 100 wt. %. 
(2) Azeotropic Dehydration Process 
Then, a predetermined quantity of n-propyl acetate as an azeotropic agent 
was added to the bottom product thus obtained through the above operation, 
and a mixture composed of 5.4 wt. % of methanol, 3.9 wt. % of water, 0.6 
wt. % of formaldehyde, 14.5 wt. % of methyl glyoxylate, 1.5 wt. % of 
methyl glycolate, and 74.1 wt. % of n-propyl acetate was obtained. 
Subsequently, the mixture was supplied to an azeotropic dehydration column 
2 having 30 stages in a condensing section, 20 stages in a recovering 
section, and an inside diameter of 30 mm, at a rate of 0.45 kg/h, so that 
the mixture was subjected to azeotropic distillation (azeotropic 
dehydration). Here, a pressure inside the system was maintained at 300 
mmHg, and temperatures at a material supply stage, a column bottom, and a 
column top were 80.degree. C., 150.degree. C., and 75.degree. C., 
respectively. 
As a result, a bottom product composed of 6.7 wt. % of methanol, 0.1 wt. % 
of water, 84.2 wt. % of methyl glyoxylate, 8.9 wt. % of methyl glycolate, 
and 0.1 wt. % of n-propyl acetate was obtained from the column bottom, 
while a distillate composed of 5.2 wt. % of methanol, 4.7 wt. % of water, 
0.6 wt. % of formaldehyde, and 89.5 wt. % of n-propyl acetate was obtained 
from the column top. A mass balance of the methyl glyoxylate before and 
after the above operation was 100 wt. %. 
(3) Fractionating Process 
Subsequently, the bottom product obtained through the azeotropic 
dehydration process was supplied to a fractionating distillation column 3 
having 50 stages in a condensing section, 20 stages in a recovering 
section and an inside diameter of 30 mm, at a rate of 0.45 kg/h, so that 
methyl glyoxylate was obtained by the fractionating. Here, a pressure 
inside the system and a reflux ratio were maintained at 600 mmHg and 10, 
respectively, while temperatures at a material supply stage, a column 
bottom, and a column top were 120.degree. C., 155.degree. C., and 
110.degree. C., respectively. 
As a result, methyl glyoxylate with a purity of 99.4 percent was obtained 
from the column top, and in this fraction, 0.1 wt. % of methanol, 0.2 wt. 
% of water, and 0.3 wt. % of n-propyl acetate were contained as 
impurities. From the column bottom, a bottom product composed of 11.5 wt. 
% of methanol, 0.1 wt. % of water, 73.0 wt. % of methyl glyoxylate, and 
15.4 wt. % of methyl glycolate was obtained. A mass balance of the methyl 
glyoxylate before and after the above fractionating operation was 100 wt. 
%. 
[EXAMPLE 2] 
(1) Coarse distillation Process 
Light-boiling-point components including water were removed by the same 
operation as that in Example 1 except that a starting material (crude 
glyoxylate) composed of the following was used: 50.0 wt. % of methanol; 
22.0 wt. % of water; 4.0 wt. % of formaldehyde; 18.0 wt. % of methyl 
glyoxylate; and 6.0 wt. % of methyl glycolate. 
As a result, a bottom product composed of 19.7 wt. % of methanol, 14.2 wt. 
% of water, 1.9 wt. % of formaldehyde, 47.5 wt. % of methyl glyoxylate, 
and 16.7 wt. % of methyl glycolate was obtained. Here, a mass balance of 
the glyoxylate in the whole system was 100 wt. %. 
(2) Azeotropic Dehydration Process 
Then, a predetermined quantity of n-propyl acetate as an azeotropic agent 
was added to the bottom product thus obtained through the above operation, 
and a mixture composed of 2.5 wt. % of methanol, 1.8 wt. % of water, 0.2 
wt. % of formaldehyde, 6.0 wt. % of methyl glyoxylate, 2.1 wt. % of methyl 
glycolate, and 87.4 wt. % of n-propyl acetate was obtained. The mixture 
was supplied to the same azeotropic dehydration column 2 as that in 
Example 1, at a rate of 0.45 kg/h, so that the mixture was subjected to 
azeotropic distillation. Here, a pressure inside the system was maintained 
at 300 mmHg, and temperatures at a material supply stage, a column bottom, 
and a column top were 72.degree. C., 150.degree. C., and 65.degree. C., 
respectively. 
As a result, a bottom product composed of 6.1 wt. % of methanol, 0.1 wt. % 
of water, 69.4 wt. % of methyl glyoxylate, and 24.4 wt. % of methyl 
glycolate was obtained from the column bottom, while a distillate composed 
of 2.1 wt. % of methanol, 1.9 wt. % of water, 0.3 wt. % of formaldehyde, 
and 95.7 wt. % of n-propyl acetate was obtained from the column top. A 
mass balance of the methyl glyoxylate before and after the above operation 
was 100 wt. %. 
(3) Fractionating Process 
Subsequently, the bottom product obtained through the azeotropic 
dehydration process was supplied to the same fractionating distillation 
column 3 as that in Example 1, at a rate of 0.45 kg/h, so that methyl 
glyoxylate was obtained by the fractionating. Here, a pressure inside the 
system and a reflux ratio were maintained at 600 mmHg and 10, 
respectively, while temperatures at a material supply stage, a column 
bottom, and a column top were 119.degree. C., 155.degree. C., and 
110.degree. C., respectively. 
As a result, methyl glyoxylate with a purity of 99.8 percent was obtained 
from the column top, and in this fraction, 0.1 wt. % of methanol and 0.1 
wt. % of water were contained as impurities. From the column bottom, a 
bottom product composed of 9.2 wt. % of methanol, 0.1 wt. % of water, 53.3 
wt. % of methyl glyoxylate, and 37.4 wt. % of methyl glycolate was 
obtained. A mass balance of the methyl glyoxylate before and after the 
above fractionating operation was 100 wt. %. 
[EXAMPLE 3] 
(1) Azeotropic Dehydration Process 
A predetermined quantity of isopropyl acetate as an azeotropic agent was 
added to a bottom product obtained through the same operation as that in 
the coarse distillation process of Example 1, which is composed of 20.9 
wt. % of methanol, 15.0 wt. % of water, 2.1 wt. % of formaldehyde, 56.1 
wt. % of methyl glyoxylate, and 5.9 wt. % of methyl glycolate. Then, a 
mixture composed of 4.5 wt. % of methanol, 3.3 wt. % of water, 0.5 wt. % 
of formaldehyde, 12.2 wt. % of methyl glyoxylate, 1.3 wt. % of methyl 
glycolate, and 78.2 wt. % of isopropyl acetate was obtained. 
The mixture was supplied to the same azeotropic dehydration column 2 as 
that in Example 1, at a rate of 0.45 kg/h, so that the mixture was 
subjected to azeotropic distillation. Here, a pressure inside the system 
was maintained at 300 mmHg, and temperatures at a material supply stage, a 
column bottom, and a column top were 75.degree. C., 145.degree. C., and 
69.degree. C., respectively. 
As a result, a bottom product composed of 6.3 wt. % of methanol, 0.1 wt. % 
of water, 84.7 wt. % of methyl glyoxylate, and 8.9 wt. % of methyl 
glycolate was obtained from the column bottom, while a distillate composed 
of 4.2 wt. % of methanol, 3.8 wt. % of water, 0.5 wt. % of formaldehyde, 
and 91.5 wt. % of isopropyl acetate was obtained from the column top. A 
mass balance of the methyl glyoxylate before and after the above operation 
was 100 wt. %. 
(2) Fractionating Process 
Subsequently, the bottom product obtained through the azeotropic 
dehydration process was supplied to the same fractionating distillation 
column 3 as that in Example 1, at a rate of 0.45 kg/h, so that methyl 
glyoxylate was obtained by the fractionating. Here, a pressure inside the 
system and a reflux ratio were maintained at 600 mmHg and 10, 
respectively, while temperatures at a material supply stage, a column 
bottom, and a column top were 120.degree. C., 155.degree. C., and 
110.degree. C., respectively. As a result, methyl glyoxylate with a purity 
of 99.8 percent was obtained from the column top, and in this fraction, 
0.1 wt. % of methanol and 0.1 wt. % of water were contained as impurities. 
From the column bottom, a bottom product composed of 10.5 wt. % of 
methanol, 0.1 wt. % of water, 74.6 wt. % of methyl glyoxylate, and 14.8 
wt. % of methyl glycolate was obtained. A mass balance of the methyl 
glyoxylate before and after the above fractionating operation was 100 wt. 
%. 
[COMATIVE EXAMPLE 1] 
(1) Azeotropic Dehydration Process 
A predetermined quantity of dichloromethane as an azeotropic agent for 
comparison was added to a bottom product obtained through the same 
operation as that in the coarse distillation process of Example 1, which 
is composed of 20.9 wt. % of methanol, 15.0 wt. % of water, 2.1 wt. % of 
formaldehyde, 56.1 wt. % of methyl glyoxylate, and 5.9 wt. % of methyl 
glycolate. Then, a mixture composed of 1.3 wt. % of methanol, 0.9 wt. % of 
water, 0.1 wt. % of formaldehyde, 3.6 wt. % of methyl glyoxylate, 0.4 wt. 
% of methyl glycolate, and 93.7 wt. % of dichloromethane was obtained. 
The mixture was supplied to the same azeotropic dehydration column 2 as 
that in Example 1, at a rate of 0.45 kg/h, so that the mixture was 
subjected to azeotropic distillation. Here, a pressure inside the system 
was maintained at 300 mmHg, and temperatures at a material supply stage, a 
column bottom, and a column top were 20.degree. C., 150.degree. C., and 
17.degree. C., respectively. 
As a result, a bottom product composed of 8.6 wt. % of methanol, 1.7 wt. % 
of water, 81.2 wt. % of methyl glyoxylate, and 8.5 wt. % of methyl 
glycolate was obtained from the column bottom, while a distillate composed 
of 1.0 wt. % of methanol, 0.9 wt. % of water, 0.1 wt. % of formaldehyde, 
and 98.0 wt. % of dichloromethane was obtained from the column top. A mass 
balance of the methyl glyoxylate before and after the above operation was 
100 wt. %. 
(2) Fractionating Process 
Subsequently, the bottom product obtained through the azeotropic 
dehydration process was subjected to fractionating in the same manner as 
that in Example 1 by the use of the same fractionating distillation column 
3 as that in Example 1, so that methyl glyoxylate was obtained. 
As a result, methyl glyoxylate with a purity of 97.7 percent was obtained 
from the column top, and in this fraction, 0.2 wt. % of methanol and 2.1 
wt. % of water were contained as impurities. From the column bottom, a 
bottom product composed of 14.5 wt. % of methanol, 1.5 wt. % of water, 
69.4 wt. % of methyl glyoxylate, and 14.6 wt. % of methyl glycolate was 
obtained. A mass balance of the methyl glyoxylate before and after the 
above fractionating operation was 100 wt. %. 
[COMATIVE EXAMPLE 2] 
(1) Azeotropic Dehydration Process 
Cyclohexane as an azeotropic agent for comparison was added to a bottom 
product obtained through the same operation as that in the coarse 
distillation process of Example 1, which is composed of 20.9 wt. % of 
methanol, 15.0 wt. % of water, 2.1 wt. % of formaldehyde, 56.1 wt. % of 
methyl glyoxylate, and 5.9 wt. % of methyl glycolate. Then, a mixture 
composed of 2.5 wt. % of methanol, 1.8 wt. % of water, 0.2 wt. % of 
formaldehyde, 6.7 wt. % of methyl glyoxylate, 0.7 wt. % of methyl 
glycolate, and 88.1 wt. % of cyclohexane was obtained. 
The mixture was supplied to the same azeotropic dehydration column 2 as 
that in Example 1, at a rate of 0.45 kg/h, so that the mixture was 
subjected to azeotropic distillation. Here, a pressure inside the system 
was maintained at 300 mmHg, and temperatures at a material supply stage, a 
column bottom, and a column top were 53.degree. C., 150.degree. C., and 
45.degree. C., respectively. 
As a result, a bottom product composed of 7.7 wt. % of methanol, 2.0 wt. % 
of water, 81.7 wt. % of methyl glyoxylate, and 8.6 wt. % of methyl 
glycolate was obtained from the column bottom, while a distillate composed 
of 2.0 wt. % of methanol, 1.8 wt. % of water, 0.3 wt. % of formaldehyde, 
and 95.9 wt. % of cyclohexane was obtained from the column top. A mass 
balance of the methyl glyoxylate before and after the above operation was 
100 wt. %. 
(2) Fractionating Process 
Subsequently, the bottom product obtained through the azeotropic 
dehydration process was subjected to fractionating in the same manner as 
that in Example 1 by the use of the same fractionating distillation column 
3 as that in Example 1, so that methyl glyoxylate was obtained. As a 
result, methyl glyoxylate with a purity of 97.5 percent was obtained from 
the column top, and in this fraction, 0.2 wt. % of methanol and 2.3 wt. % 
of water were contained as impurities. From the column bottom, a bottom 
product composed of 13.2 wt. % of methanol, 1.7 wt. % of water, 70.3 wt. % 
of methyl glyoxylate, and 14.8 wt. % of methyl glycolate was obtained. A 
mass balance of the methyl glyoxylate before and after the above 
fractionating operation was 100 wt. %. 
As clear from the results of the examples and the comparative examples, by 
the purifying method of the present invention, high-purity glyoxylates can 
be obtained from crude glyoxylates. 
[EXAMPLE 4] 
(1) Coarse distillation Process 
Methanol accounting for 35.8 wt. %, water accounting for 24.7 wt. %, 
formaldehyde accounting for 6.4 wt. %, methyl glyoxylate which is a 
glyoxylate, accounting for 28.8 wt. %, and methyl glycolate which is a 
glycolate, accounting for 4.3 wt. %, were supplied as starting material 
(crude glyoxylate) at a rate of 0.2 kg/h to a thin film evaporator of the 
forced-agitation liquid-film type having a 450 cm.sup.2 heating surface. 
Here, a temperature of the heating surface was set to 90.degree. C., and a 
pressure inside was maintained at 350 mmHg (47 kPa). As a result, a 
distillate composed of 54.7 wt. % of methanol, 36.7 wt. % of water, 6.4 
wt. % of formaldehyde, and 2.2 wt. % of methyl glyoxylate was obtained 
from the column top, while a bottom product composed of 22.7 wt. % of 
methanol, 16.5 wt. % of water, 6.4 wt. % of formaldehyde, 47.2 wt. % of 
methyl glyoxylate, and 7.3 wt. % of methyl glycolate was obtained from the 
column bottom. 
Here, no glyoxylic acid was produced due to hydrolyzation of methyl 
glyoxylate, and a mass balance of methyl glyoxylate through the coarse 
distillation process was 100 wt. %. 
(2) Azeotropic Dehydration Process 
Then, n-propyl acetate as an azeotropic agent was added to the bottom 
product thus obtained through the above operation, and a mixture composed 
of 10.3 wt. % of methanol, 7.4 wt. % of water, 2.9 wt. % of formaldehyde, 
21.3 wt. % of methyl glyoxylate, 3.3 wt. % of methyl glycolate, and 54.8 
wt. % of n-propyl acetate was obtained. 
Subsequently, the mixture was supplied to an azeotropic dehydration column 
2 having 30 stages in a condensing section, 20 stages in a recovering 
section, and an inside diameter of 30 mm, at a rate of 0.25 kg/h, so that 
the mixture was subjected to azeotropic dehydration. Here, a pressure 
inside the system and a reflux ratio were maintained at the atmospheric 
pressure and 0.2, respectively, while temperatures at a material supply 
stage, a column bottom, and a column top were 116.degree. C., 157.degree. 
C., and 85.degree. C., respectively. 
As a result, a bottom product composed of 4.0 wt. % of methanol, 0.1 wt. % 
of water, 83.0 wt. % of methyl glyoxylate, 12.9 wt. % of methyl glycolate, 
and 0.1 wt. % of n-propyl acetate was obtained from the column bottom, 
while a distillate composed of 12.4 wt. % of methanol, 10.0 wt. % of 
water, 3.9 wt. % of formaldehyde, and 73.7 wt. % of n-propyl acetate was 
obtained from the column top. A mass balance of the methyl glyoxylate 
before and after the above operation was 100 wt. %. 
(3) Fractionating Process 
Subsequently, the bottom product obtained through the above azeotropic 
dehydration process was supplied to a fractionating distillation column 3 
having 50 stages in a condensing section (height of packing section of 
1200 mmL), 20 stages (height of packing section of 300 mmL) in a 
recovering section, and an inside diameter of 24 mm, at a rate of 0.13 
kg/h, so that methyl glyoxylate was obtained by the fractionating. Here, a 
pressure inside the system and a reflux ratio were maintained at 600 mmHg 
(80 kPa) and 3, respectively, while temperatures at a material supply 
stage, a column bottom, and a column top were 124.degree. C., 165.degree. 
C., and 113.degree. C., respectively. 
As a result, methyl glyoxylate with a purity of 99.7 percent was obtained 
from the column top, and in this fraction, 0.1 wt. % of methanol, 0.1 wt. 
% of water, and 0.1 wt. % of n-propyl acetate were contained as 
impurities. From the column bottom, a bottom product composed of 5.3 wt. % 
of methanol, 0.1 wt. % of water, 77.4 wt. % of methyl glyoxylate, and 17.0 
wt. % of methyl glycolate was obtained. A mass balance of the methyl 
glyoxylate before and after the above fractionating operation was 100 wt. 
%. 
[EXAMPLE 5] 
(1) Coarse distillation Process 
The same coarse distillation process as that in Example 4 was carried out 
except that a starting material composed of 35.4 wt. % of methanol, 25.4 
wt. % of water, 3.4 wt. % of formaldehyde, 30.5 wt. % of methyl 
glyoxylate, and 5.3 wt. % of methyl glycolate was used, and that a 
temperature of the heating surface was set to 120.degree. C. As a result, 
a distillate composed of 52.3 wt. % of methanol, 35.8 wt. % of water, 4.0 
wt. % of formaldehyde, and 6.5 wt. % of methyl glyoxylate was obtained 
from the column top, while a bottom product composed of 15.7 wt. % of 
methanol, 12.9 wt. % of water, 2.7 wt. % of formaldehyde, 58.8 wt. % of 
methyl glyoxylate, and 9.9 wt. % of methyl glycolate was obtained from the 
column bottom. 
Here, no glyoxylic acid was produced due to hydrolyzation of methyl 
glyoxylate, and a mass balance of methyl glyoxylate through the coarse 
distillation process was 100 wt. %. 
(2) Azeotropic Dehydration Process 
n-propyl acetate as an azeotropic agent was added to the bottom product 
thus obtained through the above operation, and a mixture composed of 8.1 
wt. % of methanol, 6.6 wt. % of water, 1.4 wt. % of formaldehyde, 30.1 wt. 
% of methyl glyoxylate, 5.1 wt. % of methyl glycolate, and 48.7 wt. % of 
n-propyl acetate was obtained. The azeotropic dehydration operation was 
carried out in the same manner as that in Example 4 except that this 
mixture was used. 
As a result, a bottom product composed of 2.2 wt. % of methanol, 0.1 wt. % 
of water, 83.5 wt. % of methyl glyoxylate, 14.0 wt. % of methyl glycolate, 
and 0.1 wt. % of n-propyl acetate was obtained from the column bottom, 
while a distillate composed of 11.3 wt. % of methanol, 10.3 wt. % of 
water, 2.2 wt. % of formaldehyde, and 76.2 wt. % of n-propyl acetate was 
obtained from the column top. A mass balance of the methyl glyoxylate 
before and after the above operation was 100 wt. %. 
(3) Fractionating Process 
Subsequently, the bottom product obtained through the above azeotropic 
dehydration process was subjected to the same fractionating process as 
that in Example 1. As a result, methyl glyoxylate with a purity of 99.8 
percent was obtained from the column top, and in this fraction, 0.1 wt. % 
of water and 0.1 wt. % of n-propyl acetate were contained as impurities. 
From the column bottom, a bottom product composed of 2.9 wt. % of 
methanol, 0.1 wt. % of water, 78.1 wt. % of methyl glyoxylate, and 18.8 
wt. % of methyl glycolate was obtained. A mass balance of the methyl 
glyoxylate before and after the above fractionating operation was 100 wt. 
%. 
[EXAMPLE 6] 
(1) Coarse distillation Process 
Methanol accounting for 37.0 wt. %, water accounting for 26.1 wt. %, 
formaldehyde accounting for 3.5 wt. %, methyl glyoxylate accounting for 
28.4 wt. %, and methyl glycolate accounting for 5.0 wt. % were used as 
starting material (crude glyoxylate). The material was subjected to the 
same coarse distillation process as that in Example 5, except that a 
packed column for recovery of methyl glyoxylate, which has a height of 
packing section of 150 mm corresponding to 3 distillation stages, was 
connected with the thin film evaporator at a vapor outlet thereof, and 
that a reflux ratio was set to 0.2. 
As a result, a distillate composed of 56.5 wt. % of methanol, 38.2 wt. % of 
water, and 5.3 wt. % of formaldehyde was obtained from the column top, 
while a bottom product composed of 12.2 wt. % of methanol, 10.7 wt. % of 
water, 1.2 wt. % of formaldehyde, 64.5 wt. % of methyl glyoxylate, and 
11.4 wt. % of methyl glycolate was obtained from the column bottom. 
Here, no glyoxylic acid was produced due to hydrolyzation of methyl 
glyoxylate, and a mass balance of methyl glyoxylate through the coarse 
distillation process was 100 wt. %. 
(2) Azeotropic Dehydration Process 
n-propyl acetate as an azeotropic agent was added to the bottom product 
thus obtained through the above operation, and a mixture composed of 6.8 
wt. % of methanol, 6.0 wt. % of water, 0.7 wt. % of formaldehyde, 36.1 wt. 
% of methyl glyoxylate, 6.4 wt. % of methyl glycolate, and 44.1 wt. % of 
n-propyl acetate was obtained. The azeotropic dehydration operation was 
carried out in the same manner as that in Example 4 except that this 
mixture was used. 
As a result, a bottom product composed of 1.6 wt. % of methanol, 0.1 wt. % 
of water, 83.5 wt. % of methyl glyoxylate, 14.8 wt. % of methyl glycolate, 
and 0.1 wt. % of n-propyl acetate was obtained from the column bottom, 
while a distillate composed of 10.8 wt. % of methanol, 10.5 wt. % of 
water, 1.2 wt. % of formaldehyde, and 77.6 wt. % of n-propyl acetate was 
obtained from the column top. A mass balance of the methyl glyoxylate 
before and after the above operation was 100 wt. %. 
(3) Fractionating Process 
Subsequently, the bottom product obtained through the above azeotropic 
dehydration process was subjected to the fractionating process in the same 
manner as that in Example 4. As a result, methyl glyoxylate with a purity 
of 99.8 percent was obtained from the column top, and in this fraction, 
0.1 wt. % of water and 0.1 wt. % of n-propyl acetate were contained as 
impurities. From the column bottom, a bottom product composed of 2.1 wt. % 
of methanol, 0.1 wt. % of water, 78.1 wt. % of methyl glyoxylate, and 19.7 
wt. % of methyl glycolate was obtained. A mass balance of the methyl 
glyoxylate before and after the above fractionating operation was 100 wt. 
%. 
[EXAMPLE 7] 
(1) Coarse distillation Process 
The same coarse distillation operation was carried out except that methanol 
accounting for 35.8 wt. %, water accounting for 24.7 wt. %, formaldehyde 
accounting for 6.4 wt. %, methyl glyoxylate accounting for 28.8 wt. %, and 
methyl glycolate accounting for 4.3 wt. % were used as starting material 
(crude glyoxylates). 
As a result, a distillate composed of 54.7 wt. % of methanol, 36.7 wt. % of 
water, 6.4 wt. % of formaldehyde, and 2.2 wt. % of methyl glyoxylate was 
obtained from the column top, while a bottom product composed of 22.7 wt. 
% of methanol, 16.5 wt. % of water, 6.4 wt. % of formaldehyde, 47.2 wt. % 
of methyl glyoxylate, and 7.3 wt. % of methyl glycolate was obtained from 
the column bottom. 
Here, no glyoxylic acid was produced due to hydrolyzation of methyl 
glyoxylate, and a mass balance of methyl glyoxylate through the coarse 
distillation process was 100 wt. %. 
(2) Azeotropic Dehydration Process 
Cyclohexane as an azeotropic agent was added to the bottom product thus 
obtained through the above operation, and a mixture composed of 7.2 wt. % 
of methanol, 5.2 wt. % of water, 2.0 wt. % of formaldehyde, 15.0 wt. % of 
methyl glyoxylate, 2.3 wt. % of methyl glycolate, and 68.3 wt. % of 
cyclohexane was obtained. The azeotropic dehydration operation was carried 
out in the same manner as that in Example 4 except that this mixture was 
used. 
As a result, a bottom product composed of 4.0 wt. % of methanol, 1.3 wt. % 
of water, 82.1 wt. % of methyl glyoxylate, 12.6 wt. % of methyl glycolate, 
and a trace of cyclohexane was obtained from the column bottom, while a 
distillate composed of 7.9 wt. % of methanol, 6.1 wt. % of water, 2.5 wt. 
% of formaldehyde, and 83.5 wt. % of cyclohexane was obtained from the 
column top. A mass balance of the methyl glyoxylate before and after the 
above operation was 100 wt. %. 
(3) Fractionating Process 
Subsequently, the bottom product obtained through the above azeotropic 
dehydration process was subjected to the fractionating process in the same 
manner as that in Example 4. As a result, methyl glyoxylate with a purity 
of 98.9 percent was obtained from the column top, and in this fraction, 
0.1 wt. % of water, 1.1 wt. % of methanol, and a trace of cyclohexane were 
contained as impurities. From the column bottom, a bottom product composed 
of 5.2 wt. % of methanol, 1.4 wt. % of water, 76.2 wt. % of methyl 
glyoxylate, and 16.8 wt. % of methyl glycolate was obtained. A mass 
balance of the methyl glyoxylate before and after the above fractionating 
operation was 100 wt. %. 
[CONVENTIONAL EXAMPLE 1] 
(1) Coarse distillation Process 
The same crude glyoxylate as that in Example 1 was supplied to a tray-type 
distillation column having 10 stages, at a rate of 0.2 kg/h. Here, a 
pressure inside the system was maintained at 350 mmHg, while temperatures 
at a material supply stage, a column bottom, and a column top were 
70.degree. C., 75.degree. C., and 62.degree. C. As a result, a distillate 
composed of 61.8 wt. % of methanol, 31.7 wt. % of water, and 6.5 wt. % of 
formaldehyde was obtained from the column top, while a bottom product 
composed of 9.7 wt. % of methanol, 14.5 wt. % of water, 6.4 wt. % of 
formaldehyde, 52.3 wt. % of methyl glyoxylate, 9.2 wt. % of methyl 
glycolate, and 7.9 wt. % of glyoxylic acids was obtained from the column 
bottom. 
Here, a mass balance of methyl glyoxylate through the distillation 
operation as the coarse distillation process was 85 wt. %, and the rest 15 
wt. % was lost through the production of glyoxylic acids due to 
hydrolyzation of methyl glyoxylate. 
(2) Azeotropic Dehydration Process 
Then, cyclohexane as an azeotropic agent was added to the bottom product 
thus obtained through the above operation, and a mixture composed of 3.4 
wt. % of methanol, 5.0 wt. % of water, 2.2 wt. % of formaldehyde, 18.1 wt. 
% of methyl glyoxylate, 3.2 wt. % of methyl glycolate, 2.7 wt. % of 
glyoxylic acids, and 65.5 wt. % of cyclohexane was obtained. The 
azeotropic dehydration operation was carried out in the same manner as 
that in Example 1, except that this mixture was used. 
As a result, a bottom product composed of 1.4 wt. % of methanol, 1.1 wt. % 
of water, 73. 5 wt. % of methyl glyoxylate, 13.0 wt. % of methyl 
glycolate, 11.2 wt. % of unknown components, and a trace of cyclohexane 
was obtained from the column bottom, while a distillate composed of 4.0 
wt. % of methanol, 6.3 wt. % of water, 2.9 wt. % of formaldehyde, and 86.8 
wt. % of cyclohexane was obtained from the column top. 
(3) Fractionating Process 
Subsequently, the bottom product obtained through the above azeotropic 
dehydration process was subjected to the same fractionating operation as 
that in Example 1. As a result, methyl glyoxylate with a purity of 98.8 
percent was obtained from the column top, and in this fraction, 0.1 wt. % 
of methanol, 1.1 wt. % of water, and a trace of cyclohexane were contained 
as impurities. From the column bottom, a bottom product composed of 1.8 
wt. % of methanol, 1.1 wt. % of water, 65.0 wt. % of methyl glyoxylate, 
17.2 wt. % of methyl glycolate, and 14.8 wt. % of unknown components was 
obtained. 
[EXAMPLE 8] 
(1) Coarse distillation Process 
Methanol accounting for 35.8 wt. %, water accounting for 24.7 wt. %, 
formaldehyde accounting for 6.4 wt. %, methyl glyoxylate accounting for 
28.8 wt. %, and methyl glycolate accounting for 4.3 wt. % were, as 
starting material (crude glyoxylate), supplied to the same 
forced-agitation thin-film type evaporator (low-boiling-point component 
distillation device) as that in Example 4, where low-boiling-point 
components including water were removed. By doing so, a bottom product 
composed of 22.7 wt. % of methanol, 16.5 wt. % of water, 6.4 wt. % of 
formaldehyde, 47.2 wt. % of methyl glyoxylate, and 7.2 wt. % of methyl 
glycolate was obtained. 
Here, no glyoxylic acid was produced due to hydrolyzation of methyl 
glyoxylate, and a mass balance of methyl glyoxylate through the coarse 
distillation process was 100 wt. %. 
(2) Azeotropic Dehydration Process 
n-propyl acetate as an azeotropic agent was added to the bottom product 
thus obtained through the above operation, and a mixture composed of 10.3 
wt. % of methanol, 7.4 wt. % of water, 2.9 wt. % of formaldehyde, 21.3 wt. 
% of methyl glyoxylate, 3.3 wt. % of methyl glycolate, and 54.8 wt. % of 
n-propyl acetate was obtained. 
Subsequently, the mixture was supplied to a tray column (azeotropic 
dehydration column) having 30 stages in a condensing section, 20 stages in 
a recovering section, and an inside diameter of 30 mm, at a rate of 0.25 
kg/h, so that the mixture was subjected to azeotropic dehydration. Here, a 
pressure inside the system and a reflux ratio were set to atmospheric 
pressure and 0.3, respectively, while temperatures at a material supply 
stage, a column bottom, and a column top were 116.degree. C., 157.degree. 
C., and 85.degree. C., respectively. 
As a result, a bottom product composed of 4.0 wt. % of methanol, 0.1 wt. % 
of water, 83.0 wt. % of methyl glyoxylate, 12.8 wt. % of methyl glycolate, 
and 0.1 wt. % of n-propyl acetate was obtained from the column bottom, 
while a distillate composed of 12.4 wt. % of methanol, 10.0 wt. % of 
water, 3.9 wt. % of formaldehyde, and 73.7 wt. % of n-propyl acetate was 
obtained from the column top. A mass balance of the methyl glyoxylate 
before and after the above operation was 100 wt. %. 
(3) Fractionating Process 
Subsequently, the bottom product obtained through the above azeotropic 
dehydration process was supplied to a fractionating distillation-use 
packed column having 50 stages in a condensing section, 20 stages in a 
recovery section, and an inside diameter of 30 mm, at a rate of 0.2 kg/h. 
Herein, a pressure inside the system and a reflux ratio were set to 600 
mmHg (80 kPa) and 3, respectively, while temperatures at a material supply 
stage, a column bottom, and a column top were 124.degree. C., 165.degree. 
C., and 113.degree. C., respectively. 
As a result, methyl glyoxylate with a purity of 99.7 percent was obtained 
from the column top, and in this fraction, 0.1 wt. % of methanol, 0.1 wt. 
% of water, and 0.1 of n-propyl acetate were contained as impurities. From 
the column bottom, a bottom product composed of 5.3 wt. % of methanol, 0.1 
wt. % of water, 77.4 wt. % of methyl glyoxylate, and 17.0 wt. % of methyl 
glycolate was obtained. A mass balance of the methyl glyoxylate before and 
after the above fractionating operation was 100 wt. %. 
[EXAMPLE 9] 
(1) Coarse distillation Process 
By carrying out the coarse distillation process in the same manner as that 
in Example 8, a bottom product composed of 22.7 wt. % of methanol, 16.5 
wt. % of water, 6.4 wt. % of formaldehyde, 47.2 wt. % of methyl 
glyoxylate, and 7.2 wt. % of methyl glycolate was obtained. 
Here, no glyoxylic acid was produced due to hydrolyzation of methyl 
glyoxylate, and a mass balance of methyl glyoxylate through the coarse 
distillation process was 100 wt. %. 
(2) Azeotropic Dehydration Process 
The bottom product obtained through the fractionating operation in Example 
8 was added to the bottom product obtained through the above coarse 
distillation operation, and n-propyl acetate as an azeotropic agent was 
also added thereto. As a result, a mixture composed of 7.6 wt. % of 
methanol, 3.6 wt. % of water, 1.4 wt. % of formaldehyde, 50.2 wt. % of 
methyl glyoxylate, 10.4 wt. % of methyl glycolate, and 26.2 wt. % of 
n-propyl acetate was obtained. 
Subsequently, the mixture was subjected to the same azeotropic dehydration 
operation as that in Example 8. As a result, a bottom product composed of 
5.5 wt. % of methanol, 0.1 wt. % of water, 81.3 wt. % of methyl 
glyoxylate, 16.8 wt. % of methyl glycolate, and 0.1 wt. % of n-propyl 
acetate was obtained from the column bottom, while a distillate composed 
of 10.9 wt. % of methanol, 9.1 wt. % of water, 3.6 wt. % of formaldehyde, 
and 68.4 wt. % of n-propyl acetate was obtained from the column top. A 
mass balance of the methyl glyoxylate before and after the above operation 
was 100 wt. %. 
(3) Fractionating Process 
Subsequently, the bottom product obtained through the above azeotropic 
dehydration process was subjected to the same fractionating operation as 
that in Example 8. As a result, methyl glyoxylate with a purity of 99.5 
percent was obtained from the column top, and in this fraction, 0.1 wt. % 
of water, and 0.4 of n-propyl acetate were contained as impurities. From 
the column bottom, a bottom product composed of 6.9 wt. % of methanol, 0.1 
wt. % of water, 73.8 wt. % of methyl glyoxylate, and 21.0 wt. % of methyl 
glycolate was obtained. A mass balance of the methyl glyoxylate before and 
after the above fractionating operation was 100 wt. %. 
[EXAMPLE 10] 
(1) Coarse distillation Process 
By carrying out the coarse distillation process in the same manner as that 
in Example 8, a bottom product composed of 22.7 wt. % of methanol, 16.5 
wt. % of water, 6.4 wt. % of formaldehyde, 47.2 wt. % of methyl 
glyoxylate, and 7.2 wt. % of methyl glycolate was obtained. 
Here, no glyoxylic acid was produced due to hydrolyzation of methyl 
glyoxylate, and a mass balance of methyl glyoxylate through the coarse 
distillation process was 100 wt. %. 
(2) Azeotropic Dehydration Process 
By adding isopropyl acetate to the bottom product obtained through the 
above coarse distillation operation, a mixture composed of 6.5 wt. % of 
methanol, 4.7 wt. % of water, 1.8 wt. % of formaldehyde, 13.6 wt. % of 
methyl glyoxylate, 2.1 wt. % of methyl glycolate, and 71.2 wt. % of 
isopropyl acetate was obtained. 
Subsequently, the mixture was supplied to the same azeotropic dehydration 
column as that in Example 8, at a rate of 0.3 kg/h. As a result, a bottom 
product composed of 1.9 wt. % of methanol, 0.2 wt. % of water, 64.4 wt. % 
of methyl glyoxylate, 9.9 wt. % of methyl glycolate, and 23.6 wt. % of 
isopropyl acetate was obtained from the column bottom, while a distillate 
composed of 7.8 wt. % of methanol, 6.0 wt. % of water, 2.3 wt. % of 
formaldehyde, and 83.9 wt. % of isopropyl acetate was obtained from the 
column top. 
Subsequently, the bottom product obtained was again supplied to the same 
azeotropic dehydration column, at a rate of 0.2 kg/h. As a result, a 
bottom product composed of 1.6 wt. % of methanol, 0.1 wt. % of water, 85.2 
wt. % of methyl glyoxylate, 13.1 wt. % of methyl glycolate, and a trace of 
isopropyl acetate was obtained from the column bottom, while a distillate 
composed of 2.8 wt. % of methanol, 0.4 wt. % of water, and 96.8 wt. % of 
isopropyl acetate was obtained from the column top. A mass balance of the 
methyl glyoxylate before and after the above operation was 100 wt. %. 
(3) Fractionating Process 
Subsequently, the bottom product obtained through the last azeotropic 
dehydration process was subjected to the same fractionating operation as 
that in Example 8. As a result, methyl glyoxylate with a purity of 99.5 
percent was obtained from the column top, and in this fraction, 0.1 wt. % 
of water, and 0.1 wt. % of isopropyl acetate were contained as impurities. 
From the column bottom, a bottom product composed of 2.0 wt. % of 
methanol, 0.1 wt. % of water, 80.9 wt. % of methyl glyoxylate, and 17.0 
wt. % of methyl glycolate was obtained. A mass balance of the methyl 
glyoxylate before and after the above fractionating operation was 100 wt. 
%. 
The invention being thus described, it will be obvious that the same may be 
varied in many ways. Such variations are not to be regarded as a departure 
from the spirit and scope of the invention, and all such modifications as 
would be obvious to one skilled in the art are intended to be included 
within the scope of the following claims. 
Industrial Applicability 
The glyoxylate purifying method and the distillation device for 
purification of glyoxylates enable easy and efficient purification of 
high-purity glyoxylates that are suitably used as materials for 
synthesizing sodium polyglyoxylate which is an effective builder component 
for, for example, a surface active agent.