Semi-continuous producing process for ethyl formate

CN 1039226 C
ABSTRACT translated from Chinese
Ethyl semi-continuous production process, which formic acid and ethanol as raw materials, sulfuric acid
as a catalyst, using the new ratio of raw materials and semi-continuous production of ethyl esterification
process. Present technology is mature, stable operation, formic acid yield was 95.4%. Compared with the
prior art, the present invention has the consumption of raw materials, low production cost, equipment,
production capacity, product quality and other advantages. The present invention is applicable to a
fragrance grade, pharmaceutical grade and reagent grade ethyl formate production.

CLAIMS(3) translated from Chinese

1. Ethyl semi-continuous production process, which comprises formic acid and ethanol as a raw material,
sulfuric acid as catalyst, ingredients, esterification and recovery processes such as the production of
carboxylic acid ethyl ester, characterized in that: the ratio of formic acid primer: ethanol = 1:2.5 to 5.0
(molar ratio), the ratio of formic acid dropwise addition: ethanol = 1:1.0 ~ 1.1 (mole ratio); primer after the
esterification reaction be substantially reached equilibrium, the feed was continuously added dropwise
ester reaction pot, while the ethyl ester continuously distilled from the tower top, condensed cooling, 60 to
65% as reflux back into the ethyl total overhead, and the rest as a finished product out of the ester
reaction system, water and raw water and formic acid during the esterification reaction of ethanol
produced contained retained in the esterification reaction pot.
2. The process according to claim 1, characterized in that the material is out of balance dropping amount:
back-flow: = 1:1.0 ~ 1.5:0.5 discharge amount to 1.0 (volume ratio).
3. The process according to claim 1, characterized in that the feed is added dropwise at 14 to 15 times
the weight of the base coat by weight of formic acid, and the esterification column top temperature above
54.1 , the pot temperature of the reaction liquid 75 when the end of addition; when the temperature
is higher than the top of the esterification Tata 54.5 , the pot temperature of the reaction solution was
78 , stop collecting ethyl.

DESCRIPTION translated from Chinese

Ethyl semi-continuous production process
The present invention relates to carboxylic acid ethyl ester production process, particularly to perfume
grade, pharmaceutical grade and reagent grade ethyl production process.
Ethyl is a colorless volatile liquid, easily hydrolyzed, miscible with benzene, ether, ethanol, slightly soluble
in water. Ethyl in the food industry for the preparation of food flavors and fruity wine flavor, but also raw
materials in the pharmaceutical industry and organic synthesis industry, has also been widely used as
solvents, fumigants, larvicidal agent.

After retrieving Chinese Patent Index CD-ROM discs, Chinese Patent Classification Annual Index,
Chemical Abstracts (CA) and the World Patents Abstracts (WPI, WPA), prior to the invention of the
present invention has not been found to have similar production processes. About Ethyl synthesis method
is more representative of the literature, for example: "The world of Fine Chemicals Handbook"
(Information Institute of the Ministry of Chemical Industry Science and Technology editor published in
December 1982 1st edition, 457), "synthetic food flavors "(Light Industry Press, December 1985 1st
edition, 360), the outlines of Japan, the United States, the manufacturing method of ethyl" Chemical
Products Guide Manual - organic chemicals on the books "(Ministry of Chemical Industry Science and
Technology Information Institute, Chemical Industry Press, February 1985 1st edition, 263) describes the
process route in five domestic factories, but the present invention and such processes are not the same.
Since formic acid containing 15 to 16% water, ethanol containing 7-8% water, the esterification reaction
process in turn produces about 24% of water by weight ethyl formate, ethyl formate and hydrolysis and
easily, so How to remove the bulk of the water within the esterification reaction system, the key has been
prepared ethyl.
Ethyl domestic manufacturers most of the traditional single-pot batch esterification process which is the
esterification reaction system of the water is removed from the top, as follows: formic acid and ethanol by
a ratio of ingredients, adding a small amount sulfuric acid as a catalyst, was heated under reflux for
esterification; esterification at reflux with constant water form a ternary azeotrope overhead from the trap
located in the separation, i.e., ethyl formate, ethanol and water azeotrope distilled off from the top of the
form, after entering the trap cooled condensed layered, ester, alcohol mixture the upper (as the saturated
water) back into the top of the tower, the lower the water (as an ester, an alcohol saturated with) the
esterification reaction is removed system; After the completion of the dehydration esterification, collecting
64 ~ 100 distillation fraction, the esterification reaction pot generated ethyl, unreacted formic acid and
ethanol was distilled off all; added anhydrous sulfuric acid solution in distilled sodium, anhydrous calcium
chloride or the like of the desiccant is dried and filtered; the filtrate was fractionated, collected 53 ~ 58
fraction as ethyl finished. Press this process, the yield of formic acid is generally about 80%, this
traditional process exists primarily high consumption of raw materials, equipment, production capacity,
and long production cycle and other issues.
Object of the present invention is to provide a high yield, good economy, production equipment and the
operation capacity ethyl reliable production of new technology.
Object of the present invention is achieved by the following method: formic acid (content of 84 to 85%)
and ethanol (content of 92 to 93%) as a raw material, sulfuric acid as a catalyst, base material ratio of
formic acid: ethanol = 1:2.5 ~ 5.0 (mole ratio), dropwise addition ratio of formic acid: ethanol = 1:1.0 ~ 1.1
(mole ratio); primer after the esterification reaction be substantially reached equilibrium, the feed was
continuously dropwise added to the esterification reaction pot, while The ethyl esterification is
continuously distilled off from the tower top, condensed to cool, 60 to 65% as reflux back into the ethyl
total overhead, the remainder of the finished product is removed as the esterification reaction

system. Throughout the semi-continuous esterification process, controlled by the ratio of raw materials,
temperature control, as well as out of balance control materials for dropping amount: back flow: the
quantity = 1:1.0 ~ 1.5:0.5 to 1.0 (volume ratio), the resulting ethyl esterification reaction system within a
large number of ethanol and water form an azeotrope, so that esterification tower top distilled ethyl
without rectification had reached spice level standards, The aqueous system while the esterification
reaction within almost all remain in the esterification reaction pot, and finally discharged from the
esterification reaction pot was almost pure water. The spice level as above using ethyl glycol extractive
distillation, which reached reagent grade and pharmaceutical grade standards.
Wujiang owned perfumery proved nearly three years of production, compared with the prior art, the
present invention has the following advantages: (1) low consumption of raw materials, high yield (95.5%
per ton in the content of ethyl meter, formic acid alone consumption of 0.736 tons, ethanol consumption
0.765 tons, the yield was 95.4% formic acid, 10 to 15% increase over the prior art); (2) Device production
capacity (per unit volume of reactor calculation) increased by 4.1 times; ( 3) Products of good quality
(without rectification can achieve spice level standard).
1 is a semi-continuous esterification of carboxylic acid ethyl ester process equipment diagram.
FIG: esterification Fanyingguo [1], esterification column [2], the condenser [3], the cooler [4], the reservoir
[5], the flowmeter [6], [7], [8] and other auxiliary equipment, such as a temperature of [T], pressure gauge
[P] and the like.
DRAWINGS 1 through embodiment of the present invention will be described in detail:
1. The formulation of the present invention using acid (content of 84 to 85%) and ethanol (content of 92 to
93%) as a raw material, sulfuric acid as a catalyst, base material ratio of formic acid: ethanol = 1:2.5 to
5.0 (molar ratio), dropwise addition ratio of formic acid: ethanol = 1:1.0 to 1.1 (molar ratio).
2. The whole was refluxed for esterification of 0.8 to 1.0% by weight of bottom materials and primer was
added 1000 liters of concentrated sulfuric acid esterification Fanyingguo [1], to the esterification reaction
pot [1] of the jacket into the steam, open mixing, heat for about 1 hour total reflux esterification, when
esterification tower [2] The top temperature stabilized at 53.5 ~ 54.0 , the total reflux esterification end.
3. After the semi-continuous esterification total reflux esterification process, which began operating semicontinuous esterification. Under the control of column top temperature of 54.0 ~ 54.1 and material out
of balance condition, by the dropwise addition flowmeter [6] by 200 to 300 l / hr was continuously added
to the esterification reaction pot bottom [1], while carboxylic acid ethyl ester was continuously distilled off
from the top of the esterification column [2], via the condenser [3], the cooler [4] After entering the
reservoir [5], a part of ethyl formate was distilled through a flow meter [ 7] by 200 to 450 l / hr back into the
top of the column, another portion of ethyl formate was distilled through a flow meter [8] by 100 to 300 l /
hr out of the reaction system. When the entire semi-continuous esterification process to join the drip feed

of 14 to 15 times the weight of the base coat weight of formic acid, and esterification Overhead
temperatures above 54.1 , the pot temperature of the reaction solution was 75 , dropping
end . When the temperature is higher than the top of the esterification Tata 54.5 , the pot temperature
of the reaction solution was 78 , stop collecting ethyl. The combined ethyl above distilled liquid, you can
spice level as ethyl. For the preparation of pharmaceutical grade and reagent grade ethyl, then the
fragrance level using ethyl glycol extractive distillation can be.
4. Ethyl recover after the end of the collection, started collecting ester-containing ethanol. After ester
containing ethanol content commuted by the preparation for the pot bottom material. When the end of
ester-containing ethanol to collect the top temperature higher than 78.0 , the pot liquid temperature
reached 88 .
After collecting ester containing ethanol, ethanol began to collect light. After concentrating light ethanol
preparation for the pot bottom material or drip feeding. When the light collected by the end of ethanol to
the top temperature higher than 95.0 , the pot liquid temperature up to 98 . In this case, the
remainder of the pot is almost pure water, its weight is 4.3 to 4.5 times by weight of formic acid primer,
this waste water was discarded.
Select four batches are ethyl, with the flavor level (U.S. FCCIII), pharmaceutical grade, reagent grade
(chemically pure) standard control as follows:
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Test results show that the use of semi-continuous production of ethyl esterification process without
rectification had reached spice level standards, after distillation, can achieve reagent grade and
pharmaceutical grade standards.