CN104610061B - The preparation method of electron level ethyl lactate - Google Patents
The preparation method of electron level ethyl lactate Download PDFInfo
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- CN104610061B CN104610061B CN201510063085.2A CN201510063085A CN104610061B CN 104610061 B CN104610061 B CN 104610061B CN 201510063085 A CN201510063085 A CN 201510063085A CN 104610061 B CN104610061 B CN 104610061B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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Abstract
The invention discloses the preparation method of a kind of electron level ethyl lactate.The present invention is with food grade lactic acid ethyl ester as raw material; first remove major part metal ion therein through ion exchange resin absorption; remove moisture and light, heavy constituent impurity through rectification under vacuum again, under high pure nitrogen is protected, finally carry out sub-boiling distillation removing metal ion, obtain electron level ethyl lactate.Use content of ethyl lactate >=99.99% obtained by the present invention, each ion concentration of lead, copper, ferrum, magnesium, arsenic, calcium, aluminum, zinc, manganese, hydrargyrum, chromium, nickel, potassium, sodium all≤1ppb, moisture≤100ppm, acidity≤65ppm, meet electronics rank.The whole preparation process of the present invention is not related to the discharge of waste water,waste gas and industrial residue, relatively low to equipment requirements, and distillation process, without the biggest reflux ratio, can reduce energy consumption significantly with cost-effective, relatively rapid efficiently, whole process environmental protection is pollution-free.
Description
Technical field
The present invention relates to the purification process of ethyl lactate, in particular to a kind of electron level lactic acid second
The preparation method of ester.
Background technology
Electron level ethyl lactate is mainly used in the cleaning of precise electronic components and parts, has fragrance
Taste, low volatility, effectively improve the strong and stimulating abnormal smells from the patient of conventional solvent；It is that high boiling point is molten
Agent (145～190 DEG C), has extremely strong molten to oils and fats, Polymeric Soil, water-soluble stains
Solution ability and the dissolubility of uniqueness；As abluent, compared with other abluent, there is loss little,
Cost performance is high, has no adverse effects cleaned material.
The purification technique of electron level ethyl lactate, Chinese patent CN102320969A discloses
A kind of by the system approach that food grade lactic acid ethyl ester rectification and purification is electron level ethyl lactate.Should
In method, distillation process needs the biggest reflux ratio, and equipment requirements is higher, and production efficiency is relatively
Low, energy consumption is relatively big, and product is easily polluted by impurity in air, and purity is unsecured.
Summary of the invention
Present invention aim to the deficiency overcome existing for prior art, it is provided that Yi Zhonggao
Imitate the preparation method of electron level ethyl lactate energy-conservation, free from environmental pollution.
For achieving the above object, the preparation side of the electron level ethyl lactate designed by the present invention
Method, comprises the following steps:
1) ion exchange resin absorption: food grade lactic acid ethyl ester is first used macroreticular weakly base benzene
Ethylene series anion resin absorption, then with macropore acidulous acrylic acid's cation resin ion
Resin and the absorption of neutral ion exchanger resin, remove major part metal ion therein；
2) rectification under vacuum: by step 1) process after ethyl lactate add in rectifying column and carry out
Rectification under vacuum, rectifying column bottom temperature 61～145 DEG C, tower top temperature is 32～90 DEG C, condensation
Coolant-temperature gage is 2～10 DEG C, and reflux ratio is 10:1～15:1, remove moisture and light, heavy constituent is miscellaneous
Matter；
3) sub-boiling distillation: by through step 2) ethyl lactate that processes joins sub-boiling distillation device
In, under high pure nitrogen is protected ethyl lactate is heated to below boiling point 5～10 DEG C, removing gold
Belonging to ion, more than 99.99% and metal ion content is respectively less than the electronics of 1ppb to obtain content
Level ethyl lactate.
Preferably, step 1 of the present invention) in ion exchange resin absorption, every kind of use from
Sub-exchange column length is not less than 3m；Flow velocity 4～10m/h.
Preferably, step 2 of the present invention) in rectification under vacuum, rectifying column bottom temperature is
69～71 DEG C, tower top temperature is 38～42 DEG C, and condensate temperature is 2～5 DEG C, and reflux ratio is
12:1, bottom pressure 700～900pa, refluxes 3～5 hours.
Step 2 of the present invention) in rectification under vacuum, the tower height of rectifying column used is 1.3m, in tower
Footpath is 34mm, and the filler in rectifying column used is triangle helical packing, net ring filler or glass
Glass spring filler.Filler used is preferably 316L type 1.5mm × 1.5mm triangle helical packing,
Theoretical cam curve is 41～45.
Step 3 of the present invention) in sub-boiling distillation, described sub-boiling distillation device need to first pass through pretreatment
Re-using, preprocess method is first to soak 24 hours with chloroazotic acid, more repeatedly rush with ultra-pure water
Wash, reach 18.25M Ω cm@25 DEG C to washing out resistivity of water.
Ethyl lactate is heated to below boiling point 5～10 DEG C under high pure nitrogen is protected by the present invention
Carrying out sub-boiling distillation, owing to ethyl lactate is not up to boiling point, and the gas phase of liquid equilibrium is the most just
No longer it is made up of a large amount of steam thing grains, but with molecularity and liquid equilibrium, therefore,
Steam is seldom carried secretly or does not carry metal ion and solid particle secretly.This deposit with molecularity
It is the steam of gas-phase space, on condensation tube wall, is condensed into liquid, thus obtained breast again
The content of acetoacetic ester is more than 99.99%, and impurity metal ion content is not above 1ppb.
The present invention with food grade lactic acid ethyl ester as raw material, through ion exchange resin absorption, rectification,
Sub-boiling distillation, content of ethyl lactate >=99.99% obtained, lead, copper, ferrum, magnesium, arsenic,
The each ion concentration of calcium, aluminum, zinc, manganese, hydrargyrum, chromium, nickel, potassium, sodium all≤1ppb, moisture
Content≤100ppm, acidity≤65ppm, meet electronics rank.Compared with prior art, originally
Invention has the following characteristics that
1, ion exchange resin absorption and the distillation process of the present invention is carried out i.e. in general room
Can, it is not necessary to again dust free room is carried out, can investment reduction cost significantly.
2, distillation process is without the biggest reflux ratio, only need to carry out at 10:1～15:1,
Improve production efficiency, energy consumption can be reduced significantly with cost-effective.
3, sub-boiling distillation is carried out under high pure nitrogen is protected, and not only avoids impurity in air dirty
Dye, also improves distillation efficiency while increasing high pure nitrogen air-flow.
4, the present invention uses anion-cation exchange resin, repeatable utilization, amberlite
Fat is after a period of time uses, and ionic adsorption effect can be decreased obviously, permissible through Regeneration Treatment
Circulation is used for multiple times；Equipment will not be caused corrosion, reduce equipment Meteorological again.
5, rectifying column used by the present invention, a small amount of heavy constituent at the bottom of tower, can be as food through decolouring
Grade ethyl lactate is continuing with, and the light component of tower top can take off through rectification again because water content exceeds standard
Water, whole process does not has the waste of raw material substantially.
6, the whole preparation process of the present invention is not related to the discharge of waste water,waste gas and industrial residue, right
Equipment requirements is relatively low, relatively rapid efficiently, whole process environmental protection is pollution-free.
Detailed description of the invention
In order to preferably explain the present invention, below in conjunction with specific embodiment, the present invention is made into one
The detailed description of step, but they do not constitute restriction to the present invention.Other people do according to the present invention
The nonessential amendment of some gone out and adjustment, still fall within protection scope of the present invention.Other is not
The part described in detail is prior art.
Chloroazotic acid described in the present invention is 1: 3 by concentrated nitric acid and concentrated hydrochloric acid by volume
Ratio mixes.
Embodiment 1
1) ion exchange resin absorption: by 2000ml content 99% food grade lactic acid ethyl ester,
Pass sequentially through equipped with macroreticular weakly base styrene series anion resin absorption, macropore faintly acid third
The ion exchange column of olefin(e) acid cation resin ion resin, the length of every kind of ion exchange column
For 3m, flow velocity 6m/h, after ion exchange column, in ethyl lactate major part metal from
Son can control within 100ppb, but moisture slightly rises.
2) rectification under vacuum: the ethyl lactate attached through ion-exchange absorption is added laboratory certainly
Carrying out rectification under vacuum in rectifying column processed, the tower height of rectifying column is 1.3m, and tower internal diameter is 34mm,
Filler used is preferably 316L type 1.5mm × 1.5mm triangle helical packing, theoretical cam curve
It is 41～45；Rectifying column bottom temperature is 69～71 DEG C, and tower top temperature is 38～42 DEG C, cold
Solidifying coolant-temperature gage is 2～5 DEG C, bottom pressure 700～900pa, refluxes 3 hours；First extraction is few
Amount water and ethyl lactate blend about 50ml, then use doing of the full extraction of repeatedly infinite reflux
Method, when extraction sample reaches 99.99%, stablizes the continuous extraction of reflux ratio 12:1,
3) sub-boiling distillation: sub-boiling distillation device first passes through pretreatment and re-uses, preprocess method
For first soaking 24 hours with chloroazotic acid, more repeatedly rinse with ultra-pure water, to the resistance washing out water
Rate reaches 18.25M Ω cm@25 DEG C；Will be through step 2) process after ethyl lactate add
In pretreated sub-boiling distillation device, first replace sub-boiling distillation device 4～6 with high pure nitrogen
Secondary, drain air, under high pure nitrogen is protected, ethyl lactate is heated to below boiling point
5～10 DEG C, remove metal ion, obtain 1750ml electron level ethyl lactate altogether.Wherein,
The content of ethyl lactate is 99.99%, lead, copper, ferrum, magnesium, arsenic, calcium, aluminum, zinc,
The each ion concentration of manganese, hydrargyrum, chromium, nickel, potassium, sodium all≤1ppb, moisture≤100ppm,
Acidity≤65ppm.
Embodiment 2
1) ion exchange resin absorption: by 2000ml content 99% food grade lactic acid ethyl ester,
Pass sequentially through equipped with macroreticular weakly base styrene series anion resin absorption, macropore faintly acid third
Olefin(e) acid cation resin ion resin and the ion exchange column of neutral ion exchanger resin, often
Plant a length of 3m, the flow velocity 4m/h of ion exchange column, after ion exchange column, lactic acid
In ethyl ester, major part metal ion can control within 100ppb, but moisture slightly rises.
2) rectification under vacuum: the ethyl lactate attached through ion-exchange absorption is added laboratory certainly
Carrying out rectification under vacuum in rectifying column processed, the tower height of rectifying column is 1.3m, and tower internal diameter is 34mm,
Filler used is preferably 316L type 1.5mm × 1.5mm triangle helical packing, theoretical cam curve
It is 41～45；Rectifying column bottom temperature is 80～84 DEG C, and tower top temperature is 43～46 DEG C, cold
Solidifying coolant-temperature gage is 2～5 DEG C, bottom pressure 700～900pa, refluxes 3 hours；First extraction is few
Amount water and ethyl lactate blend about 70ml, then use doing of the full extraction of repeatedly infinite reflux
Method, when extraction sample reaches 99.99%, stablizes the continuous extraction of reflux ratio 10:1,
3) sub-boiling distillation: sub-boiling distillation device first passes through pretreatment and re-uses, preprocess method
For first soaking 24 hours with chloroazotic acid, more repeatedly rinse with ultra-pure water, to the resistance washing out water
Rate reaches 18.25M Ω cm@25 DEG C；Will be through step 2) process after ethyl lactate add
In pretreated sub-boiling distillation device, first replace sub-boiling distillation device 4～6 with high pure nitrogen
Secondary, drain air, under high pure nitrogen is protected, ethyl lactate is heated to below boiling point
5～10 DEG C, remove metal ion, obtain 1630ml electron level ethyl lactate altogether.Wherein,
The content of ethyl lactate is 99.99%, lead, copper, ferrum, magnesium, arsenic, calcium, aluminum, zinc,
The each ion concentration of manganese, hydrargyrum, chromium, nickel, potassium, sodium all≤1ppb, moisture≤100ppm,
Acidity≤65ppm.
Embodiment 3
1) ion exchange resin absorption: by 2000ml content 99% food grade lactic acid ethyl ester,
Pass sequentially through equipped with macroreticular weakly base styrene series anion resin absorption, macropore faintly acid third
Olefin(e) acid cation resin ion resin and the ion exchange column of neutral ion exchanger resin, often
Plant a length of 3m, the flow velocity 10m/h of ion exchange column, after ion exchange column, breast
In acetoacetic ester, major part metal ion can control within 100ppb.
2) rectification under vacuum: the ethyl lactate attached through ion-exchange absorption is added laboratory certainly
Carrying out rectification under vacuum in rectifying column processed, the tower height of rectifying column is 1.3m, and tower internal diameter is 34mm,
Filler used is preferably 316L type 1.5mm × 1.5mm triangle helical packing, theoretical cam curve
It is 41～45；Rectifying column bottom temperature is 62～65 DEG C, and tower top temperature is 34～37 DEG C, cold
Solidifying coolant-temperature gage is 2～5 DEG C, bottom pressure 700～900pa, refluxes 5 hours；First extraction is few
Amount water and ethyl lactate blend about 40ml, then use doing of the full extraction of repeatedly infinite reflux
Method, when extraction sample reaches 99.99%, stablizes the continuous extraction of reflux ratio 15:1, removes water
Divide and light, the impurity that grades of recombinating；
3) sub-boiling distillation: sub-boiling distillation device first passes through pretreatment and re-uses, preprocess method
For first soaking 24 hours with chloroazotic acid, more repeatedly rinse with ultra-pure water, to the resistance washing out water
Rate reaches 18.25M Ω cm@25 DEG C；Will be through step 2) process after ethyl lactate add
In pretreated sub-boiling distillation device, first replace sub-boiling distillation device 4～6 with high pure nitrogen
Secondary, drain air, under high pure nitrogen is protected, ethyl lactate is heated to below boiling point
5～10 DEG C, remove metal ion, obtain 1810ml electron level ethyl lactate altogether.Wherein,
The content of ethyl lactate is 99.99%, lead, copper, ferrum, magnesium, arsenic, calcium, aluminum, zinc,
The each ion concentration of manganese, hydrargyrum, chromium, nickel, potassium, sodium all≤1ppb, moisture≤100ppm,
Acidity≤65ppm.
Claims (1)
1. the preparation method of an electron level ethyl lactate, it is characterised in that: it include with
Lower step:
1) ion exchange resin absorption: food grade lactic acid ethyl ester is first used macroreticular weakly base benzene
Ethylene series anion resin absorption, then with macropore acidulous acrylic acid's cation resin and in
Property ion exchange resin absorption, remove therein major part metal ion；Used every kind from
The length of sub-exchange column is not less than 3m, flow velocity 4～10m/h；
2) rectification under vacuum: by step 1) process after ethyl lactate add in rectifying column and carry out
Rectification under vacuum, removes moisture and light, heavy constituent impurity, and rectifying column bottom temperature is 69～71 DEG C,
Tower top temperature is 38～42 DEG C, and condensate temperature is 2～5 DEG C, and reflux ratio is 12:1, bottom
Pressure 700～900pa, refluxes 3～5 hours；The tower height of described rectifying column is 1.3m, in tower
Footpath is 34mm, and the filler in rectifying column used is triangle helical packing, net ring filler or glass
Glass spring filler；
3) sub-boiling distillation: sub-boiling distillation device need to first pass through pretreatment and re-use, pretreatment side
Method is first to soak 24 hours with chloroazotic acid, more repeatedly rinse with ultra-pure water, to the electricity washing out water
Resistance rate reaches 18.25M Ω cm@25 DEG C；Again will be through step 2) process after ethyl lactate
Join in sub-boiling distillation device, under high pure nitrogen is protected ethyl lactate is heated to boiling point with
Lower 5～10 DEG C, remove metal ion, obtain content more than 99.99% and metal ion content
It is respectively less than the electron level ethyl lactate of 1ppb.
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| JP6760299B2 (en) * | 2015-10-02 | 2020-09-23 | 三菱瓦斯化学株式会社 | High-purity carboxylic acid ester and its manufacturing method |
| CN109160876B (en) * | 2018-11-06 | 2022-04-15 | 湖南东为化工新材料有限公司 | Preparation method of electronic grade cyclohexanone |
| CN109455683A (en) * | 2018-11-23 | 2019-03-12 | 宜宾海丰和锐有限公司 | A method of purifying hydrazine hydrate prepares electron level hydrazine hydrate |
| CN109970555A (en) * | 2018-12-28 | 2019-07-05 | 深圳光华伟业股份有限公司 | The preparation method of electron level n propyl propionate |
| CN113004119A (en) * | 2019-12-19 | 2021-06-22 | 安集微电子（上海）有限公司 | Preparation method of electronic-grade reagent |
| CN112898154A (en) * | 2021-01-21 | 2021-06-04 | 宁波南大光电材料有限公司 | Method for removing water in ethyl lactate |
| CN112920161A (en) * | 2021-01-27 | 2021-06-08 | 宁波南大光电材料有限公司 | Electronic-grade dioxane and preparation method thereof |
| KR20240009454A (en) * | 2021-05-19 | 2024-01-22 | 다우 글로벌 테크놀로지스 엘엘씨 | Purification process of organic amines |
| CN115353121A (en) * | 2022-09-01 | 2022-11-18 | 阜新泽程化工有限责任公司 | Industrial production method of electronic pure ammonium sulfite |
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| CN102320969A (en) * | 2011-06-10 | 2012-01-18 | 天津大学 | System and method for rectifying and purifying food grade ethyl lactate into electronic grade ethyl lactate |
| CN102381973A (en) * | 2011-09-19 | 2012-03-21 | 南京大学 | Production process of ultra-high purity (electronic grade) lactate product |
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