CN101570467B

CN101570467B - Method for purifying high-purity organic solvent methanol

Info

Publication number: CN101570467B
Application number: CN2009100692548A
Authority: CN
Inventors: 宋金链; 张玉芝
Original assignee: Tianjin Concord Technology Co Ltd
Current assignee: Tianjin Concord Technology Co Ltd
Priority date: 2009-06-15
Filing date: 2009-06-15
Publication date: 2012-05-02
Anticipated expiration: 2029-06-15
Also published as: CN101570467A

Abstract

The invention relates to a method for purifying high-purity organic solvent methanol. The steps are as follows: through oxidation, reduction and rectification, and filtration; and the finished productof high-purity methanol can be obtained. The method adopts methanol of 99.5 percent as a raw material and utilizes the qualitative difference of impurities to purify the impurities containing a littl e unsaturated hydrocarbon and alcohol by the operations of oxidation, reduction and rectification, and impurity removal; and the product of pesticide residue grade and gradient elution grade chromatographic methanol with purity of more than 99.9 percent can be obtained, the yield coefficient is more than 95 percent, and the pesticide residue grade and gradient elution grade chromatographic pure methanol with purity of more than 90 percent is obtained.

Description

The purification process of high-purity organic solvent methanol

Technical field

The invention belongs to the chemical reagent field, relate to a kind of purification preparation method of high-purity organic solvent, especially the purification process of high-purity organic solvent methanol.

Background technology

The method for preparing the residual level of farming, gradient elution level chromatogram methyl alcohol is reported seldom at home.The residual reagent of farming is the high purity reagent that in Detecting Pesticide, uses, and its purity requirement is higher than common chromatographically pure reagent.Because the production of agricultural-food causes the pesticide residue in the agricultural-food to exceed standard to the serious dependence of agricultural chemicals, has influenced the foreign trade of human consumer's edible safety and agricultural-food.For this reason, country has strengthened the dynamics of Detecting Pesticide, has increased the detection kind of agricultural chemicals, has improved the detection tolerance range.Therefore, pesticide residue in the agricultural-food being detected in time, accurately is to stop key one ring that pesticide residue exceed standard in the agricultural-food.

At present, the agricultural residual level and the gradient elution level reagent of China mainly rely on import, and is very urgent to the research work in this field.Therefore, the preparation and the purification process of the residual level of research farming, gradient elution level chromatogram methanol reagent are significant.

According to retrieval, the document of domestic purifying aspect about high-purity methyl alcohol is very few, so demand developing a kind of purification process of high-purity methyl alcohol urgently.

Summary of the invention

The objective of the invention is to overcome the weak point of prior art, the purification process of the high-purity organic solvent methanol that a kind of technology is simple, yield is high, product purity is high is provided.

The objective of the invention is to realize through following technical scheme:

A kind of purification process of high-purity organic solvent methanol, step is:

(1) oxidation: methanol feedstock is squeezed into reaction kettle, adds oxygenant and sulfuric acid, add oxygenant amount be 0.5～1.0% of methanol feedstock quality, to add the vitriolic amount be methanol feedstock quality 0.1～0.4%, backflow 2h～4h steams methyl alcohol;

(2) reduction rectifying: the methyl alcohol that steams is squeezed into the reduction rectifying still, and the amount that adds reductive agent is 0.2～0.8% of a methanol quality, reduces rectifying; Utilize heat-conducting oil heating, 100 ℃～200 ℃ of control thermal oil temperature, the methanol liquid temperature is 70 ℃～78 ℃ in the rectifying still; 64 ℃～67 ℃ of head temperature, control reflux ratio 10: 4～5 is removed starting fraction; Distillate filters, and promptly obtains high-purity methyl alcohol finished product

And the purity of said methanol feedstock is 99.5%.

And said oxygenant is hydrogen peroxide or potassium permanganate.

And said reductive agent is a hydrolith.

Advantage of the present invention and positively effect are:

1, the present invention is that 99.5% methyl alcohol is raw material with content; Utilize the difference on the contaminant characteristics, will wherein contain a small amount of unsaturated hydrocarbons and alcohols impurity and remove, carry out the rectifying purifying again through redox; Can obtain purity greater than 99.9% chromatogram methanol product; Yield can obtain agricultural residual level, gradient elution level chromatogram methanol product greater than 90% thus greater than 95%, and index is seen table 1.

2, the present invention adopt hydrogen peroxide or potassium permanganate as oxygenant, hydrolith as reductive agent; Carry out redox reaction; Adopt distillation and rectification process that methyl alcohol is carried out purifying, have the product purity height, easy and simple to handle, stable, be suitable for advantage such as scale prodn.

Embodiment

Below in conjunction with embodiment, the present invention is further specified, following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.

Embodiment 1:

A kind of purification process of high-purity organic solvent methanol, the step of purifying is:

(1) oxidation: with content is that 99.5% material benzenemethanol 15kg squeezes into the 20L stills for air blowing, adds oxidants hydrogen peroxide 75g, acidic medium sulfuric acid 15g, and backflow 4h steams the methyl alcohol after the oxidation rapidly;

(2) reduction rectifying: the methyl alcohol after the oxidation is squeezed into reduction kettle, add reductive agent hydrolith 30g, reduce rectifying.Use heat-conducting oil heating; The methanol liquid temperature is 70 ℃～78 ℃ in 100 ℃～150 ℃ of control thermal oil temperature, the rectifying still; 64 ℃～67 ℃ of head temperature; Control reflux ratio 10: 4～5 (all being presented on the instrument controlling box) is suitably controlled rectification temperature and is regulated reflux ratio, can control the moisture of methyl alcohol fluid.Remove starting fraction, distillate obtains high-purity methyl alcohol finished product with 0.45 μ mPVDF filtering with microporous membrane after the assay was approved, bottling, and inflated with nitrogen is preserved.

Embodiment 2:

(1) oxidation: with content is that 99.5% raw material chromatogram methyl alcohol 10kg squeezes into the 20L stills for air blowing, adds oxidant potassium permanganate 100g, acidic medium sulfuric acid 4.5g, and backflow 4h steams the methyl alcohol after the oxidation rapidly;

(2) reduction rectifying: the methyl alcohol after the oxidation is squeezed into the reduction rectifying still; Add reductive agent hydrolith 80g, reduce rectifying, utilize heat-conducting oil heating; 150 ℃～200 ℃ of control thermal oil temperature; The methanol liquid temperature is 70 ℃～78 ℃ in the rectifying still, 64 ℃～67 ℃ of head temperature, control reflux ratio 10: 4～5 (all being presented on the instrument controlling box).Suitably control rectification temperature and regulate reflux ratio, can control the moisture of methyl alcohol fluid.Remove starting fraction, distillate promptly obtains high-purity methyl alcohol finished product with 0.45 μ mPVDF filtering with microporous membrane after the assay was approved, bottling, and inflated with nitrogen is preserved.

Detect: the agricultural residual level of producing, gradient elution level chromatogram methyl alcohol is (the quartzy cuvette of 1cm in ultraviolet wavelength 205nm～260nm scope; Water is made reference); Absorbancy satisfies the index request in the table 1; Content is greater than 99.9%, and the recovery is greater than 95%, and wherein 90% product has reached agricultural residual level and gradient elution level index.Detect through the residual level of farming, promptly after 300 times of the sample concentration, all be lower than the peak height of 10ng/L γ-phenyl-hexachloride with the peak height of detected all impurity peaks of GC-ECD gas chromatograph, residual grade of farming is qualified; The test of liquid chromatography gradient elution: the absorbancy that the peak is arranged in the 254nm place is all less than 0.005AU, and gradient elution level chromatogram methyl alcohol is qualified.Agricultural residual grade, the gradient elution level chromatogram methyl alcohol of preparing through purifying like this can satisfy every profession and trade in Detecting Pesticide and the scientific research application demand with GEC methyl alcohol.

The residual level of table 1 farming gradient elution level chromatogram methyl alcohol technical indicator

Claims

1. the purification process of a high-purity organic solvent methanol, it is characterized in that: the step of purification process is:

(2) reduction rectifying: the methyl alcohol that steams is squeezed into the reduction rectifying still, and the amount that adds reductive agent is 0.2～0.8% of a methanol quality, reduces rectifying; Utilize heat-conducting oil heating, 100 ℃～200 ℃ of control thermal oil temperature, the methanol liquid temperature is 70 ℃～78 ℃ in the rectifying still; 64 ℃～67 ℃ of head temperature, control reflux ratio 10: 4～5 is removed starting fraction; Distillate filters, and promptly obtains high-purity methyl alcohol finished product, and the purity of said high-purity methyl alcohol finished product is greater than 99.9%;

The purity of said methanol feedstock is 99.5%, and said oxygenant is hydrogen peroxide or potassium permanganate, and said reductive agent is a hydrolith.