CN104744212B - The method of purification of solvent gradient methanol - Google Patents
The method of purification of solvent gradient methanol Download PDFInfo
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- CN104744212B CN104744212B CN201310754190.1A CN201310754190A CN104744212B CN 104744212 B CN104744212 B CN 104744212B CN 201310754190 A CN201310754190 A CN 201310754190A CN 104744212 B CN104744212 B CN 104744212B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a kind of method of purification of solvent gradient methanol, it is characterised in that the impurity in material benzenemethanol is removed by processes such as modified activated carbon, ion exchange resin absorption, obtains purity >=99.99%（wt）Solvent gradient methanol.The method of purification of solvent gradient methanol provided by the invention, it can obtain the solvent gradient methanol that can be applied to gradient elution field.
Description
Technical field
The present invention relates to solvent purifications field, more particularly to a kind of method of purification of solvent gradient methanol.
Background technology
Gradient elution (gradient elution) is also known as gradient elution or program elution.In gas-chromatography, in order to
Improve the separation to wide boiling range sample and shorten analytical cycle, the method for widely used temperature programming.It is and right in liquid chromatogram
The method that the sample of complicated components then uses gradient elution.I.e. in same analytical cycle, constantly change stream by certain procedures
The concentration proportioning of dynamic phase, referred to as gradient elution.So as to so that the larger component of nature difference in a complex sample can press
Each suitable capacity factor measure k reaches good separation purpose.
Mobile phase is made up of the eluting solvent of several opposed polarities, by change each solvent forms in mobile phase ratio come
Change the polarity of mobile phase, make the component of each outflow have suitable capacity factor measure k, and make all components in sample can be
Optimal separation is realized in shortest time.Specifically, when sample enters chromatogram column inlet with the mobile phase of gradient start, due to
Eluting solvent A contents are relatively low in starting point mobile phase, compound B-11 (retention is moderate) and compound B2 in sample (retention compared with
Chromatographic column entrance is stranded in because capacity factor measure k is higher by force), is not almost moved.After a period of time, A content increases to
Certain numerical value, B1 k values reach sufficiently small (such as less than 10), and its rate travel in post significantly increases, and with A's
Increase, its rate travel is further quick, flows out chromatographic column when tB1 (residence time of sample in the chromatography column), is detected
Device detects and is recorded into chromatographic peak B1.A content continues to increase, and at some subsequent time point, B2 k values also drop to 10
Hereinafter, B2 rate travel also begins to accelerate, and to be eluted out chromatographic column in tB2 with B1 similar modes, is detected by detector
To and be recorded into chromatographic peak B2.
As the eluting solvent in mobile phase, purity requirement is high, avoids the uncertain factor such as impurity interference detector from detecting
Sample component, ensure eluting solvent using when there is high reproducibility.Methanol is as a kind of conventional solvent gradient, purification ten
Divide difficulty.The method that industrial synthesizing methanol almost all uses carbon monoxide pressurized catalysis hydrogenation, technical process include gas making,
The processes such as cleaning up, methanol-fueled CLC and crude carbinol rectifying, caused many organic impurities in process are contained in product, such as
Various hydro carbons, heterocyclic arene etc., their boiling range is close with methanol, even if using very outstanding rectifying device, it is also not possible to
The solvent gradient methanol of high-purity is obtained after impurity is removed.
The content of the invention
The invention aims to overcome deficiency of the prior art, there is provided a kind of gradient for improving methanol purity is washed
The method of purification of desolventizing methanol.
To realize object above, the present invention is achieved through the following technical solutions：
The method of purification of solvent gradient methanol, it is characterised in that comprise the following steps：
A. material benzenemethanol is taken, the adsorbent post equipped with modified activated carbon is passed into and carries out adsorption treatment；Contain for removing
The organic compound of carbon-carbon double bond, such as alkene, aromatic hydrocarbon etc.；
B. the methanol obtained by step a is passed through the adsorbent post equipped with ion exchange resin and carries out adsorption treatment, remove aldehyde
Class and impurity metal ion, obtain the solvent gradient methanol of purity >=99.99% (wt).
Preferably, modified activated carbon is the activated carbon of surface attachment oxidizing acid.The oxidizing acid includes but unlimited
In concentrated nitric acid, dust technology, the concentrated sulfuric acid, hypochlorous acid, chloric acid, chlorous acid, perchloric acid, nitrous acid.
Preferably, ion exchange resin surface attachment acetonitrile or alcohol compound.Alcohol compound includes but is not limited to
Methanol.
Preferably, in the step a, before material benzenemethanol is passed through into adsorption column, sodium carbonate is added into material benzenemethanol, will
PH value is adjusted in the range of 7~8；Shaking, makes sodium carbonate fully be reacted with the organic acid impurities in material benzenemethanol, produces salt
Sediment；After stratification, water layer is discarded, and the organic layer dissolved with isopropanol is filtered, retains the filtrate dissolved with methanol.
Preferably, in the step a, before material benzenemethanol is passed through into adsorbent post, first it is passed into equipped with molecular sieve
Adsorbent post.
Preferably, molecular sieve surface is attached with aluminium hydroxide, for removing arene and polar compounds species impurity.
Preferably, in addition to step c, the methanol after absorption is subjected to rectifying；Rectifying still heating-up temperature is 100~200
DEG C, methanol liquid temperature is 70~78 DEG C in kettle, to go out liquid temperature degree be 64~67 DEG C, control reflux ratio 10: 4~5.
The method of purification of solvent gradient methanol provided by the invention, can obtain purity >=99.99% (wt) methanol,
Meet the high-purity requirement of solvent gradient, the methanol that purification obtains is applied to gradient elution field, expanding should
Use scope.Method of purification provided by the invention, filled up the production blank of domestic high purity methanol, reduce needed for import into
This, while alleviate the degree pind down by foreign technology.Method of purification provided by the invention, product yield >=98%, high income,
Also have the advantages that energy consumption is low, production process is easy, it is stable, suitable for industrialized production.
Embodiment
The present invention is described in detail with reference to embodiment：
Embodiment 1
The method of purification of solvent gradient methanol, it is characterised in that comprise the following steps：
A. the material benzenemethanol that purity is 99.5% (wt) is taken, sodium carbonate is added and adjusts the pH of solution to 7, and shaking makes carbon
Sour sodium fully reacts with the organic acid impurities in material benzenemethanol, generates precipitation of salts thing；Stratification, discards water layer, and filtering has
Machine layer, retain filtrate.
Above-mentioned filtrate is passed through to the adsorbent post for the molecular sieve for having aluminium hydroxide equipped with surface attachment, further removed organic
Moisture in layer, while remove the impurity such as the aromatic hydrocarbon in methanol, polar compound；After absorption, methanol water content control≤
0.02%；Moisture after extraction in methanol is removed using molecular sieve in this step, as moisture ＞ 0.05% need to be changed point
It is further continued for carrying out molecular sieve adsorption processing after son sieve；And then, above-mentioned efflux is passed through the adsorbent equipped with modified activated carbon
Post, modified activated carbon is the activated carbon soaked through concentrated nitric acid, for removing the organic compound of carbon-carbon double bonds, such as alkene,
Aromatic hydrocarbon etc.；Because carbon-carbon double bond is the group of absorbable ultraviolet-visible, so removing the organic compound of carbon-carbon double bonds
The light transmittance for the methanol being greatly improved after purification.
B., above-mentioned efflux is passed through to the adsorbent post for the ion exchange resin for having acetonitrile equipped with surface attachment, for removing
The impurity such as aldehydes, metal ion.
C. the above-mentioned methanol after adsorption treatment is squeezed into rectifying column and carries out rectifying, rectifying still heating-up temperature is 100 DEG C, kettle
It is 64 DEG C that middle methanol liquid temperature, which is 70 DEG C, goes out liquid temperature degree, control reflux ratio 10: 4.Bottle, fill after smart distillate detection is qualified
Nitrogen preserves, and produces the solvent gradient methanol of purity >=99.99% (wt).
Embodiment 2
The method of purification of solvent gradient methanol, it is characterised in that comprise the following steps：
A. the material benzenemethanol that purity is 99.5% (wt) is taken, sodium carbonate is added and adjusts the pH of solution to 8, and shaking makes carbon
Sour sodium fully reacts with the organic acid impurities in material benzenemethanol, generates precipitation of salts thing；Stratification, water layer and precipitation are discarded,
Organic layer is filtered, retains filtrate.
Above-mentioned filtrate is passed through to the adsorbent post for the molecular sieve for having aluminium hydroxide equipped with surface attachment, further removed organic
Moisture in layer, while remove the impurity such as the aromatic hydrocarbon in methanol, polar compound；After absorption, methanol water content control≤
0.02%；Moisture after extraction in methanol is removed using molecular sieve in this step, as moisture ＞ 0.05% need to be changed point
It is further continued for carrying out molecular sieve adsorption processing after son sieve；And then, above-mentioned efflux is passed through the adsorbent equipped with modified activated carbon
Post, modified activated carbon is the activated carbon soaked through the concentrated sulfuric acid, for removing the organic compound of carbon-carbon double bonds, such as alkene,
Aromatic hydrocarbon etc.；Because carbon-carbon double bond is the group of absorbable ultraviolet-visible, so removing the organic compound of carbon-carbon double bonds
The light transmittance for the methanol being greatly improved after purification.
B., above-mentioned efflux is passed through to the adsorbent post for the ion exchange resin for having methanol equipped with surface attachment, for removing
The impurity such as aldehydes, metal ion.
C. the above-mentioned methanol after adsorption treatment is squeezed into rectifying column and carries out rectifying, rectifying still heating-up temperature is 200 DEG C, kettle
Bottled after it is 67 DEG C that middle methanol liquid temperature, which is 78 DEG C, goes out liquid temperature degree, 10: the 5 smart distillate detection of control reflux ratio is qualified, nitrogen charging
Gas preserves, and produces the solvent gradient methanol of purity >=99.99% (wt).
Embodiment 3
The method of purification of solvent gradient methanol, it is characterised in that comprise the following steps：
A. the material benzenemethanol that purity is 99.5% (wt) is taken, sodium carbonate is added and adjusts the pH of solution to 7.5, and shaking makes
Sodium carbonate fully reacts with the organic acid impurities in material benzenemethanol, generates precipitation of salts thing；Stratification, discard water layer and sink
Form sediment, filter organic layer, retain filtrate.
Above-mentioned filtrate is passed through to the adsorbent post for the molecular sieve for having aluminium hydroxide equipped with surface attachment, further removed organic
Moisture in layer, while remove the impurity such as the aromatic hydrocarbon in methanol, polar compound；After absorption, methanol water content control≤
0.02%；Moisture after extraction in methanol is removed using molecular sieve in this step, as moisture ＞ 0.05% need to be changed point
It is further continued for carrying out molecular sieve adsorption processing after son sieve；And then, above-mentioned efflux is passed through the adsorbent equipped with modified activated carbon
Post, modified activated carbon is the activated carbon soaked through hypochlorous acid, for removing the organic compound of carbon-carbon double bonds, such as alkene,
Aromatic hydrocarbon etc.；Because carbon-carbon double bond is the group of absorbable ultraviolet-visible, so removing the organic compound of carbon-carbon double bonds
The light transmittance for the methanol being greatly improved after purification.
B., above-mentioned efflux is passed through to the adsorbent post for the ion exchange resin for having acetonitrile equipped with surface attachment, for removing
The impurity such as aldehydes, metal ion.
C. the above-mentioned methanol after adsorption treatment is squeezed into rectifying column and carries out rectifying, rectifying still heating-up temperature is 150 DEG C, kettle
Bottled after it is 65 DEG C that middle methanol liquid temperature, which is 75 DEG C, goes out liquid temperature degree, 10: the 4 smart distillate detection of control reflux ratio is qualified, nitrogen charging
Gas preserves, and produces the solvent gradient methanol of purity >=99.99% (wt).
Embodiment 4
The method of purification of solvent gradient methanol, it is characterised in that comprise the following steps：
A. the material benzenemethanol that purity is 99.5% (wt) is taken, sodium carbonate is added and adjusts the pH of solution to 8, and shaking makes carbon
Sour sodium fully reacts with the organic acid impurities in material benzenemethanol, generates precipitation of salts thing；Stratification, water layer and precipitation are discarded,
Organic layer is filtered, retains filtrate.
Above-mentioned filtrate is passed through to the adsorbent post for the molecular sieve for having aluminium hydroxide equipped with surface attachment, further removed organic
Moisture in layer, while remove the impurity such as the aromatic hydrocarbon in methanol, polar compound；After absorption, methanol water content control≤
0.02%；Moisture after extraction in methanol is removed using molecular sieve in this step, as moisture ＞ 0.05% need to be changed point
It is further continued for carrying out molecular sieve adsorption processing after son sieve；And then, above-mentioned efflux is passed through the adsorbent equipped with modified activated carbon
Post, modified activated carbon is the activated carbon soaked through perchloric acid, for removing the organic compound of carbon-carbon double bonds, such as alkene,
Aromatic hydrocarbon etc.；Because carbon-carbon double bond is the group of absorbable ultraviolet-visible, so removing the organic compound of carbon-carbon double bonds
The light transmittance for the methanol being greatly improved after purification；
B., above-mentioned efflux is passed through to the adsorbent post for the ion exchange resin for having acetonitrile equipped with surface attachment, for removing
The impurity such as aldehydes, metal ion.
C. the above-mentioned methanol after adsorption treatment is squeezed into rectifying column and carries out rectifying, rectifying still heating-up temperature is 200 DEG C, kettle
Bottled after it is 66 DEG C that middle methanol liquid temperature, which is 77 DEG C, goes out liquid temperature degree, 10: the 5 smart distillate detection of control reflux ratio is qualified, nitrogen charging
Gas preserves, and produces the solvent gradient methanol of purity >=99.99% (wt).
The technical indicator of solvent gradient methanol after the purification of embodiment 1~4 is as shown in Table 1：
Table one
| Title | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Material benzenemethanol |
| Purity (wt%) | ≥99.99 | ≥99.99 | ≥99.99 | ≥99.99 | ≥99.5 |
| Moisture (wt%) | ≤0.02 | ≤0.02 | ≤0.02 | ≤0.02 | ≤0.1 |
Embodiment in the present invention is only used for that the present invention will be described, and is not construed as limiting the scope of claims limitation,
Other substantially equivalent replacements that those skilled in that art are contemplated that, all fall in the scope of protection of the present invention.
Claims (5)
1. the method for purification of solvent gradient methanol, it is characterised in that comprise the following steps：
A. material benzenemethanol is taken, the adsorbent post equipped with modified activated carbon is passed into and carries out adsorption treatment；Modified activated carbon is table
The activated carbon of oxidizing acid is adhered in face；
B. the methanol obtained by step a is passed through adsorbent post equipped with ion exchange resin and carries out adsorption treatment, obtain purity >=
99.99% (wt) solvent gradient methanol；
In the step a, before material benzenemethanol is passed through into adsorption column, sodium carbonate, shaking, stratification are added into material benzenemethanol
Afterwards, water layer is discarded, organic layer is filtered, retains the filtrate dissolved with methanol.
2. the method for purification of solvent gradient methanol according to claim 1, it is characterised in that ion exchange resin table
Face is attached with acetonitrile or alcohol compound.
3. the method for purification of solvent gradient methanol according to claim 1, it is characterised in that, will in the step a
Material benzenemethanol is passed through before adsorbent post, is first passed into the adsorbent post equipped with molecular sieve.
4. the method for purification of solvent gradient methanol according to claim 3, it is characterised in that molecular sieve surface adheres to
There is aluminium hydroxide.
5. the method for purification of the solvent gradient methanol according to claim 1,3 or 4, it is characterised in that also include step
Rapid c, the methanol after absorption is subjected to rectifying；Rectifying still heating-up temperature is 100~200 DEG C, in kettle methanol liquid temperature be 70~
78 DEG C, go out liquid temperature degree for 64~67 DEG C, control reflux ratio 10: 4~5.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105085174A (en) * | 2014-05-16 | 2015-11-25 | 上海星可高纯溶剂有限公司 | Purification method of gradient elution solvent methanol |
| CN114315519A (en) * | 2020-09-27 | 2022-04-12 | 太仓沪试试剂有限公司 | Method for purifying high-purity organic solvent methanol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2003037474A1 (en) * | 2001-10-31 | 2003-05-08 | Honeywell International Inc. | Purification of organic solvents |
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