CN112390705B - 1,3-butanediol deodorization purification method - Google Patents
1,3-butanediol deodorization purification method Download PDFInfo
- Publication number
- CN112390705B CN112390705B CN201910748055.3A CN201910748055A CN112390705B CN 112390705 B CN112390705 B CN 112390705B CN 201910748055 A CN201910748055 A CN 201910748055A CN 112390705 B CN112390705 B CN 112390705B
- Authority
- CN
- China
- Prior art keywords
- butanediol
- organic solvent
- crude
- odor
- phase separation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C07C29/86—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for purifying 1,3-butanediol, which selects a specific aliphatic hydrocarbon organic solvent according to the method for purifying 1,3-butanediol, wherein the solubility of the 1,3-butanediol in the aliphatic hydrocarbon organic solvent is small, the two are basically immiscible, so that the two can be directly mixed, then 1,3-butanediol can be automatically separated from the organic solvent, and the purpose of removing the odor of crude 1,3-butanediol can be achieved after 1,3-butanediol layer is distilled. Other ketone, ester, ether organic solvents such as methyl isobutyl ketone, ethyl acetate, diethyl ether, etc. since 1,3-butanediol has comparable solubility therein, in order to facilitate phase separation of such organic solvents from 1,3-butanediol, a certain amount of water needs to be added to 1,3-butanediol. By adopting the deodorization method, water does not need to be added into the crude 1,3-butanediol to promote phase separation, so that the distillation dehydration process with high energy consumption is omitted.
Description
Technical Field
The invention relates to a method for purifying chemicals, in particular to a method for deodorizing 1,3-butanediol.
Background
1,3-butanediol (1,3-Butylene Glycol,1,3-BDO) is a chemical product with wide application, and can be used for preparing synthetic resin, plasticizer, surfactant and the like. 1,3-butanediol also has good hygroscopicity, nonvolatility, odorless property, low toxicity, good water solubility, etc., and can be used as moisturizer and softener for textile, tobacco and paper, antibacterial agent for cheese or meat, etc.; the product is mainly used as humectant in cosmetics, has good antibacterial effect, and can be used for producing various astringent, ointment and toothpaste. When 1,3-butanediol is used as the humectant, 1,3-butanediol having no odor is preferably used. However, the industrial crude 1,3-butanediol tends to have an unpleasant odor, which may be mainly caused by the trace impurities contained therein.
As a method for deodorizing 1,3-butanediol, WO00/07969 discloses a method in which after an alkali metal is added to crude 1,3-butanediol from which high boiling substances are removed, and heat treatment is performed, 1,3-butanediol is distilled off, and an alkali metal compound and a high boiling substance are separated as a residue, and then low boiling substances are distilled off from 1,3-butanediol fraction. US8445733B1 provides a method for odor removal of crude 1,3-butanediol using activated carbon, which can be activated with phosphoric acid when the activated carbon is spent, allowing the activated carbon to be recycled. CN1558890a discloses a method of mixing crude 1,3-butanediol with water, extracting with an organic solvent, phase separating into an aqueous layer and an organic layer containing 1,3-butanediol, and distilling to remove water and impurities to obtain odorless 1,3-butanediol. The odor removal methods have the defects of complex process, loss of a target product 1,3-butanediol, generation of a large amount of waste and the like, and the odor of the 1,3-butanediol is gradually accumulated and increased after storage, so that the use requirements cannot be met.
Disclosure of Invention
In view of the above problems of the prior art, according to one aspect of the present invention, there is provided a method for purifying high purity odorless 1,3-butanediol, characterized in that:
directly mixing the odorous crude 1,3-butanediol with an organic solvent, fully stirring and mixing, standing and separating the mixture, and directly obtaining a 1,3-butanediol layer. 1,3-butanediol to organic solvent volume ratio of 0.1 to 1, preferably 0.5.
Preferably, the organic solvent is selected from organic solvents having low solubility in 1,3-butanediol, preferably one or more of aliphatic hydrocarbons such as n-hexane, n-heptane, cyclohexane and petroleum ether, more preferably n-hexane or cyclohexane.
Preferably, the crude 1,3-butanediol can be 1,3-butanediol with little or no water, if the crude 1,3-butanediol contains little water, after phase separation, the 1,3-butanediol layer can be further distilled to remove water. The gas chromatographic purity of the crude 1,3-butanediol is less than or equal to 99.2%.
Preferably, the temperature at the time of the mixing is also not particularly limited, and the temperature is preferably 5 to 70 ℃.
The crude 1,3-butanediol used as the raw material of the present invention may be 1,3-butanediol having an odor or 1,3-butanediol having an increased odor over time.
The method for producing crude 1,3-butanediol is not particularly limited. A reaction product obtained by hydrogenation reduction of 3-hydroxybutyraldehyde may be distilled to remove ethanol or the like as a by-product; alternatively, the fraction from which ethanol has been removed may be subjected to one or more known purification steps, for example, distillation or addition of an alkali metal compound and heat treatment to obtain a product, which is used as crude 1,3-butanediol.
In addition, crude 1,3-butanediol is also commercially available.
Preferably, the mixing of the crude 1,3-butanediol with the organic solvent may be carried out by batch or continuous methods according to the purification method of the present invention.
As a batch type embodiment, crude 1,3-butanediol and an organic solvent may be added to a stirred tank, stirred for 10 seconds to 1 hour, and then allowed to stand for 1 minute to 10 hours to undergo phase separation; the crude 1,3-butanediol may also be repeatedly added with the organic solvent and subjected to phase separation. The number of repetitions is preferably from 1 to 4, the amount of organic solvent added per time being from 20 to 50% by volume, based on the volume of crude 1,3-butanediol.
As the continuous embodiment, an apparatus generally used for continuous extraction, for example, a packed column, a plate column or the like can be used.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description is made, it should be understood that the terms used in the present specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the invention, so it should be understood that other equivalents and modifications could be made thereto without departing from the spirit and scope of the invention.
According to the purification method disclosed by the invention, a specific aliphatic hydrocarbon organic solvent is selected, 1,3-butanediol has low solubility in the solvent and is basically immiscible, so that the solvent and the solvent can be directly mixed, then 1,3-butanediol can be automatically separated from the organic solvent, and the purpose of removing the odor of crude 1,3-butanediol can be achieved after the 1,3-butanediol layer is distilled. Other ketone, ester, ether organic solvents such as methyl isobutyl ketone, ethyl acetate, diethyl ether, etc. since 1,3-butanediol has comparable solubility therein, in order to facilitate phase separation of such organic solvents from 1,3-butanediol, a certain amount of water needs to be added to 1,3-butanediol. By adopting the deodorization method, water does not need to be added into the crude 1,3-butanediol to promote phase separation, so that the distillation dehydration process with high energy consumption is omitted.
The purification method can improve the gas chromatography purity of 1,3-butanediol from 99.2% to over 99.6%.
When the extracting agents such as esters, ketones, ethers and the like are adopted, such as ethyl acetate, methyl isobutyl ketone, diethyl ether and the like, as 1,3-butanediol has a considerable solubility in the organic solvents, in order to promote the 1,3-butanediol to be separated from the extracting agents, water and 1,3-butanediol are added to be dissolved into one phase, so that a corresponding distillation and water removal process is required during subsequent treatment, and the energy consumption is increased. In addition, although water can promote the phase separation of 1,3-butanediol from these organic solvents, a portion of 1,3-butanediol remains dissolved in the organic solvent after phase separation, causing losses. 1,3-butanediol is almost insoluble in aliphatic hydrocarbon organic solvents such as n-hexane, n-heptane, cyclohexane and petroleum ether, spontaneous phase separation is easy to occur without adding extra water, the loss of 1,3-butanediol in the extraction process is small, and a distillation dehydration process is not needed, so that the energy consumption is reduced.
The following examples are given by way of illustration of embodiments of the invention and are not to be construed as limiting the invention, and it will be understood by those skilled in the art that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
Example 1:
the raw material 1,3-butanediol is 1,3-butanediol obtained by distillation and refining after hydrogenation reduction reaction of 3-hydroxybutyraldehyde. Colorless, gas chromatography purity of 99.2%, and obvious odor.
100g of the crude 1,3-butanediol starting material and 100g of cyclohexane were mixed, stirred for 10 minutes, allowed to stand for delamination, and the 1,3-butanediol layer was separated and repeated four times, yielding 1,3-butanediol layer of 100. + -. 0.5g in total. The operation processes of phase separation, transfer, etc. cause a small amount of errors.
The separated 1,3-butanediol layer is distilled and refined under reduced pressure, the vacuum degree is 120Pa, the kettle bottom temperature is 120 ℃, 91g of 1,3-butanediol fraction at 59-60 ℃ can be collected, the purity of a gas chromatography is 99.6%, and no odor exists.
In addition, it is to be noted that the loss of quality of the product in the above-mentioned deodorizing operation is due to the fact that a portion of the sample remains in the distillation apparatus, as is well known to those skilled in the art. The mass loss does not occur during the phase separation and does not result in product loss due to the dissolution of 1,3-butanediol in cyclohexane.
Example 2:
the raw material of the crude 1,3-butanediol is 1,3-butanediol obtained by distillation and refining after the hydrogenation reduction reaction of 3-hydroxybutyraldehyde. Colorless, gas chromatography purity of 99.2%, and obvious odor.
5-20 mesh quartz sand was packed in a glass packed column (inner diameter 25mm, height 500 mm), 100mL of 1, 3-butanediol was fed at a rate of 10 mL/hr from the top, and 400mL of n-hexane was fed at a rate of 40 mL/hr from the bottom. 1,3-butanediol and n-hexane are separated in the column bottom appendix, and a 1,3-butanediol layer emerges from the column bottom.
And (3) distilling and refining the separated 1,3-butanediol layer under reduced pressure, wherein the vacuum degree is 120Pa, the kettle bottom temperature is 120 ℃, 90g of 1,3-butanediol fraction at 59-60 ℃ can be collected, the purity of a gas chromatography is 99.6%, and no odor exists.
Comparative example 1
The raw material 1,3-butanediol is 1,3-butanediol obtained by distillation and refining after hydrogenation reduction reaction of 3-hydroxybutyraldehyde. Colorless, gas chromatography purity of 99.2%, and obvious odor.
100g of the crude 1,3-butanediol starting material was mixed with 100g of ethyl acetate, stirred for 10 minutes and then allowed to stand still until no separation occurred.
Comparative example 2
The raw material of the crude 1,3-butanediol is 1,3-butanediol obtained by distillation and refining after the hydrogenation reduction reaction of 3-hydroxybutyraldehyde. Colorless, gas chromatography purity of 99.2%, and obvious odor.
100g of the crude 1,3-butanediol starting material, 100g of water and 100g of ethyl acetate were mixed, stirred for 10 minutes and allowed to stand for separation. This operation was repeated four times, giving 1,3-butanediol and 161g of aqueous phase. The separated 1,3-butanediol aqueous solution is distilled and refined under reduced pressure, the vacuum degree is 120Pa, the kettle bottom temperature is 120 ℃, and 56g of 1,3-butanediol fraction (the purity of gas chromatography is 99.6%) at 59-60 ℃ can be collected. Since 1,3-butanediol is still dissolved in ethyl acetate, losses are incurred during the phase separation.
Test example 1
Evaluation of the odor of 1,3-butanediol after purification can be detected according to the following method described in the prior art (chinese patent CN1558890 a).
Preparation of standard sample: using a 10% (by weight) aqueous solution of 1,3-butanediol obtained by ordinary distillation purification as a standard, 5 standard samples of 100g each having different odor concentrations were prepared according to the following Table 1 and placed in a 200ml wide-necked flask.
Evaluation method of odor: 40g of 1,3-butanediol purified in examples 1 and 2 was added to distilled water to a concentration of 1,3-butanediol of about 10% by weight, and then placed in a 100ml wide-necked flask and capped, stirred vigorously for 1 minute, and the bottle cap was opened to smell odor and compared with a standard odor sample to determine the odor grade of the sample.
TABLE 1
| Odor class | 1 | 2 | 3 | 4 | 5 |
| The composition ratio is as follows: stock solution/distilled water (weight/weight) | 1/20 | 1/50 | 1/100 | 1/200 | 1/400 |
Odor grade in table 1:1. the odor is felt; 2. between 1 and 3; 3. feeble odor is felt; 4. between 3 and 5; 5. no odor was felt.
Evaluation results were as follows: the evaluation result of 1,3-butanediol obtained according to examples 1 and 2 of the present invention by the above evaluation method was odor grade 5. The evaluation result of 1,3-butanediol having an odor value of 3 was obtained in comparative example 2.
Test example 2
100g of 1,3-butanediol purified in example 1, example 2 and comparative example 2 was placed in a container, sealed with nitrogen, and stored in a constant temperature environment of 40 ℃. After 3 months, the odor evaluation was performed according to test example 1. The evaluation results show that after 3 months, the odor grade of 1,3-butanediol obtained by purification in examples 1 and 2 of the present invention is still 5, that is, the odor is not increased significantly. The evaluation result of 1,3-butanediol having an odor value of 5363 obtained in comparative example 2 was odor grade 2.
Claims (7)
1. A method for purifying high-purity odorless 1,3-butanediol is characterized by comprising the following steps:
directly mixing odorous crude 1,3-butanediol with an organic solvent, fully stirring and mixing, standing and separating phases to directly obtain a 1,3-butanediol layer, wherein the volume ratio of 1,3-butanediol to the organic solvent is 0.1 to 1, and extracting for 2 to 5 times;
the organic solvent is n-hexane or cyclohexane;
the crude 1,3 butanediol is 1,3 butanediol with little or no water, the crude 1,3 butanediol has a gas chromatography purity of 99.2% or less.
2. The purification process of claim 1, wherein the volume ratio of 1,3-butanediol to organic solvent is 0.5 to 5:1, and the extraction is 3 times.
3. The purification process of claim 1, wherein the volume ratio of 1,3-butanediol to organic solvent is 1:1.
4. The purification method according to claim 1, wherein the temperature at the time of mixing is 5 to 70 ℃.
5. The purification process of claim 1, wherein the mixing of the crude 1,3-butanediol with the organic solvent is carried out by batch or continuous mode.
6. The purification method according to claim 5, wherein the batch mode is implemented by adding crude 1,3-butanediol and an organic solvent into a stirring tank, stirring for 10 seconds to 1 hour, and then standing for 1 minute to 10 hours for phase separation; or repeatedly adding the organic solvent into the crude 1,3-butanediol for phase separation, wherein the repeated operation times are 1-4 times, and the volume of the organic solvent added in each time is 20-50% of the volume of the crude 1,3-butanediol.
7. The purification process according to claim 5, wherein the continuous mode is carried out by using a packed column or a tray column which is generally used in continuous extraction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910748055.3A CN112390705B (en) | 2019-08-14 | 2019-08-14 | 1,3-butanediol deodorization purification method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910748055.3A CN112390705B (en) | 2019-08-14 | 2019-08-14 | 1,3-butanediol deodorization purification method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112390705A CN112390705A (en) | 2021-02-23 |
| CN112390705B true CN112390705B (en) | 2022-11-01 |
Family
ID=74601285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910748055.3A Active CN112390705B (en) | 2019-08-14 | 2019-08-14 | 1,3-butanediol deodorization purification method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112390705B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7086254B1 (en) * | 2021-06-04 | 2022-06-17 | Ｋｈネオケム株式会社 | Product 1,3-butylene glycol |
| CN114890869B (en) * | 2022-06-30 | 2024-04-09 | 中国天辰工程有限公司 | Refining and deodorizing method for 1, 3-butanediol |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB703108A (en) * | 1951-09-13 | 1954-01-27 | Fairweather Harold G C | Purification of butanediol |
| JPH07258129A (en) * | 1994-03-17 | 1995-10-09 | Daicel Chem Ind Ltd | Purification of 1,3-butylene glycol |
| JP2001213824A (en) * | 2000-02-04 | 2001-08-07 | Daicel Chem Ind Ltd | Method of producing purified 1,3-butylene glycol |
| JP2003096006A (en) * | 2001-09-26 | 2003-04-03 | Kyowa Yuka Co Ltd | 1,3-butylene glycol and its producing method |
| WO2016026726A1 (en) * | 2014-08-20 | 2016-02-25 | Basf Se | Process for purifying 1,4-butanediol by extraction |
| CN109422624A (en) * | 2017-09-05 | 2019-03-05 | 东营市海科新源化工有限责任公司 | A kind of preparation method of 1,3 butylene glycol |
| CN110668917A (en) * | 2019-10-31 | 2020-01-10 | 天津市汇筑恒升科技有限公司 | Synthesis device and synthesis method of 1, 3-butanediol |
| WO2021132360A1 (en) * | 2019-12-28 | 2021-07-01 | 株式会社ダイセル | Method for producing 1,3-butylene glycol, and 1,3-butylene glycol product |
-
2019
- 2019-08-14 CN CN201910748055.3A patent/CN112390705B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB703108A (en) * | 1951-09-13 | 1954-01-27 | Fairweather Harold G C | Purification of butanediol |
| JPH07258129A (en) * | 1994-03-17 | 1995-10-09 | Daicel Chem Ind Ltd | Purification of 1,3-butylene glycol |
| JP2001213824A (en) * | 2000-02-04 | 2001-08-07 | Daicel Chem Ind Ltd | Method of producing purified 1,3-butylene glycol |
| JP2003096006A (en) * | 2001-09-26 | 2003-04-03 | Kyowa Yuka Co Ltd | 1,3-butylene glycol and its producing method |
| CN1558890A (en) * | 2001-09-26 | 2004-12-29 | Э���ͻ���ʽ���� | 1, 3-butylene glycol and process for producing the same |
| WO2016026726A1 (en) * | 2014-08-20 | 2016-02-25 | Basf Se | Process for purifying 1,4-butanediol by extraction |
| CN109422624A (en) * | 2017-09-05 | 2019-03-05 | 东营市海科新源化工有限责任公司 | A kind of preparation method of 1,3 butylene glycol |
| CN110668917A (en) * | 2019-10-31 | 2020-01-10 | 天津市汇筑恒升科技有限公司 | Synthesis device and synthesis method of 1, 3-butanediol |
| WO2021132360A1 (en) * | 2019-12-28 | 2021-07-01 | 株式会社ダイセル | Method for producing 1,3-butylene glycol, and 1,3-butylene glycol product |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112390705A (en) | 2021-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112390705B (en) | 1,3-butanediol deodorization purification method | |
| JP7191835B2 (en) | Method for purifying natural vanillin | |
| JP3369707B2 (en) | Purification method of 1,3-butylene glycol | |
| WO2021132369A1 (en) | 1,3-butylene glycol product | |
| KR20020050265A (en) | Method for Production of Formic Acid | |
| CA2801580A1 (en) | Process for the preparation of formic acid | |
| CN103467475B (en) | The purification process of 1, 8-Cineole | |
| KR20010102420A (en) | High-purity 1,3-butylene glycol, process for producing 1,3-butylene glycol, and process for producing by-product butanol and butyl acetate | |
| RU2338737C2 (en) | Method of obtaining formaldehyde raw material with low water content | |
| TW460448B (en) | A process for the removal of formaldehyde species from a liquid organic mixture and a process for the production of methyl methacrylate | |
| NO141617B (en) | PROCEDURE FOR ALKALIC EXTRACTION OF CELLULOSIC PREPARATION OF BLACHEMAN | |
| JP2003096006A (en) | 1,3-butylene glycol and its producing method | |
| RU2006132486A (en) | METHOD FOR PRODUCING VEGETABLE OILS WITH HYDROXYL FUNCTIONAL GROUPS | |
| CN110914228B (en) | Method for decoloring and deodorizing polyols | |
| JP2001213825A (en) | High-purity 1,3-butylene glycol | |
| US2859117A (en) | Treatment of alcoholic liquors | |
| JP2004115404A (en) | Method for producing low odorous water-soluble polyol | |
| US7235275B2 (en) | Process for preparing orange oil | |
| KR101995009B1 (en) | Purifying method of alkanediol | |
| CN114867705A (en) | 1, 3-butanediol | |
| US6207867B1 (en) | Method for purifying β-phenylethyl alcohol | |
| KR20160074499A (en) | Method for the preparation of 1,4-butane diol having an apha color index of less than 30 | |
| JP7408005B1 (en) | Production method of high purity 1,3-butylene glycol | |
| JP2614105B2 (en) | How to deodorize ethylene glycol | |
| KR20230130346A (en) | Purification method for 2,3-butanediol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |