CN111718236B - Preparation method of aliphatic diol - Google Patents
Preparation method of aliphatic diol Download PDFInfo
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- CN111718236B CN111718236B CN202010659849.5A CN202010659849A CN111718236B CN 111718236 B CN111718236 B CN 111718236B CN 202010659849 A CN202010659849 A CN 202010659849A CN 111718236 B CN111718236 B CN 111718236B
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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
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
Abstract
The invention discloses a preparation method of aliphatic dihydric alcohol, which takes an epoxy compound as a raw material and long-chain organic acid as a surfactant to prepare the aliphatic dihydric alcohol by pressure hydration under the catalysis of solid phosphoric acid. The method of the invention adopts the surfactant to promote the mixed mass transfer of the epoxy compound and water, and simultaneously synergistically promotes the high-selectivity ring-opening hydration reaction performance of the solid phosphoric acid catalyst to the epoxy compound, and prepares the aliphatic diol with high selectivity under low water ratio, mainly solves the defects of high reaction water ratio, large energy consumption and low product selectivity in the prior technical scheme, and can be used for the industrial production of the aliphatic diol.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing aliphatic diol by catalytic hydration of an epoxy compound.
Background
Aliphatic diols such as ethylene glycol, propylene glycol, hexylene glycol and the like are used as important organic chemical raw materials, and are mainly used for synthesizing polyester resins, antifreezes, cosmetics, photographic materials, lubricants, medical intermediates, various fine chemicals and the like. Conventional methods for producing aliphatic diols are widely used industrially, using epoxides, which are obtained by hydration with water in the presence of a catalyst-free or strongly acidic catalyst, such as sulfuric acid (S.A. Miller, "ethylene and its industrial derivatives", p. 588-594, Ernest Benn Co., Ltd., 1969; Kirk-Othmer, Encyclopedia of Chemical Technology, Volume 11, Fourth Edition, page 700,1994).
This reaction is believed to be a nucleophilic substitution reaction whereby opening of the alkylene oxide occurs and water acts as a nucleophile. Since the initially formed monoalkylene glycol also acts as a nucleophile, a mixture of monoalkylene glycol, dialkylene glycol and higher alkylene glycol is usually formed. To increase the selectivity of the monoalkylene glycol, it is common to increase the water content of the mixture to suppress the occurrence of side reactions. The water used for the reaction is generally 10 to 25 times greater per mole of epoxide. However, even with a very large excess of water, the selectivity to ethylene glycol in a typical commercial process for ethylene glycol is only 88-90%. Thus, this method has a significant drawback: that is, after the completion of the hydration reaction, since a large amount of energy is consumed for concentrating, dehydrating and fractionating the reaction mixture, these methods are extremely uneconomical and costly in terms of economical efficiency.
Later it was found that basic catalysts have an effect of accelerating hydration. They also generally exacerbate side reactions and increase the amount of by-products compared to the above-mentioned catalyst-free or strongly acidic catalysts. In order to overcome the defects of non-catalytic hydration, many research institutions pay attention to the preparation of dihydric alcohol by catalytic hydration of epoxide, and successively develop catalytic systems such as anion exchange resin (CN 1282310A, RU 2149864), organic quaternary phosphonium salt (RU 96121781.2), double catalyst (CN 86107894A) consisting of carboxylic acid and carboxylate, macrocyclic chelating compound (WO99/23053), niobium oxide catalyst (CN1765861A), organic metal tin catalyst (CN104437607B), metal organic framework catalyst (CN111097531A) with cage structure, solid acid catalyst (CN110354899A) polymerized by free radicals such as ionic liquid and the like. The disadvantages of the anion exchange resin catalytic system are poor heat resistance, severe swelling and short service life; the carboxylic acid and the carboxylate have the disadvantages of difficult separation and recovery; the organic quaternary phosphonium salts and macrocyclic chelating compounds have disadvantages in that the catalyst cost is high, separation and recovery are difficult, and the use of a large amount of carbon dioxide limits their popularization and industrial application. Although the niobium oxide catalyst or the organometallic tin catalyst can be used in a high-temperature reaction system, the cost is high, and the environmental pollution problem of heavy metals is involved. The preparation processes of the metal organic framework catalyst with the cage structure and the solid acid catalyst polymerized by free radicals such as ionic liquid and the like are complex, and are not suitable for industrial application. Although the above-mentioned research work has made some progress in various catalyst systems, it is still impossible to carry out industrial mass production at low cost.
Therefore, a new catalytic hydration technology is still needed to be developed to realize that the epoxy compound can be used for preparing the aliphatic diol with high selectivity at a lower water ratio; meanwhile, the catalyst is convenient to recycle.
Disclosure of Invention
The invention aims to provide a preparation method of aliphatic dihydric alcohol, which takes an epoxy compound as a raw material and long-chain organic acid as a surfactant to obtain the aliphatic dihydric alcohol by pressure hydration under the catalysis of solid phosphoric acid. The method of the invention adopts the surfactant to promote the mixed mass transfer of the epoxy compound and water, and simultaneously synergistically promotes the high-selectivity ring-opening hydration reaction performance of the solid phosphoric acid catalyst to the epoxy compound, and prepares the aliphatic diol with high selectivity under low water ratio, mainly solves the defects of high reaction water ratio, high energy consumption and low product selectivity in the prior technical scheme, and can be used for the industrial production of the aliphatic diol.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the preparation method of the aliphatic diol is characterized in that an epoxy compound is used as a raw material, a long-chain organic acid is used as a surfactant, and the aliphatic diol is prepared by pressurized hydration reaction under the action of a solid phosphoric acid catalyst.
In a specific embodiment, the epoxy compound is C2-C10The aliphatic epoxy compound of (2) may be, for example, ethylene oxide, propylene oxide, cyclopentane oxide, chloropropylene oxide or cyclohexane oxide, preferably hexane oxide or pentane oxide.
In a particular embodiment, the long-chain organic acid is selected from any one of caproic acid, caprylic acid, sebacic acid, dodecanoic acid or octadecanoic acid, preferably caprylic acid or dodecanoic acid, more preferably dodecanoic acid.
In a particular embodiment, the surfactant is used in an amount of 0.1 to 1 wt%, preferably 0.5 to 1 wt%, more preferably 0.6 to 0.8 wt% of the mass of the epoxy compound.
In a particular embodiment, the hydration reaction has a water to epoxide molar ratio of from 2 to 10, preferably from 2 to 5, more preferably from 3 to 4.
In a specific embodiment, the amount of the solid phosphoric acid catalyst used in the hydration reaction is 5 to 20%, preferably 5 to 10%, and more preferably 6 to 8% by weight of the amount of the epoxide.
In a particular embodiment, the temperature of the hydration reaction is between 90 and 150 ℃, preferably 100 and 120 ℃.
In a specific embodiment, the pressure of the hydration reaction is in the range of 0.2 to 3MPa, preferably 0.5 to 1MPa, gauge.
In a particular embodiment, the hydration reaction time is between 0.5 and 4h, preferably between 1 and 2 h.
In a specific embodiment, the solid support of the solid phosphoric acid catalyst is any one of diatomite, kaolin, activated carbon, zeolite, molecular sieve, alumina, silica, spinel, mullite or montmorillonite, preferably diatomite or molecular sieve.
The method for preparing the solid phosphoric acid catalyst is not particularly limited, and any method known in the art, such as an impregnation method, may be used. The shape of the solid phosphoric acid catalyst is also not limited, and may be, for example, a powder, or various shapes made of powder, including, but not limited to, a block, a bar, a raschig ring, a pellet, a sphere, a cylinder, etc. The preparation method of the solid phosphoric acid catalyst is, for example, that the solid carrier is soaked in phosphoric acid for a period of time, dried and roasted. The dipping time, the drying temperature, the roasting time and the like can refer to the prior art, and the catalytic activity of the prepared solid phosphoric acid catalyst can be ensured.
In the present invention, the hydration reaction is generally carried out in a liquid phase. Any batch, continuous, semi-continuous reactor is suitable for the hydration reaction of the present invention. Meanwhile, the present invention is not limited to the type of the reactor, and for example, an autoclave, a fixed bed or a moving bed reactor may be used. Therefore, the method has high universality, does not depend on a specific reactor form or a catalyst with a specific structure, and is easy to popularize and apply on a large scale.
After the hydration reaction is complete, the catalyst may be removed by conventional means, such as filtration. For reactors such as fixed beds and the like, the catalyst does not run off, so that the problem of separation of the catalyst does not exist. After the catalyst is removed from the product after the reaction is finished, the aliphatic diol with high purity can be obtained by rectification, and the catalyst can be continuously utilized.
Compared with the prior art, the invention has the following advantages:
1) in the preparation method of the aliphatic diol, the adopted catalyst solid phosphoric acid is medium-strong acid, so that the polymerization side reaction caused by strong acid and strong base catalyst is reduced, the selectivity of the aliphatic diol reaches 94-99%, meanwhile, the catalyst is easy to separate from the product and can be continuously utilized, the catalyst is recycled for 5 times, and the selectivity of the aliphatic diol is still kept above 93%.
2) In the preparation method of the aliphatic dihydric alcohol, the long-chain organic acid is added as the surfactant, and under the reaction system of the surfactant, the mixed mass transfer of the epoxy compound and water is facilitated in the reaction, and the long-chain organic acid can also form a synergistic effect with the solid phosphoric acid catalyst, so that the effect of promoting the high-selectivity ring-opening reaction of the epoxy compound is achieved, the generation of polymerization byproducts is inhibited, and the selectivity of the obtained dihydric alcohol is more than 94%.
3) According to the preparation method of the aliphatic diol, the reaction water ratio is greatly reduced from 10-25 to below 10 in the prior art, and can be reduced to 2-5, so that energy and water resources can be remarkably saved, the process flow is simplified, the production capacity of a device is improved, and the preparation method is more suitable for industrial mass production.
4) The preparation method of the aliphatic diol has no limitation on the reactor form, can be a reaction kettle, a fixed bed or a fluidized bed and the like, has cheap and easily obtained catalyst, high universality and simple popularization.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention as claimed.
The alkylene oxide, the surfactant and the catalyst used as the starting materials in the examples were commercially available reagents.
Hexane epoxide, pentane epoxide: aladdin Biotechnology Ltd;
solid phosphoric acid: ningbo Subock energy environmental protection science and technology, Inc.;
octanoic acid, dodecanoic acid, sodium dodecylbenzenesulfonate: chemical agents of the national drug group, ltd.
GC instrument model: shimadzu GC-2010-plus
GC parameters: chromatographic column DB-5, column temperature: the initial temperature was 50 deg.C, the temperature was raised to 300 deg.C, and the temperature was maintained for 10 min.
Sample inlet temperature: 280 ℃, detector temperature: 300 ℃, air flow: 400ml/min, hydrogen flow: 40ml/min, tail gas blowing flow: 30ml/min, pressure: 77.7 kPa.
Examples 1 to 8
In an autoclave with the capacity of 1000 ml and provided with a stirrer, a thermometer and a pressure gauge, adding alkylene oxide and water with a certain molar ratio, 0.1-1% of organic acid surfactant and 5-20% of solid phosphoric acid catalyst by mass of the alkylene oxide, charging nitrogen to keep the pressure at 2-30bar (gauge pressure), raising the reaction temperature to 90-150 ℃, keeping the rotating speed at 500 r/min, and reacting for 0.5-4 hours. After the reaction is finished, cooling to room temperature, carrying out qualitative and quantitative analysis on the reaction liquid by using gas chromatography, calculating the conversion rate of the alkylene oxide and the selectivity of the dihydric alcohol product, wherein the raw material ratio, the reaction conditions and the reaction result in the reaction process are shown in table 1. The catalyst is filtered and recovered, washed by ethanol and water and dried in vacuum for later use.
Examples 9 to 10
Loading 10g solid phosphoric acid particles into a stainless steel fixed bed reactor with the inner diameter of 8 mm and the length of 300 mm, mixing raw material cyclohexene oxide with 2-10 times of molar weight of water and 0.1-1% of lauric acid by mass, and using a metering pump to adjust the liquid space velocity for 0.5-1h-1Feeding, reacting under the conditions of reaction pressure of 0.2-3MPa and hot spot temperature of 90-150 ℃ to prepare hexanediol, carrying out qualitative and quantitative analysis on the product by using gas chromatography, and calculating the conversion rate of epoxy hexane and the selectivity of hexanediol, wherein the reaction conditions and results are shown in Table 1.
Example 11
The reaction conditions were the same as in example 1 except that the fresh solid phosphoric acid catalyst was changed to the recovered catalyst, and the reaction results were as follows.
Comparative example 1
100.2g (1 mol) of cyclohexene oxide, 360g (20 mol) of water and 0.5g of a liquid sulfuric acid catalyst were charged into an autoclave having a capacity of 1000 ml and equipped with a stirrer, a thermometer and a pressure gauge, the pressure was maintained at 10bar (gauge pressure) by introducing nitrogen gas, the reaction temperature was raised to 120 ℃ and the rotational speed was maintained at 500 rpm, and the reaction was carried out for 1 hour. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was subjected to qualitative and quantitative analysis by gas chromatography, as shown in Table 1, the conversion of cyclohexene oxide was 100%, and the selectivity of hexanediol was 86%.
Comparative examples 2 to 4
In an autoclave with the capacity of 1000 ml and provided with a stirrer, a thermometer and a pressure gauge, alkylene oxide and water in a certain molar ratio, 5-10% of solid phosphoric acid catalyst (based on the mass of alkylene oxide) and 0-1% of surfactant (based on the mass of alkylene oxide) are added, nitrogen is filled to keep the pressure at 5-10bar (gauge pressure), the reaction temperature is increased to 100 ℃ and 120 ℃, the rotation speed is kept at 500 r/min, and the reaction is carried out for 1-2 hours. After the reaction, the reaction solution was cooled to room temperature, and the reaction solution was subjected to qualitative and quantitative analysis by gas chromatography to calculate the conversion rate of alkylene oxide and the selectivity of glycol, and the reaction conditions and results are shown in table 1.
TABLE 1 catalytic hydrolysis reaction Performance of alkylene oxides under different conditions
Description of the drawings: xAlkane(s)Conversion of alkylene oxide, SDiolsSelectivity to the main product monoalkylene glycol.
As can be seen from comparison of examples 1-11 and comparative examples 1-4, the solid phosphoric acid catalyst and the long-chain organic acid surfactant of the reaction system of the invention are used in combination, so that the ring-opening hydration reaction of the epoxy compound can be catalyzed to prepare the aliphatic diol under the condition of 2-5 low water ratio, the reaction selectivity of the aliphatic diol is effectively improved, the selectivity is as high as more than 94%, and the reaction selectivity can be more than 93% even if the catalyst is repeatedly used. Meanwhile, the occurrence of polymerization side reaction is reduced. On the contrary, compared with the reaction system without adding long-chain organic acid as the surfactant (comparative examples 1, 3 and 4) and the reaction system with adding the conventional surfactant (comparative example 2), the reaction system of the long-chain organic acid and the solid phosphoric acid catalyst has higher reaction selectivity, which shows that the addition of the long-chain organic acid has good synergistic effect and effectively promotes the ring-opening hydration reaction with high selectivity of the epoxy compound.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (16)
1. A preparation method of aliphatic diol is characterized in that an epoxy compound is used as a raw material, long-chain organic acid is used as a surfactant, and the aliphatic diol is prepared by pressurized hydration reaction under the action of a solid phosphoric acid catalyst;
the epoxy compound is C2-C10An aliphatic epoxy compound of (a);
the long-chain organic acid is any one of caproic acid, caprylic acid, sebacic acid, dodecanoic acid or octadecanoic acid.
2. The method according to claim 1, wherein the epoxy compound is cyclohexene oxide or pentane oxide.
3. The method according to claim 1, wherein the long-chain organic acid is octanoic acid or dodecanoic acid.
4. The method according to claim 1, wherein the surfactant is used in an amount of 0.1 to 1 wt% based on the amount of the epoxy compound.
5. The method according to claim 4, wherein the surfactant is used in an amount of 0.5 to 1 wt% based on the amount of the epoxy compound.
6. The method according to any one of claims 1 to 5, wherein the hydration reaction is carried out at a molar ratio of water to epoxide of 2 to 10.
7. The method according to claim 6, wherein the hydration reaction is carried out at a molar ratio of water to epoxide of 2 to 5.
8. The method according to any one of claims 1 to 5, wherein the amount of the solid phosphoric acid catalyst used in the hydration is 5 to 20% by mass of the epoxy compound.
9. The method according to claim 8, wherein the amount of the solid phosphoric acid catalyst used in the hydration reaction is 5 to 10% by mass of the epoxy compound.
10. The method according to any one of claims 1 to 5, wherein the temperature of the hydration reaction is 90 to 150 ℃.
11. The method as claimed in claim 10, wherein the temperature of the hydration reaction is 100-120 ℃.
12. The method according to any one of claims 1 to 5, wherein the pressure of the hydration reaction is 0.2 to 3MPa in gauge.
13. The method according to claim 12, wherein the hydration pressure is 0.5 to 1MPa in gauge pressure.
14. The method according to any one of claims 1 to 5, wherein the hydration reaction time is 0.5 to 4 hours.
15. The method according to any one of claims 1 to 5, wherein the hydration reaction time is 1 to 2 hours.
16. The method for preparing aliphatic diol according to any one of claims 1 to 5, wherein the solid support of the solid phosphoric acid catalyst is any one of diatomaceous earth, kaolin, activated carbon, molecular sieves, alumina, silica, spinel, mullite and montmorillonite.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4762954A (en) * | 1986-08-23 | 1988-08-09 | Degussa Aktiengesellschaft | Continuous method for the production of 1,2-diols |
| US5693870A (en) * | 1993-10-22 | 1997-12-02 | The Dow Chemical Company | Apparatus for producing alkylene glycols, alkyene glycols having higher primary hydroxyl content, method of producing glycols having higher primary hydroxyl content, method of producing acrylate esters |
| CN1765861A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Aliphatic dihydroxy alcohol preparation method |
| CN103864572A (en) * | 2012-12-18 | 2014-06-18 | 中国科学院大连化学物理研究所 | Method for preparing diol |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4762954A (en) * | 1986-08-23 | 1988-08-09 | Degussa Aktiengesellschaft | Continuous method for the production of 1,2-diols |
| US5693870A (en) * | 1993-10-22 | 1997-12-02 | The Dow Chemical Company | Apparatus for producing alkylene glycols, alkyene glycols having higher primary hydroxyl content, method of producing glycols having higher primary hydroxyl content, method of producing acrylate esters |
| CN1765861A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Aliphatic dihydroxy alcohol preparation method |
| CN103864572A (en) * | 2012-12-18 | 2014-06-18 | 中国科学院大连化学物理研究所 | Method for preparing diol |
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