CN115010578A - Preparation method of alkoxide - Google Patents
Preparation method of alkoxide Download PDFInfo
- Publication number
- CN115010578A CN115010578A CN202210478957.1A CN202210478957A CN115010578A CN 115010578 A CN115010578 A CN 115010578A CN 202210478957 A CN202210478957 A CN 202210478957A CN 115010578 A CN115010578 A CN 115010578A
- Authority
- CN
- China
- Prior art keywords
- alkoxide
- alcohol
- preparation
- ball milling
- slurry
- 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.)
- Granted
Links
Images
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
- C07C29/68—Preparation of metal alcoholates
- C07C29/70—Preparation of metal alcoholates by converting hydroxy groups to O-metal groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of alkoxide, which comprises the steps of mixing industrial alcohol and flake caustic soda or potash according to a certain proportion, placing the mixture in a ball milling tank, and carrying out ball milling for a certain time to obtain mixed slurry; settling the mixed slurry by standing to obtain lower slurry and upper liquid; drying the lower layer slurry to obtain alkoxide solid; the upper layer liquid is a mixed liquid of alcohol and alkoxide corresponding to the alcohol and water. In the prior art, generally, it is thought that metal alkoxide is difficult to stably exist as long as water exists in a reaction medium, and meanwhile, the reaction speed of preparing the metal alkoxide by an alkaline method at normal temperature is extremely slow, so that the method is extremely unfavorable for industrial production of the metal alkoxide; the invention adopts a brand new technical route, the preparation of corresponding alkoxide by taking industrial alcohol and flake caustic soda or potash as raw materials through a ball milling method can be carried out at normal temperature, energy is saved, alkoxide-alcohol-water solution generated in the preparation process can be directly used as a product, and can also be recycled as a raw material for recycling after dehydration, the preparation method is environment-friendly and has no emission, and meanwhile, the preparation reaction has low requirements on the raw material and low cost.
Description
Technical Field
The invention belongs to the field of chemistry and chemical engineering, and particularly relates to a preparation method of alkoxide.
Background
The production methods of alkoxides are basically the same, and the process data are different. The current background art for alkoxides is described below using sodium methoxide as an example.
Sodium methoxide is one of alkoxide generated from methanol and has a chemical formula of CH 3 ONa, commonly used in organic synthesisA strong base. Sodium methoxide is usually stored as a solution in an alcohol solvent such as methanol or ethanol. Methanol is dissolved in ether to generate turbid liquid, and the turbid liquid is decomposed into methanol and sodium hydroxide when meeting water: CH (CH) 3 ONa+H 2 O→CH 3 OH+NaOH。
The sodium methoxide product has two forms: the liquid is a methanol solution of sodium methoxide, and the content of the sodium methoxide is 27.5-31%. The liquid sodium methoxide is colorless or yellowish viscous liquid, is sensitive to oxygen, is inflammable and explosive, and is very easy to absorb moisture. The solid is pure sodium methoxide, is colorless amorphous powder, is sensitive to oxygen, is inflammable, is dissolved in methanol and ethanol, is decomposed into methanol and sodium hydroxide when meeting water, is decomposed in air at the temperature of over 126.6 ℃, is insoluble in benzene and toluene, and has strong irritation and strong corrosivity.
Sodium methoxide is mainly used as a condensing agent and a strong basic catalyst to prepare medicines such as vitamin B1, vitamin B6, vitamin A, sulfadiazine and the like. Sodium methoxide is also an organically synthesized catalyst used in the pesticide production and oil and fat processing industries, as a catalyst for treating edible fats and oils, and as an analytical reagent widely used in the industries of perfumes, dyes and the like.
The current methods for preparing sodium methoxide are two methods, namely an alkali method and a metal sodium method.
The sodium methoxide produced by the alkaline process is obtained by the action of methanol and sodium hydroxide, and the reaction formula is as follows:
CH 3 OH+NaOH——CH 3 ONa+H 2 O
(1) preparing methanol alkali liquor: crushing solid sodium hydroxide, proportionally adding the crushed solid sodium hydroxide into an alkali dissolving pot containing methanol (99.8%), starting a liquid alkali circulating pump, controlling the temperature to be below 70 ℃ to dissolve the sodium hydroxide, cooling to 40 ℃, pumping into a settling tank, and standing for 12 hours for later use when the content reaches 20-23%.
(2) Preparation of sodium methoxide: introducing water vapor into an interlayer of a vaporization pot and a reaction tower for heating, controlling the temperature to be 85-100 ℃, adding anhydrous methanol into the vaporization pot at the flow rate of 180L/h, simultaneously adding methanol alkali liquor into the vaporization pot at the flow rate of 25kg/h, evaporating methanol gas containing 2% of moisture generated by reaction from the top of the reaction tower, and introducing the methanol gas into a purification distillation tower for moisture removal so as to enable the anhydrous methanol to be recycled. The temperature of the bottom of the reaction tower (namely a vaporization pot) is controlled to be 65-70 ℃, the materials at the bottom of the reaction tower are checked to contain 27-31 percent of sodium methoxide and less than 1 percent of free alkali, and the product is obtained.
Sodium methoxide produced by a sodium metal method process takes sodium metal and methanol as raw materials, and a chemical reaction is carried out by adopting an intermittent production process to produce a sodium methoxide methanol solution. The reaction formula is as follows:
2CH 3 OH+2Na——2CH 3 ONa+H 2 ↑
the production process mainly comprises four parts:
(1) and a feeding process, namely conveying the industrial methanol to a methanol metering tank by a pump, and putting 120kg of metal sodium into the reaction kettle.
(2) And (3) a nitrogen replacement procedure, namely closing the feeding and emptying valves, introducing nitrogen into the reaction kettle to ensure that the index of the pressure gauge reaches 0.1MPa, opening the emptying valve to relieve pressure, repeating the process for three times, then refluxing, and keeping the emptying valve in an open state to continuously introduce the nitrogen.
(3) And a reaction process, namely introducing cooling water into the condenser, immediately adding methanol into the condenser through a methanol metering tank, reacting, and stopping introducing nitrogen after reacting for 5-10 min. And continuously adding methanol, metering 820kg of methanol within 2-3 h, closing a methanol feeding valve, and continuously reacting for 2-3 h until no bubbles are generated in the reaction liquid.
(4) And a blending procedure, namely adding the product into a blending storage tank, sampling and analyzing, blending to the required concentration, and barreling.
Compared with the sodium method production process, the sodium method production process has the advantages that the sodium method is higher in sodium methoxide content, stable and reliable, the alkali method is used for obtaining sodium methoxide, free alkali is low, sodium method sodium methoxide can remove a large amount of 'alcohol' and other impurities in sodium in the reaction, and the sodium method is higher in Na content in sodium methoxide obtained by the alkali method than the sodium method 2 CO 3 Low content, and high quality and yield.
The method for preparing sodium ethoxide by using the ball milling method disclosed in CN106045813A opens up a new process for preparing alkoxide, but the method still has some problems to be solved, such as the need to reduce the temperature of the reaction by using a water cooling system provided in the ball mill, continuously remove the water generated in the reaction by using calcium oxide, and continuously extract the generated sodium ethoxide by using a circulating pump so as to rapidly and forwardly perform the reaction; the introduction amount of ethanol is also required to be controlled, so that the water lost in the first reaction is ensured to be compensated, and the forward direction of the second reaction is promoted to be carried out; furthermore, the concentration of the prepared product needs to be controlled, precipitation needs to be avoided, and the final product is sodium ethoxide solution with the concentration of 18-21%. Therefore, in the prior art, quicklime is used for removing water, so that the requirements on raw materials are correspondingly higher while solid waste is generated, particularly, the control on each link in the process is relatively strict, and the requirement on the whole production process is higher.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing alkoxide by a ball milling method, which aims at overcoming the defects in the prior art, the corresponding alkoxide solid can be prepared by the ball milling method at normal temperature under the condition that water exists by taking alcohol and caustic soda flakes or potash as raw materials, and alkoxide-alcohol-water solution generated in the preparation process can be directly used as a product and can also be recycled as the raw materials for reutilization after water is removed, so that the method is environment-friendly and free of emission, and meanwhile, the preparation reaction has low requirements on the raw materials and low cost.
The technical scheme adopted by the invention for solving the problems is as follows:
a preparation method of alkoxide, specifically, mixing alcohol and flake caustic soda (or potash) in proportion, placing the mixture into a ball milling tank, ball milling for a certain time, and taking out to obtain mixed slurry; settling the mixed slurry by standing to obtain lower slurry and upper liquid; drying the lower layer slurry to obtain alkoxide solid; the upper layer liquid is a mixed liquid of alcohol and alkoxide corresponding to the alcohol and water.
The reaction equation involved in the above preparation method is:
C n H 2n+1 OH+NaOH——C n H 2n+1 ONa+H 2 o, wherein n is 1, 2, 3, 4, Na may be replaced by K.
According to the scheme, the alcohol, the caustic soda flakes and the potash are in industrial grade and can be used for the method.
According to the scheme, the alcohol comprises methanol, ethanol, propanol, butanol and other alcohols which are liquid at normal temperature, and the alkoxide is an alkoxide correspondingly generated by the alcohol, namely, the corresponding alkoxide, namely sodium alkoxide or potassium alkoxide, is obtained by converting hydrogen ions in the alcohol into sodium ions (or potassium ions).
According to the scheme, the water content of the alcohol is not more than 5 wt%; the potassium alkali purity of the flake alkali is not less than 96%, and the main impurity is Na 2 CO 3 。
According to the scheme, the mass ratio of the alcohol to the caustic soda flakes (or the potash) is in the range of (1.5-5: 1).
According to the scheme, after the alcohol and the caustic soda flakes (or the potash) are mixed, other raw materials are not required to be added, and the mixture is directly subjected to ball milling. Wherein, the ball milling conditions are as follows: the ball milling atmosphere needs to be sealed, and air is isolated; the ball milling temperature is within the range of 0-30 ℃, and is generally room temperature; the ball milling time is 0.5-8 hours; the ball milling speed is generally 6 to 300 rpm. The ball milling process does not need to remove water, and the purity of the product can be controlled only by controlling the proportion of the raw materials. The water generated by the reaction does not cause rapid reverse reaction in a certain concentration range, and is beneficial to removing carbonate impurities. Carbonates are more soluble in water and are mainly present in the liquid, reducing the content of impurities in the settled solids.
According to the scheme, the standing atmosphere is a closed environment and air is isolated so as to avoid autoxidation of the product in the air, and the standing temperature is within the range of 0-30 ℃, and is generally room temperature; the standing time is generally 12-48 hours.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts alcohol and flake caustic soda or potash as raw materials and adopts a ball milling method to prepare alkoxide. The method is obtained unexpectedly in other experimental processes, and later-stage related experiments prove that the method can successfully prepare alkoxide. In the prior art, generally, it is thought that metal alkoxide is difficult to stably exist as long as water exists in a reaction medium, and meanwhile, the reaction speed of preparing the metal alkoxide by an alkaline method at normal temperature is extremely slow, so that the method is extremely unfavorable for industrial production of the metal alkoxide; the invention adopts a brand new technical route, alcohol and flake caustic soda or potash are taken as raw materials, the corresponding alkoxide solid can be prepared by a normal-temperature ball milling method under the condition of water, the alkoxide-alcohol-water solution generated in the preparation process can be directly used as a product, and can also be recycled as a raw material for reutilization after water removal, the environment is protected, no emission is caused, and meanwhile, the preparation reaction has low requirements on the raw materials and low cost.
Drawings
Fig. 1 and 2 show XRD patterns of solid sodium methoxide obtained in example 1 under two different medium ball conditions, respectively.
Fig. 1 corresponds to a zirconium ball and fig. 2 corresponds to an iron ball.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the present invention is not limited to the following examples.
Example 1
A preparation method of sodium methoxide comprises the following specific steps:
(1) taking 1000ml of methanol and 400g of caustic soda flakes, sequentially putting the methanol and the caustic soda flakes into a 3L ball milling tank, then putting grinding balls (zirconium balls or iron balls) into the 3L ball milling tank, sealing and isolating the tank from air, and carrying out ball milling for 8 hours at room temperature at 180 rpm;
(2) taking out the materials obtained after ball milling in the step (1), separating out grinding balls, and standing for 8 hours at room temperature in a closed air-isolated container to separate slurry from liquid to obtain lower-layer slurry and upper-layer liquid respectively;
(3) the upper layer liquid is a mixed liquid of sodium methoxide, methanol and water;
(4) and dehumidifying the lower layer slurry in a vacuum drying oven at the temperature of 60 ℃, and obtaining the solid sodium methoxide.
Table 1 shows the results of detecting solid sodium methoxide obtained in example 1 under two different medium ball conditions. As can be seen from Table 1, the main product of the reaction is sodium methoxide, the mass fraction of the sodium methoxide can reach more than 93 percent, and a small amount of sodium carbonate, free alkali and other impurities are contained; in addition, the medium ball slightly affects the purity of the product, wherein the iron ball grinding ball has little influence on the purity, and the mass fraction of sodium methoxide can reach 96.9%.
TABLE 1
As can be seen from FIG. 1, the reaction product is not amorphous as obtained by conventional methods, but exists in crystalline form. This pattern failed to match in the XRD patterns of all materials at present. The product tested was dried directly without settling. The XRD pattern is a direct basis for distinguishing crystalline from amorphous. The failure of matching XRD patterns indicates that the compound is a material structure which is not discovered yet. Compared with an amorphous body, the crystalline body has lower internal energy, more stable structure and less possibility of oxidation. The alkoxide products obtained in the examples have no flammable characteristics, are flammable only, have similar flammability to wood, and need to be ignited by open fire.
Example 2
A preparation method of sodium ethoxide comprises the following specific steps:
(1) 1250ml of ethanol and 350g of caustic soda flakes are taken, then the ethanol and the caustic soda flakes are sequentially placed into a 3L ball milling tank, grinding balls (zirconium balls) are placed into the ball milling tank, air is sealed and isolated, and the ball milling is carried out at room temperature and 180rpm for 4 hours;
(2) taking out the materials obtained after ball milling in the step (1), separating out grinding balls, and then standing for 8 hours at room temperature in a closed air-isolated container to separate the slurry from the liquid so as to respectively obtain lower-layer slurry and upper-layer liquid;
(3) the upper layer liquid is a mixed liquid of sodium ethoxide, ethanol and water;
(4) and dehumidifying the lower layer slurry in a vacuum drying oven at the temperature of 80 ℃, and obtaining the solid sodium ethoxide.
Table 2 shows the results of measuring the solid sodium ethoxide obtained in example 2. As can be seen from Table 2, the main product of the reaction is sodium ethoxide, the mass fraction of the sodium ethoxide can reach more than 99.2%, and a small amount of sodium carbonate, free alkali and other impurities are contained.
TABLE 2
| Serial number | Detecting items | Unit | The result of the detection | Detection method |
| 1 | Mass fraction of sodium ethoxide | ％ | 99.2 | Titration method |
| 2 | Mass fraction of sodium carbonate | ％ | 0.08 | Titration method |
| 3 | Mass fraction of free base | ％ | 0.30 | Titration method |
| 4 | Melting Point | ℃ | 260 | GB/T 617-2006 |
| 5 | Density of | g/cm 3 | 0.867 | GB/T 611-2006 |
| 6 | Steam pressure (20 ℃ C.) | mmHg | <0.1 | GB/T 21616-2008 |
| 7 | Refractive index | - | 1.386 | GB/T 614-2006 |
The above description is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various modifications and changes without departing from the inventive concept, and these modifications and changes are all within the scope of the present invention.
Claims (7)
1. The preparation method of alkoxide is characterized in that alcohol and alkali are mixed according to a certain proportion and then are placed in a ball milling tank for ball milling to obtain mixed slurry; settling the mixed slurry by standing to obtain lower-layer slurry and upper-layer liquid; drying the lower layer slurry to obtain alkoxide solid; the upper layer liquid is a mixed liquid of alcohol, alkoxide and water;
wherein the alkali is caustic soda and/or potash, and when the alkali is caustic soda, the alkoxide is sodium alkoxide; when the alkali is potash, the alkoxide is potassium alkoxide.
2. A process for the preparation of an alkoxide according to claim 1, characterised in that both the alcohol and the flake caustic are technical grade.
3. A process for the preparation of an alkoxide according to claim 1, characterised in that the alcohol comprises methanol, ethanol, propanol, butanol; the alkoxide is correspondingly generated alkoxide of the raw material alcohol, namely hydrogen ions in the raw material alcohol are converted into sodium ions or potassium ions to obtain the corresponding alkoxide.
4. A process for the preparation of an alkoxide according to claim 1, in which the alcohol has a water content of not more than 5% by weight; the purity of caustic soda flakes and potash is not less than 96%, and the main impurity is Na 2 CO 3 Or K 2 CO 3 。
5. A process for the preparation of an alkoxide as claimed in claim 1, wherein the mass ratio of alcohol to base is in the range of (1.5 to 5: 1).
6. The method according to claim 1, wherein the ball milling conditions are as follows: the ball milling atmosphere needs to be sealed and isolated from air; the ball milling temperature is within the range of 0-30 ℃; the ball milling time is 0.5-8 hours; the ball milling speed is 6-300 rpm.
7. A process for the preparation of an alkoxide according to claim 1, characterised in that the conditions of rest are as follows: the standing atmosphere is a closed environment and air is isolated; standing at the temperature of 0-30 ℃; the standing time is 4-48 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210478957.1A CN115010578B (en) | 2022-05-05 | 2022-05-05 | Preparation method of alkoxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210478957.1A CN115010578B (en) | 2022-05-05 | 2022-05-05 | Preparation method of alkoxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115010578A true CN115010578A (en) | 2022-09-06 |
| CN115010578B CN115010578B (en) | 2023-08-08 |
Family
ID=83067622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210478957.1A Active CN115010578B (en) | 2022-05-05 | 2022-05-05 | Preparation method of alkoxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115010578B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106045813A (en) * | 2016-01-04 | 2016-10-26 | 武汉理工大学 | Ball milling method for preparation of sodium ethoxide |
-
2022
- 2022-05-05 CN CN202210478957.1A patent/CN115010578B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106045813A (en) * | 2016-01-04 | 2016-10-26 | 武汉理工大学 | Ball milling method for preparation of sodium ethoxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115010578B (en) | 2023-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EA024994B1 (en) | Polycarboxylic acid extraction | |
| EP1478593A1 (en) | Aqueous borohydride compositions | |
| CN109734637A (en) | A kind of methionine crystalline mother solution processing method | |
| CN100515956C (en) | Method for extracting nickel sulfate from waste solution of copper electrolysis | |
| CN103113197B (en) | Method for comprehensively utilizing trichlorosucrose production waste gas | |
| CN115010578A (en) | Preparation method of alkoxide | |
| CN113292467B (en) | Method for purifying vitamin A oil mother liquor by using alcohol-containing alkali liquor | |
| CN102583252B (en) | Method for producing sodium periodate | |
| CZ293993B6 (en) | Process for preparing substantially anhydrous magnesium chloride | |
| CN106831334A (en) | A kind of continuous production processes of alkaline process petrohol potassium | |
| US20070297964A1 (en) | Compositions comprising magnesium borohydride and magnesium hydridoborohydride and method for manufacturing the same | |
| CN103318958B (en) | Separation and refining method of arsenic trioxide | |
| CN106745287A (en) | A kind of preparation method of high-pure anhydrous manganese chloride | |
| CN102786176B (en) | Comprehensive utilization method of catalytic cracking gasoline sludge | |
| CN109455742B (en) | Method for simply producing pharmaceutic adjuvant anhydrous sodium sulfite | |
| CN101153006A (en) | Gluconic acid cobalt and method of preparing the same | |
| CN106587090B (en) | A method of synthesizing four water eight borate two sodium using liquid boron rock | |
| CN114534288B (en) | Separation and solvent recovery method of salt-containing mixed solution | |
| CN101921177B (en) | Preparation method of citronellol | |
| CN1031993C (en) | Method for separating unsaponifiables from organic acid | |
| CN215947020U (en) | Processing system of waste lye that extraction trioxymethylene produced | |
| CN110835290B (en) | Synthetic method of methyl cedryl ether | |
| JP2012131658A (en) | Method for producing lithium borofluoride | |
| CN116332804A (en) | Method for eliminating SO2 generated in taurine production process by ethanolamine method | |
| CN116178134A (en) | Process for the preparation of alkoxyacetic acids |
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 |