CN115010578B - Preparation method of alkoxide - Google Patents
Preparation method of alkoxide Download PDFInfo
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- CN115010578B CN115010578B CN202210478957.1A CN202210478957A CN115010578B CN 115010578 B CN115010578 B CN 115010578B CN 202210478957 A CN202210478957 A CN 202210478957A CN 115010578 B CN115010578 B CN 115010578B
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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
- C07C29/68—Preparation of metal alcoholates
- C07C29/70—Preparation of metal alcoholates by converting hydroxy groups to O-metal groups
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- 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
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- 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
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Abstract
The invention discloses a preparation method of alkoxide, which comprises the steps of mixing industrial alcohol and caustic soda flakes or potash in proportion, placing the mixture in a ball milling tank, and ball milling for a certain time to obtain mixed slurry; settling the mixed slurry by standing to obtain lower-layer slurry and upper-layer liquid; drying the lower slurry to obtain alkoxide solid; the upper layer liquid is a mixed liquid of alcohol, alkoxide corresponding to the alcohol and water. In the prior art, the metal alkoxide is generally considered to be difficult to stably exist as long as water exists in a reaction medium, and the reaction speed for preparing the metal alkoxide by an alkaline method at normal temperature is extremely low, so that the method is extremely unfavorable for industrial production of the metal alkoxide; the invention adopts a brand new technical route, the ball milling method for preparing the corresponding alkoxide by taking industrial alcohol and caustic soda flakes or potash as raw materials 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 the alkoxide-alcohol-water solution can be recycled as a raw material after water removal, is environment-friendly and has no emission, and meanwhile, the preparation reaction has low requirement 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 alkoxide production process is essentially the same and the process data differs. The present background art of alkoxides is described below with sodium methoxide as an example.
Sodium methoxide is one of alkoxides of methanol, and has a chemical formula of CH 3 ONa, a strong base commonly used in organic synthesis. Sodium methoxide is usually stored as a solution in an alcoholic solvent such as methanol or ethanol. Dissolving methanol in ether to generate suspension, and decomposing the suspension into methanol and sodium hydroxide when meeting water: CH (CH) 3 ONa+H 2 O→CH 3 OH+NaOH。
Sodium methoxide products come in two forms: liquid and solid, wherein the liquid is methanol solution of sodium methoxide, and the sodium methoxide content is 27.5-31%. The liquid sodium methoxide is colorless or yellowish viscous liquid, is sensitive to oxygen, inflammable and explosive and is very easy to absorb moisture. The solid is pure sodium methoxide, is colorless amorphous powder, is sensitive to oxygen, inflammable, soluble in methanol and ethanol, and can be decomposed into methanol and sodium hydroxide when meeting water, and can be decomposed in air with the temperature of more than 126.6 ℃ and insoluble in benzene and toluene, so that the solid has strong irritation and strong corrosiveness.
Sodium methoxide is mainly used as condensing agent and strong alkaline catalyst for preparing vitamins B1 and B6 and medicaments such as A and sulfadiazine. Sodium methoxide is also a catalyst for organic synthesis, is used in pesticide production and oil processing industries, is used as a catalyst for treating edible fat and edible oil, and can be widely used in industries such as perfume, dye and the like as an analysis reagent.
The existing methods for preparing sodium methoxide are two methods, namely an alkaline 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, adding the crushed solid sodium hydroxide into an alkali dissolving pot containing methanol (99.8%) in proportion, starting a liquid alkali circulating pump, controlling the temperature below 70 ℃ to dissolve the sodium hydroxide, cooling to 40 ℃ when the content reaches 20% -23%, pouring the sodium hydroxide into a precipitation tank, and standing for 12 hours for later use.
(2) Preparation of sodium methoxide: introducing steam into the interlayer of the vaporization pot and the reaction tower, heating, controlling the temperature to be 85-100 ℃, adding anhydrous methanol into the vaporization pot at the flow of 180L/h, simultaneously adding methanol alkali liquor from the top of the reaction tower at the flow of 25kg/h, evaporating 2% water-containing methanol gas generated by the reaction from the top of the reaction tower, and separating water from the purification distillation tower to obtain anhydrous methanol for recycling. The temperature of the bottom of the reaction tower (i.e. the vaporization pot) is controlled at 65-70 ℃, and the product is obtained after the inspection that the bottom material contains 27-31% sodium methoxide and less than 1% free alkali.
Sodium methoxide is produced by using sodium metal and methanol as raw materials through a batch production process to carry out chemical reaction, so as to produce 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 step of pumping industrial methanol to a methanol metering tank and feeding 120kg of metallic sodium into the reaction kettle.
(2) And in the nitrogen replacement procedure, the charging and emptying valve is closed, nitrogen is introduced into the reaction kettle, the index of the pressure gauge reaches 0.1MPa, the emptying valve is opened for pressure relief, reflux is carried out after three times of repetition, and the emptying valve is kept in an opened state for continuously introducing nitrogen.
(3) And (3) a reaction step, namely introducing cooling water into a condenser, immediately adding methanol into the condenser through a methanol metering tank, reacting for 5-10 min, and stopping introducing nitrogen. Continuously adding methanol, metering 820kg of methanol in 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 step, namely adding the product into a blending storage tank, sampling and analyzing, blending to the required concentration, and barreling.
Compared with sodium method production process, sodium method has high content, stability and reliability, low free alkali content, and can remove large amount of alcohol and other impurities in sodium during reaction 2 CO 3 Low content, and can improve the quality and yield of the product.
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 of reducing the reaction temperature by a water cooling system of the ball mill, continuously removing water generated in the reaction by calcium oxide, and continuously extracting the generated sodium ethoxide by a circulating pump, so that the reaction is rapidly and positively carried out; it is also necessary to control the amount of ethanol introduced to ensure compensation for the water lost in the first reaction while promoting the forward progress of the second reaction; furthermore, the concentration of the prepared product is controlled, precipitation needs to be avoided, and the final product is sodium ethoxide solution with the concentration of 18-21%. Therefore, the prior art adopts quicklime to remove water, and has correspondingly higher requirements on raw materials while generating solid waste, and particularly has relatively strict control on each link in the process and higher requirements on the whole production process.
Disclosure of Invention
The invention aims to solve the technical problems that the prior art has the defects, and provides the method for preparing the alkoxide by using the ball milling method, which takes alcohol and caustic soda flakes or potash as raw materials and can prepare corresponding alkoxide solids by using the ball milling method at normal temperature under the condition that water exists, and alkoxide-alcohol-water solution generated in the preparation process can be directly used as a product, can be recycled as the raw material after water is recovered and reused, is environment-friendly and free of emission, and has low requirements on the raw material by the preparation reaction, and low cost.
The invention adopts the technical proposal for solving the problems that:
the preparation method of alkoxide comprises mixing alcohol and caustic soda flakes (or potash) in proportion, placing in a ball milling tank, ball milling for a certain time, and taking out to obtain mixed slurry; settling the mixed slurry through standing to obtain lower-layer slurry and upper-layer liquid; drying the lower slurry to obtain alkoxide solid; the upper layer liquid is a mixed liquid of alcohol, alkoxide corresponding to the alcohol and water.
The reaction equation involved in the preparation method is as follows:
C n H 2n+1 OH+NaOH——C n H 2n+1 ONa+H 2 o, wherein n=1, 2,3,4, na may be replaced by K.
According to the scheme, the alcohol, caustic soda flakes and potash are industrial grade and can be used in the invention.
According to the scheme, the alcohol comprises methanol, ethanol, propanol, butanol and the like which are liquid at normal temperature, wherein the alkoxide is the alkoxide which is correspondingly generated by the alcohol, namely, the alkoxide is obtained by converting hydrogen ions in the alcohol into sodium ions (or potassium ions), namely, sodium alkoxide or potassium alkoxide.
According to the above scheme, the water content of the alcohol is not more than 5% wt; the potash purity of the caustic soda flakes 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 potash) is in the range of (1.5-5:1).
According to the scheme, after alcohol and caustic soda flakes (or potash) are mixed, other raw materials are not needed to be added, and the ball milling is directly carried out. 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 in the range of 0-30 ℃ and is generally room temperature; ball milling time is 0.5-8 hours; the ball milling speed is generally 6 to 300rpm. The ball milling process does not need to remove water, and the purity of the product can be controlled by only controlling the proportion of raw materials. The water produced 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 predominantly present in liquids, reducing the impurity content in the solids after settling.
According to the scheme, the standing atmosphere is a closed environment and is used for isolating air, so that the autoxidation of a product in the air is avoided, and the standing temperature is within the range of 0-30 ℃ and is generally room temperature; the time for standing is generally 12 to 48 hours.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts alcohol and caustic soda flakes or potash as raw materials, and adopts a ball milling method to prepare alkoxide. The method is obtained unexpectedly in other experimental processes, and through later-stage related experiments, the method is proved to be capable of successfully preparing the alkoxide. In the prior art, the metal alkoxide is generally considered to be difficult to stably exist as long as water exists in a reaction medium, and the reaction speed for preparing the metal alkoxide by an alkaline method at normal temperature is extremely low, so that the method is extremely unfavorable for industrial production of the metal alkoxide; the invention adopts a brand new technical route, takes alcohol and caustic soda flakes or potash as raw materials, can prepare corresponding alkoxide solid by ball milling at normal temperature under the condition of existence of water, can directly use alkoxide-alcohol-water solution generated in the preparation process as a product, can also be recycled as raw materials for reutilization after water removal, is environment-friendly and has no emission, and meanwhile, the preparation reaction has low requirement on the raw materials and low cost.
Drawings
Figures 1 and 2 show the XRD patterns of the solid sodium methoxide obtained in example 1 under two different medium spheres conditions, respectively.
Fig. 1 corresponds to zirconium spheres and fig. 2 corresponds to iron spheres.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to illustrate the invention further, but are not to be construed as limiting the invention.
Example 1
The preparation method of the sodium methoxide comprises the following specific steps:
(1) Taking 1000ml of methanol and 400g of caustic soda flakes, then placing the two materials into a 3L ball milling tank, then placing grinding balls (zirconium balls or iron balls), sealing and isolating air, and ball milling for 8 hours at 180rpm at room temperature;
(2) Taking out the material 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, so as to obtain lower-layer slurry and upper-layer liquid respectively;
(3) The upper liquid is a mixed liquid of sodium methoxide, methanol and water;
(4) The lower slurry is dehumidified in a vacuum drying oven at 60 ℃ to obtain the solid sodium methoxide.
Table 1 shows the results of the solid sodium methoxide obtained in example 1 under the condition of using two different media balls, respectively. As shown in Table 1, the main reaction product is sodium methoxide, the mass fraction of which can reach more than 93%, and contains a small amount of sodium carbonate, free alkali and other impurities; in addition, the medium balls have a slight influence on the purity of the product, wherein the iron ball grinding balls have a small 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 an amorphous form obtained by the conventional method, but exists in a crystalline form. This pattern does not match in the XRD patterns of all the substances present. The product detected was directly dried without sedimentation. The XRD pattern is a direct basis for distinguishing crystalline from amorphous. The failure of the XRD patterns to match suggests that this is an undiscovered structure of matter. Compared with amorphous, the amorphous silicon oxide has lower internal energy of crystals, more stable structure and less possibility of oxidization. The alkoxide product obtained in the examples has no inflammable character, is inflammable, has combustibility similar to that of timber and needs to be ignited with open flame.
Example 2
The preparation method of the sodium ethoxide comprises the following specific steps:
(1) Taking 1250ml of ethanol and 350g of caustic soda flakes, then placing the ethanol and the caustic soda flakes into a 3L ball milling tank, then placing grinding balls (zirconium balls), sealing and isolating air, and ball milling for 4 hours at 180rpm at room temperature;
(2) Taking out the material 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, so as to obtain lower-layer slurry and upper-layer liquid respectively;
(3) The upper liquid is a mixed liquid of sodium ethoxide, ethanol and water;
(4) The lower slurry is dehumidified in a vacuum drying oven at 80 ℃ to obtain the solid sodium ethoxide.
Table 2 shows the results of the solid sodium ethoxide obtained in example 2. As shown in Table 2, the main reaction product is sodium ethoxide, the mass fraction of which can reach more than 99.2%, and contains a small amount of sodium carbonate, free alkali and other impurities.
TABLE 2
| Sequence number | Detecting items | Unit (B) | Detection result | Detection method |
| 1 | Sodium ethoxide mass fraction | ％ | 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 | Vapor pressure (20 ℃ C.) | mmHg | <0.1 | GB/T 21616-2008 |
| 7 | Refractive index | - | 1.386 | GB/T 614-2006 |
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and changes can be made by those skilled in the art without departing from the inventive concept and remain within the scope of the invention.
Claims (3)
1. The preparation method of the alkoxide is characterized in that alcohol and alkali are mixed in proportion and then are placed in a ball milling tank for ball milling, and mixed slurry is obtained; settling the mixed slurry through standing to obtain lower-layer slurry and upper-layer liquid; drying the lower slurry to obtain alkoxide solid; the upper layer liquid is a mixed liquid of alcohol, alkoxide and water;
wherein the alkali is caustic soda flakes and/or potash, and when the alkali is caustic soda flakes, the alkoxide is sodium alkoxide; when the alkali is potash, the alkoxide is potassium alkoxide; the alcohol comprises methanol, ethanol, propanol and butanol; the alkoxide is the alkoxide correspondingly generated by the raw material alcohol, namely, the hydrogen ions in the raw material alcohol are converted into sodium ions or potassium ions to obtain the corresponding alkoxide; the alcohol and caustic soda flakes are all of industrial grade;
the ball milling conditions were as follows: the ball milling atmosphere needs to be sealed and air is isolated; ball milling temperature is in the range of 0-30 ℃; ball milling time is 0.5-8 hours; the ball milling speed is 6-300 rpm;
the conditions for standing are as follows: standing the mixture in a closed environment and isolating air; the temperature of standing is within the range of 0-30 ℃; the standing time is 4 to 48 hours.
2. A process for the preparation of an alkoxide as claimed in claim 1, characterised in that the water content of the alcohol is not more than 5% by weight; the purity of caustic soda flakes and caustic potash is not less than 96%, and the main impurity is Na 2 CO 3 Or K 2 CO 3 。
3. The process for producing an alkoxide according to claim 1, wherein the mass ratio of the alcohol to the base is in the range of (1.5 to 5:1).
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