阅读说明：本技术 一种有机醇钠的生产装置及制备方法 (Production device and preparation method of organic sodium alkoxide ) 是由 牟中江 范士敏 迟国福 张磊 于 2020-07-31 设计创作，主要内容包括：本发明公开了一种有机醇钠的生产装置及制备方法,包括釜反精馏装置,向釜反精馏装置中加入金属钠然后氮气置换,开启真空装置将反应器抽至-0.1MPa,向反应器加入有机醇,在一定温度和负压力条件下反应,得到一定固含的有机醇钠溶液。本发明所述有机醇钠的制备方法,通过减压精馏降低有机醇的沸点,并将蒸出的有机醇重新回流到反应体系,能够促进物料与回流物料直接换热,降低反应体系的温度,很好的解决了有机醇沸点偏高,导致的金属钠受热熔融成球状,造成反应剧烈程度增加,引起反应失控的问题。(The invention discloses a production device and a preparation method of organic sodium alkoxide, which comprises a kettle reverse rectification device, wherein metal sodium is added into the kettle reverse rectification device, then nitrogen is replaced, a vacuum device is started to pump a reactor to-0.1 MPa, organic alcohol is added into the reactor, and the reaction is carried out under the conditions of certain temperature and negative pressure to obtain a certain solid content organic sodium alkoxide solution. According to the preparation method of the organic sodium alkoxide, the boiling point of the organic alcohol is reduced through vacuum rectification, the evaporated organic alcohol flows back to the reaction system again, direct heat exchange between the material and the backflow material can be promoted, the temperature of the reaction system is reduced, and the problems that metal sodium is heated and melted into a spherical shape due to high boiling point of the organic alcohol, the intensity of reaction is increased, and reaction is out of control are solved.)

1. A production device and a preparation method of organic sodium alkoxide are characterized in that: including cauldron anti-rectifier unit, cauldron anti-rectifier unit includes tower cauldron (1), be fixed with tower cauldron jacket (9) of heatable and cooling on tower cauldron (1), tower cauldron (1) endotheca is equipped with agitator (2), tower cauldron (1) top intercommunication has rectifying column (3), rectifying column (3) fixed surface has steam heating heat retainer (10), tower cauldron (1) bottom intercommunication has finished product jar (8), the intercommunication has total reflux condenser (4) on rectifying column (3), total reflux condenser (4) bottom intercommunication has receiving tank (5), the last intercommunication of receiving tank (5) has material backwash pump (6) and vacuum pump (7) respectively, material backwash pump (6) bottom with rectifying column (3) intercommunication, the preparation method includes following step:

(1) adding sodium metal into the tower kettle (1), sealing the tower kettle (1), replacing nitrogen for 3 times, starting a vacuum pump (7) to pump the pressure in the tower kettle (1) to-0.1 MPa;

(2) opening a feeding valve of a tower kettle (1), sucking organic alcohol dissolved with a polymerization inhibitor into the tower kettle (1), starting a stirrer (2), keeping a vacuum pipeline of a vacuum pump (7) in an open state, starting jacket steam of the tower kettle (1) to heat the tower kettle (1) to a preset temperature, starting a steam heating heat retainer (10) of a rectifying tower column (3), starting a circulating cooling water or chilled water valve of a total reflux condenser (4), starting a feeding pipeline valve and a discharging pipeline valve of a receiving tank (5), starting a material reflux pump (6) to pump materials back into the rectifying tower column (3) when a liquid level meter in the receiving tank (5) shows 25% of liquid level, forming stable rectifying-reflux circulation, controlling the temperature of the tower kettle (1) to be 50-90 ℃, controlling the pressure of a reaction system to be-0.1 MPa, and carrying out heat preservation reaction for 5-10 hours;

(3) after the reaction is finished, light yellow or light brown yellow viscous liquid is obtained, nitrogen is used for pressing the materials in the tower kettle (1) into a finished product tank (8), and the organic sodium alkoxide is obtained and stored for later use.

2. The production device and the preparation method of the sodium organoalkoxide according to claim 1, wherein: the volume of the tower kettle (1) is 5-10 m³。

3. The production device and the preparation method of the sodium organoalkoxide according to claim 1, wherein: the rectifying column (3) is a plate tower or a packed tower, the tower diameter d is 10-30 cm, the tower height L is 100-500 cm, the packed tower packing is made of stainless steel and is in a cylindrical shape, a saddle shape, a corrugated shape, a theta shape and the like, and the packing is filled in the packed tower in a random manner.

4. The production device and the preparation method of the sodium organoalkoxide according to claim 1, wherein: the total reflux condenser (4) is of a tube array type or disc type structure, materials are fed in a pipeline or an interlayer, and circulating cooling water or chilled water is fed outside the pipeline or the interlayer.

5. The production device and the preparation method of the sodium organoalkoxide according to claim 1, wherein: the vacuum pump (7) is one of a Roots vacuum pump, a water ring vacuum pump, a vacuum oil pump and other vacuum pumps, wherein the water ring vacuum pump is provided with an anti-reverse adsorption piece.

6. The production device and the preparation method of the sodium organoalkoxide according to claim 1, wherein: the sodium metal is sodium rods directly delivered from a factory, the specification of the sodium rods is 1.5 Kg/root, the sodium rods are directly placed in a tower kettle (1) in a messy manner after being wiped by oil absorption paper, and the mass feed ratio of the sodium metal to the organic alcohol is 1: (10-40), the adding sequence is that the metallic sodium is added firstly and then the organic alcohol is added.

7. The production device and the preparation method of the sodium organoalkoxide according to claim 1, wherein: the organic alcohol is mainly an initiator synthesized by polyether macromonomer for a polycarboxylic acid water reducing agent, and comprises unsaturated alcohol and saturated alcohol, wherein the unsaturated alcohol comprises one of unsaturated alcohols such as allyl alcohol, methallyl alcohol, 3-methyl-3-butene-1-ol, ethylene glycol vinyl ether, 7-octene-1-ol and 3, 7-dimethyl-7-octenol, and the saturated alcohol comprises one of saturated alcohols such as methanol, ethanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, isopropanol, n-butanol, cyclohexanol and isooctanol.

8. The production device and the preparation method of the sodium organoalkoxide according to claim 1, wherein: the polymerization inhibitor comprises one of hydroquinone, p-benzoquinone, phenothiazine, p-tert-butyl catechol and the like, and the dosage of the polymerization inhibitor is 0.01-0.05% of the mass of the organic alcohol.

9. The production device and the preparation method of the sodium organoalkoxide according to claim 1, wherein: the reaction of the metal sodium and the organic alcohol does not need heating in the reaction process, the reaction temperature is controlled to be 50-90 ℃ by means of the exothermic temperature rise of the reaction of the metal sodium and the organic alcohol.

Technical Field

The invention relates to a preparation method of organic alcohol alkali metal salt, in particular to a production device and a preparation method of organic sodium alkoxide, belonging to the field of application of fine chemical engineering technology.

Background

The polycarboxylate water reducer is a high-efficiency water reducer represented by first-generation lignosulfonate, second-generation naphthalene sulfonate, aliphatic sulfonate and the like, and a third-generation high-performance water reducer developed recently has the characteristics of high water reducing rate, good slump retaining property and the like, is popularized and applied in the fields of capital construction engineering, civil buildings, nuclear power, hydropower and the like on a large scale, is a water reducer product with the largest domestic application amount at present, and accounts for about 80 percent of the market share of the concrete water reducer.

The polyether macromonomer is a main raw material for synthesizing the polycarboxylate water reducer, accounts for 80-90% of the mass of the polycarboxylate water reducer, the polyether macromonomer used for synthesizing the polycarboxylate water reducer in the year reaches about 240 ten thousand tons, and the effective content of the polyether macromonomer has obvious influence on the performance of the finally prepared polycarboxylate water reducer.

The catalysts currently used for polyether synthesis are classified into acid catalysts, coordination catalysts and base catalysts. The acid catalyst is common concentrated sulfuric acid, concentrated hydrochloric acid, boron trifluoride diethyl etherate, Lewis acid and the like [ Zyguoguo et al, ring-opening polymerization of ethylene oxide and propylene oxide [ J ], chemical development, 2007,19(1),145-152 ]. The polyether prepared by using the acid catalyst has low molecular weight and has cyclic byproducts, and the cyclic byproducts are only used in a few polyether products; the coordination catalyst is mainly a bimetallic catalyst, DMC or MMC for short, which is developed by American general tire rubber company and aims at the polymerization of polyether polyol, and the DMC or MMC catalyst is particularly suitable for the polymerization working condition of propylene oxide, and has high polymerization rate and low polyether molecular weight distribution. When ethylene oxide is used to participate in the polymerization, the efficiency of the DMC catalyst is significantly reduced and the polyether molecular weight distribution is significantly broadened. Therefore, the current application range of DMC is limited to the production of polyether polyol prepared by propylene oxide [ Tangsiqing, etc.. production by using a bimetallic catalyst [ C ], the collection of the eleventh year meeting of the China Association of polyurethane industries, 2002,102-104 ]; the alkali catalyst is common metal sodium, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium hydride, potassium tert-butoxide, alkaline earth metal and the like, is suitable for ethylene oxide polymerization, has low polymerization efficiency on propylene oxide, easily generates allyl byproducts and causes the unsaturation degree of polyether to be increased. At present, the catalyst used in the polyether macromonomer industry is mainly an alkali catalyst, and the type of the catalyst is gradually changed from sodium hydroxide and sodium methoxide at the beginning to sodium hydride or metallic sodium with better reaction activity and higher purity.

The procedure of adding catalyst in the production process of polyether macromonomer is mainly to prime with unsaturated alcohol, then add metallic sodium or sodium hydride into the unsaturated alcohol, and transfer the materials into a polyether reactor to produce polyether macromonomer after full reaction. The safety risk of the prior process is high, on one hand, the boiling point of unsaturated alcohol is high, the reaction process with metal sodium or sodium hydride is violent and accompanied with hydrogen generation, so that the metal sodium is easy to melt into a spherical shape, and the hydrogen is easy to explode or ignite; on the other hand, various companies do not have good treatment methods for the reaction of unsaturated alcohol and metallic sodium or sodium hydride at present, the risk is avoided by adopting an open-air catalyst adding mode, and the requirement on occupational quality of operators is high.

In conclusion, the polyether macromonomer is a main raw material of the polycarboxylate superplasticizer, and the synthesis of the polyether macromonomer is mainly carried out by taking metallic sodium or sodium hydride as a catalyst at home. Because the boiling point of the unsaturated alcohol is generally above 100 ℃, the melting point of the metal sodium is reached or exceeded, in the reaction process of the unsaturated alcohol and the metal sodium, the metal sodium is easily heated, heated and melted into a spherical shape, the reaction rate is further increased, safety accidents are further aggravated, in addition, the reaction process is accompanied with hydrogen generation, and fire or explosion is easily caused when the hydrogen is not discharged in time; the specific surface area of sodium hydride is far greater than that of metal sodium, hydrogen is generated in the reaction process of the sodium hydride and unsaturated alcohol, the reaction is very violent, the sodium hydride can be added into the unsaturated alcohol only for a few times, the working procedure time is obviously prolonged, and the solvent kerosene and water of the sodium hydride are insoluble, so that the polymerization effect is adversely affected when the carboxylic acid water reducing agent is prepared. Based on the method, the invention provides a safe and efficient preparation method of the organic sodium alkoxide.

Disclosure of Invention

The present invention is directed to solving the above problems and providing an apparatus and a method for producing sodium organoalkoxide.

The invention realizes the aim through the following technical scheme, and the production device and the preparation method of the organic sodium alkoxide comprise a kettle reverse rectification device, wherein the kettle reverse rectification device comprises a tower kettle, a tower kettle outer jacket capable of heating and cooling is fixed on the tower kettle, a stirrer is sleeved in the tower kettle, the top end of the tower kettle is communicated with a rectification tower column, a steam heating heat retainer is fixed on the surface of the rectification tower column, the bottom of the tower kettle is communicated with a finished product tank, a full reflux condenser is communicated on the rectification tower column, the bottom of the full reflux condenser is communicated with a receiving tank, a material reflux pump and a vacuum pump are respectively communicated on the receiving tank, and the bottom of the material reflux pump is communicated with the rectification tower column, and the preparation method comprises the following steps:

(1) adding metal sodium into the tower kettle, sealing the tower kettle, replacing nitrogen for 3 times, starting a vacuum pump, and pumping the pressure in the tower kettle to-0.1 MPa;

(2) opening a feeding valve of a tower kettle to suck organic alcohol dissolved with a polymerization inhibitor into the tower kettle, starting a stirrer, keeping a vacuum pipeline of a vacuum pump in an open state, starting jacket steam of the tower kettle to heat the tower kettle to a preset temperature, starting a steam heating heat retainer of a rectifying tower column, starting a circulating cooling water or chilled water valve of a total reflux condenser, starting a feeding pipeline valve and a discharging pipeline valve of a receiving tank, starting a material reflux pump to pump materials back into the rectifying tower column when a liquid level meter in the receiving tank shows that 25% of liquid level is displayed, forming stable rectification-reflux circulation, controlling the temperature of the tower kettle to be 50-90 ℃, controlling the pressure of a reaction system to be-0.1 MPa, and carrying out heat preservation reaction for 5-10 hours;

(3) after the reaction is finished, light yellow or light brown yellow viscous liquid is obtained, nitrogen is used for pressing the materials in the tower kettle into a finished product tank, and the organic sodium alkoxide is obtained and stored for later use.

Preferably, the volume of the tower kettle is 5-10 m³。

Preferably, the rectification column is a plate column or a packed column, the column diameter d is 10 cm-30 cm, the column height L is 100 cm-500 cm, the packed column packing is made of stainless steel and is in a shape of cylinder, saddle, ripple, theta and the like, and the packing is packed in the packed column in a random manner.

Preferably, the total reflux condenser is of a tube array type or disc type structure, materials are fed in a pipeline or an interlayer, and circulating cooling water or chilled water is fed outside the pipeline or the interlayer.

Preferably, the vacuum pump is one of a roots vacuum pump, a water ring vacuum pump, a vacuum oil pump and the like, wherein the water ring vacuum pump is provided with an anti-reverse adsorption piece.

Preferably, the metal sodium is sodium rods directly delivered from a factory, the specification of the sodium rods is 1.5 Kg/root, the sodium rods are directly piled in a tower kettle after being wiped by oil absorption paper, and the mass feeding ratio of the metal sodium to the organic alcohol is 1: (10-40), the adding sequence is that the metallic sodium is added firstly and then the organic alcohol is added.

Preferably, the organic alcohol is mainly a starter for synthesizing polyether macromonomer for polycarboxylic acid water reducing agent, and comprises unsaturated alcohol and saturated alcohol, wherein the unsaturated alcohol comprises one of allyl alcohol, methallyl alcohol, 3-methyl-3 butene-1-ol, ethylene glycol vinyl ether, 7-octene-1-ol, 3, 7-dimethyl-7-octenol and other unsaturated alcohols, and the saturated alcohol comprises one of methanol, ethanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, isopropanol, n-butanol, cyclohexanol, isooctanol and other saturated alcohols.

Preferably, the polymerization inhibitor comprises one of hydroquinone, p-benzoquinone, phenothiazine, p-tert-butylcatechol and the like, and the dosage of the polymerization inhibitor is 0.01-0.05% of the mass of the organic alcohol.

Preferably, the reaction of the metal sodium and the organic alcohol does not need heating in the reaction process, the reaction temperature is controlled to be 50-90 ℃ by means of the exothermic temperature rise of the reaction of the metal sodium and the organic alcohol.

The invention has the beneficial effects that:

(1) according to the preparation method of the organic sodium alkoxide, the boiling point of the organic alcohol is reduced through vacuum rectification, the evaporated organic alcohol flows back to the reaction system again, direct heat exchange between the material and the backflow material can be promoted, the temperature of the reaction system is reduced, and the problems that metal sodium is heated and melted into a spherical shape due to high boiling point of the organic alcohol, the intensity of reaction is increased, and reaction is out of control are solved.

(2) The preparation method of the organic sodium alkoxide well solves the problem of hydrogen enrichment generated by the reaction of the organic alcohol and the metal sodium, and quickly removes the hydrogen in the reaction system out of the system through rectification under reduced pressure.

(3) According to the preparation method of the organic sodium alkoxide, the purity of the produced organic sodium alkoxide is high, the reaction system is in a vacuum state, the time of rectification under reduced pressure is short, and the reduction of the purity of the organic sodium alkoxide caused by the reaction of moisture in air and carbon dioxide with the organic sodium alkoxide is avoided.

Drawings

FIG. 1 is a schematic diagram of the overall structure of the tank reverse rectification apparatus of the present invention.

In the figure: 1. the system comprises a tower kettle, 2 a stirrer, 3 a rectifying tower column, 4 a total reflux condenser, 5 a receiving tank, 6 a material reflux pump, 7 a vacuum pump, 8 a finished product tank, 9 a tower kettle outer jacket, 10 a steam heating heat retainer.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In the description of the present invention, it should be noted that the terms "upper", "lower", "inner" and "outer" indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplification of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus should not be construed as limiting the present invention. Furthermore, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.

In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; the connection may be direct or indirect via an intermediate medium, and may be a communication between the two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.

The present invention is described in detail below by way of examples, which are intended to be illustrative only and not to be construed as limiting the scope of the invention, and one skilled in the art can, in light of the present disclosure, vary the reagents, and reaction process conditions within the scope of the invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

All chemical reagents in the invention are commercial industrial-grade purity products, and the use amount of each raw material is mass parts. The content of the sodium organoalkoxide in the invention is measured by a titration method and by referring to a method specified in a standard HG/T2561-2014. The molecular weight of the polyether macromonomer is tested by referring to a hydroxyl value method specified in JC/T2033-2018 polyether for concrete admixture and derivatives thereof; high performance liquid testing method tests reported in effective content references of polyether macromonomer (Xiliana et al, high performance liquid chromatography determination of polyethylene glycol mass fraction [ J ],2016,33(6),53-60) in polycarboxylic acid water reducer macromonomer; the molecular weight distribution of the polyether macromonomer was measured using aqueous phase high performance Gel Permeation Chromatography (GPC).

Referring to fig. 1, a device for producing organic sodium alkoxide and a method for preparing the same, comprising a tank reverse rectification device, the kettle reverse rectification device comprises a tower kettle 1, a tower kettle outer jacket 9 capable of heating and cooling is fixed on the tower kettle 1, a stirrer 2 is sleeved in the tower kettle 1, the top end of the tower kettle 1 is connected to the inlet at the lower end of a rectifying tower column 3, a steam heating heat retainer 10 is arranged on the outer surface of the rectifying tower column 3, the bottom of the tower kettle 1 is communicated with a finished product tank 8, the top outlet of the rectifying tower column 3 is connected to the inlet of the total reflux condenser 4, the bottom outlet of the total reflux condenser 4 is connected with the top inlet of the receiving tank 5, the bottom outlet of the receiving tank 5 is respectively communicated with a material reflux pump 6 and a vacuum pump 7, the outlet at the bottom of the material reflux pump 6 is connected to the middle upper part of the rectifying tower column 3, and the preparation method comprises the following steps:

(1) adding metal sodium into the tower kettle 1, sealing the tower kettle 1, replacing nitrogen for 3 times, starting a vacuum pump 7, and pumping the pressure in the tower kettle 1 to-0.1 MPa;

(2) opening a feeding valve of a tower kettle 1, sucking organic alcohol dissolved with a polymerization inhibitor into the tower kettle 1, starting a stirrer 2, keeping a vacuum pipeline of a vacuum pump 7 in an open state, starting jacket steam of the tower kettle 1 to heat the tower kettle 1 to a preset temperature, starting a steam heating heat retainer 10 of a rectifying tower column 3, wherein the heat retaining temperature is the same as the temperature of the tower kettle, starting a circulating cooling water or chilled water valve of a total reflux condenser 4, starting a feeding pipeline valve and a discharging pipeline valve of a receiving tank 5, and when 25% of liquid level in the receiving tank 5 is displayed, starting a material reflux pump 6 to pump the material back into the rectifying tower column 3 to form stable rectifying-reflux circulation, controlling the temperature of the tower kettle 1 to be 50-90 ℃, controlling the pressure of a reaction system to be-0.1 MPa, and carrying out heat retaining reaction for 5-10 hours;

(3) after the reaction is finished, light yellow or light brown yellow viscous liquid is obtained, nitrogen is used for pressing the materials in the tower kettle 1 into a finished product tank 8, and the organic sodium alkoxide is obtained and stored for later use.

The volume of the tower kettle 1 is 5 to10m³。

The rectifying column 3 is a plate column or a packed column, the diameter d of the column is 10-30 cm, the height L of the column is 100-500 cm, the packed column packing is made of stainless steel and is in the shape of cylinder, saddle, ripple, theta and the like, and the packing is filled in the packed column in a random manner.

The total reflux condenser 4 is of a tube array type or disc type structure, materials are fed in a pipeline or an interlayer, and circulating cooling water or chilled water is fed outside the pipeline or the interlayer.

The vacuum pump 7 is one of a Roots vacuum pump, a water ring vacuum pump, a vacuum oil pump and the like, wherein the water ring vacuum pump is provided with an anti-reverse adsorption piece.

The sodium metal is sodium rods directly delivered from a factory, the specification of the sodium rods is 1.5 Kg/root, the sodium rods are directly placed in a tower kettle 1 in a messy manner after being wiped by oil absorption paper, and the mass feed ratio of the sodium metal to the organic alcohol is 1: (10-40), the adding sequence is that the metallic sodium is added firstly and then the organic alcohol is added.

The organic alcohol is mainly an initiator synthesized by polyether macromonomer for a polycarboxylic acid water reducing agent, and comprises unsaturated alcohol and saturated alcohol, wherein the unsaturated alcohol comprises one of unsaturated alcohols such as allyl alcohol, methallyl alcohol, 3-methyl-3-butene-1-ol, ethylene glycol vinyl ether, 7-octene-1-ol and 3, 7-dimethyl-7-octenol, and the saturated alcohol comprises one of saturated alcohols such as methanol, ethanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, isopropanol, n-butanol, cyclohexanol and isooctanol.

The polymerization inhibitor comprises one of hydroquinone, p-benzoquinone, phenothiazine, p-tert-butyl catechol and the like, and the dosage of the polymerization inhibitor is 0.01-0.05% of the mass of the organic alcohol.

The reaction of the metal sodium and the organic alcohol is carried out, after the reaction is preheated in the initial stage, the subsequent reaction process does not need to be heated, the reaction temperature is controlled to be 50-90 ℃ by means of the exothermic temperature rise of the reaction of the metal sodium and the organic alcohol.