CN113235117A - Production process of high-concentration tetrapropylammonium hydroxide and high-concentration tetrapropylammonium hydroxide prepared by same - Google Patents
Production process of high-concentration tetrapropylammonium hydroxide and high-concentration tetrapropylammonium hydroxide prepared by same Download PDFInfo
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Abstract
The application discloses a production process of high-concentration tetrapropyl ammonium hydroxide and high-concentration tetrapropyl ammonium hydroxide prepared by the production process, and relates to the technical field of quaternary ammonium hydroxide production. The production process of high-concentration tetrapropylammonium hydroxide comprises the following steps: s1 electrolysis: adding water into tetrapropyl quaternary ammonium salt to prepare tetrapropyl quaternary ammonium salt water solution, and combining tetrapropyl ammonium cations with hydroxide ions generated by electrolysis by an electrolysis method to form tetrapropyl ammonium hydroxide to prepare a crude product; s2 concentration: adding n-propanol 0.05-0.2 times the weight of the crude product into the crude product, mixing well to obtain a mixed solution, heating the mixed solution to 60-80 deg.C, and concentrating for not less than 60min to obtain high-concentration tetrapropylammonium hydroxide. The production process of the high-concentration tetrapropylammonium hydroxide has the advantage of high production efficiency.
Description
Technical Field
The application relates to the technical field of quaternary ammonium hydroxide production, in particular to a production process of high-concentration tetrapropylammonium hydroxide and high-concentration tetrapropylammonium hydroxide prepared by the production process.
Background
With the development of society, the living standard of people is continuously improved, and the requirement of the society on environmental protection is higher and higher. Molecular sieves are used as porous materials with high specific surface areas and are gradually and widely used in the fields of VOC treatment, automobile exhaust purification treatment, steel plant exhaust treatment and the like. The synthesis of molecular sieve generally needs to use quaternary ammonium hydroxide as a template agent, and tetrapropylammonium hydroxide as the template agent for synthesizing molecular sieve is gradually and widely used in the synthesis process of molecular sieves such as all-silicon ZSM-5 molecular sieve, TS-1 molecular sieve and the like.
The currently common tetrapropyl ammonium hydroxide production process is to dissolve tetrapropyl quaternary ammonium salt in water and prepare tetrapropyl ammonium hydroxide aqueous solution through electrolysis, and then the tetrapropyl ammonium hydroxide aqueous solution is used in the synthesis of molecular sieves. The tetrapropylammonium hydroxide aqueous solution is used in the synthesis process of the molecular sieve, and has the function of a template agent on one hand and can provide a water source required by the synthesis of the molecular sieve on the other hand. With the development of molecular sieve synthesis technology, in order to improve the production efficiency of molecular sieves, a high-solid-content synthesis system is gradually adopted for molecular sieve synthesis, the water amount required in molecular sieve synthesis is reduced, and a tetrapropylammonium hydroxide aqueous solution with higher concentration is gradually required to be used.
In the process of producing an aqueous tetrapropylammonium hydroxide solution by electrolysis, the concentration of tetrapropylammonium hydroxide in the aqueous tetrapropylammonium hydroxide solution directly produced is low. There are two methods for increasing the concentration of the aqueous tetrapropylammonium hydroxide solution, one is to increase the electrolysis voltage or prolong the electrolysis time, and the other is to concentrate the aqueous tetrapropylammonium hydroxide solution at a high temperature to increase the concentration. When the concentration of the tetrapropylammonium hydroxide aqueous solution reaches a certain concentration, the effect of prolonging the electrolysis time is poor, and the energy consumption of the method for improving the concentration of the tetrapropylammonium hydroxide aqueous solution by increasing the electrolysis voltage or prolonging the electrolysis time is high. Therefore, the method for producing a highly concentrated aqueous solution of tetrapropylammonium hydroxide that is currently used is a method of concentration at a high temperature.
In view of the above-mentioned related technologies, the inventor believes that, when the concentration temperature is too high, tetrapropylammonium hydroxide is easily decomposed to form impurities, which affects the product quality, so that the concentration temperature in the concentration step in the currently common process for producing high-concentration tetrapropylammonium hydroxide aqueous solution is generally not higher than 60 ℃, and the concentration temperature is low, which affects the production efficiency of high-concentration tetrapropylammonium hydroxide products to a certain extent.
Disclosure of Invention
In order to improve the production efficiency of high-concentration tetrapropylammonium hydroxide products, the application provides a production process of high-concentration tetrapropylammonium hydroxide and high-concentration tetrapropylammonium hydroxide prepared by the production process.
In a first aspect, the present application provides a process for producing high-concentration tetrapropylammonium hydroxide, which adopts the following technical scheme:
a production process of high-concentration tetrapropylammonium hydroxide comprises the following steps:
s1 electrolysis: adding water into tetrapropyl quaternary ammonium salt to prepare tetrapropyl quaternary ammonium salt water solution, and combining tetrapropyl ammonium cations with hydroxide ions generated by electrolysis by an electrolysis method to form tetrapropyl ammonium hydroxide to prepare a crude product;
s2 concentration: adding n-propanol 0.05-0.2 times the weight of the crude product into the crude product, mixing well to obtain a mixed solution, heating the mixed solution to 60-80 deg.C, and concentrating for not less than 60min to obtain high-concentration tetrapropylammonium hydroxide.
By adopting the technical scheme, tetrapropyl ammonium hydroxide aqueous solution is prepared by using tetrapropyl quaternary ammonium salt through an electrolysis method, the cathode plate in the cathode chamber of the electrolysis bath provides electrons, hydrogen ions ionized in the cathode chamber absorb the electrons and flow out in a hydrogen form to form hydroxide ions, and tetrapropyl ammonium cations are dissociated to the cathode chamber and combined with the hydroxide ions to form tetrapropyl ammonium hydroxide. After tetrapropylammonium hydroxide in the cathode chamber reaches a certain concentration, the concentration of hydroxide ions is higher, so that ionization balance forward movement of hydrogen ions and hydroxide ions formed by water ionization is not facilitated, tetrapropylammonium hydroxide with higher concentration is not facilitated to be formed, the concentration of tetrapropylammonium hydroxide can be further improved by improving electrolysis voltage or prolonging electrolysis time, the energy consumption is obviously increased, and the reduction of production cost is not facilitated. The method comprises the steps of electrolyzing to form a crude product, adding a certain amount of n-propanol into the crude product, and concentrating to obtain a high-concentration tetrapropyl ammonium hydroxide aqueous solution; the n-propanol is added to form an azeotrope with water so as to reduce the boiling point, and the water and the n-propanol are separated from the crude product together, so that the concentration efficiency is improved, the concentration time is obviously shortened, the energy consumption is reduced, and the production efficiency is improved; on the other hand, the addition of the n-propanol is beneficial to inhibiting the decomposition reaction of the tetrapropylammonium hydroxide, preventing the tetrapropylammonium hydroxide from decomposing to form tripropylamine and other impurities, reducing the impurity content and improving the product quality, and meanwhile, the addition of the n-propanol can properly improve the concentration temperature, improve the concentration efficiency and improve the production efficiency. Compared with the technical scheme of preparing high-concentration tetrapropylammonium hydroxide by improving electrolytic voltage or prolonging electrolytic time, the method has the advantages that the crude product with higher concentration is not required to be used, the crude product with lower concentration can be used, the product concentration is improved through concentration, the electrolytic voltage is favorably reduced, the electrolytic time is shortened, the energy consumption is favorably reduced, and the production cost is favorably reduced.
Preferably, the tetrapropyl quaternary ammonium salt is tetrapropyl ammonium chloride, tetrapropyl ammonium bromide, tetrapropyl ammonium fluoride or tetrapropyl ammonium iodide. More preferably, the tetrapropyl quaternary ammonium salt is tetrapropyl ammonium bromide.
By adopting the technical scheme, the tetrapropylammonium bromide with easily obtained raw materials is used, so that the production cost is reduced, and the market competitiveness of products is improved.
Preferably, the step S1 is to perform electrolysis using an electrolysis cell comprising an anode chamber, a byproduct chamber, a raw material chamber and a cathode chamber which are adjacent in sequence; an anode plate is arranged in the anode chamber, a cathode plate is arranged in the cathode chamber, and the anode plate is connected with the cathode plate through a power supply; the anode chamber is communicated with the byproduct chamber through a first cationic membrane, the byproduct chamber is communicated with the raw material chamber through an anionic membrane, and the raw material chamber is communicated with the cathode chamber through a second cationic membrane; in the step S1, water is added into the anode chamber, the byproduct chamber and the cathode chamber, and in the step S1, the tetrapropyl quaternary ammonium salt water solution is added into the raw material chamber and then electrolysis is carried out.
By adopting the technical scheme, tetrapropyl ammonium hydroxide is produced by adopting a four-chamber three-membrane method for electrolysis, tetrapropyl ammonium bromide aqueous solution is added into an electrolytic cell from a raw material chamber, and water is added into the electrolytic cell; hydrogen ions in the cathode chamber are removed in a hydrogen form to form hydroxide ions, the hydroxide ions in the anode chamber are removed to form oxygen to form hydrogen ions, and the hydrogen ions enter the by-product chamber through the first cationic membrane under the driving action of electrolysis. And (3) ionizing tetrapropylammonium bromide in the raw material chamber to form bromide ions and tetrapropylammonium cations, allowing the bromide ions to enter the byproduct chamber through an anion membrane to be combined with hydrogen ions to form byproduct hydrobromic acid, and allowing the tetrapropylammonium cations to enter the cathode chamber through a second cation membrane to be combined with hydroxide radicals to form a tetrapropylammonium hydroxide aqueous solution product. This application adopts four rooms three embranes method to help preventing that bromide from dissociating to the positive pole room and forming the bromine of strong corruption, helps preventing the corruption of bromine to metal anode plate, helps better protection anode plate, helps protecting electrolysis equipment better, helps reducing the equipment maintenance cost.
Preferably, the step S2 is performed in a vacuum state, and the vacuum pressure is-0.095 to-0.08 MPa.
Through adopting above-mentioned technical scheme, concentrate the mixed solution under vacuum state, vacuum and normal propyl alcohol combined action help improving concentration efficiency, shorten the concentration time, help improving production efficiency.
Preferably, in the step S2, the mixed solution is vacuumized and concentrated in a water bath at 80 ℃ for 10-20min, the water bath is uniformly cooled to 60 ℃ for 60-90min while the concentration is continued, and then the concentration is continued at 60 ℃ for not less than 30min, so as to obtain the high-concentration tetrapropylammonium hydroxide.
By adopting the technical scheme, in the early stage of concentration, the n-propanol content in the crude product is higher, the tetrapropyl ammonium hydroxide is not easy to generate decomposition reaction, and the concentration can be carried out at higher temperature; with the concentration, the content of the n-propanol in the system is reduced, and the probability of the decomposition reaction of the tetrapropyl ammonium hydroxide is increased; this application is concentrated under higher temperature earlier stage, along with the reducing of normal propyl alcohol content in the system, reduces the concentration temperature gradually, helps preventing that tetrapropyl ammonium hydroxide from taking place decomposition, improves concentration efficiency under the prerequisite of guaranteeing the product quality, helps improving production efficiency.
Preferably, in the step S1, the materials in the anode chamber, the byproduct chamber, the raw material chamber and the cathode chamber are circulated by a circulation pump, the circulation flow rates of the materials in the anode chamber and the byproduct chamber are the same as the circulation flow rate of the materials in the cathode chamber, and the circulation flow rate of the materials in the raw material chamber is 1.2-1.5 times of the circulation flow rate of the materials in the anode chamber.
Through adopting above-mentioned technical scheme, through circulating the material of raw materials room, byproduct room, anode chamber and cathode chamber respectively, help avoiding the material gathering near negative plate or anode plate, help accelerating the electrolytic reaction, help reducing the accessory substance, improve the product quality, help improving production efficiency. And the circulation flow of the raw material chamber is larger, which is beneficial to accelerating the migration of tetrapropylammonium cations to the cathode chamber and the migration of bromide ions to the byproduct chamber and improving the production efficiency.
Preferably, the electrolysis temperature of the step S1 is not more than 58 ℃.
By adopting the technical scheme, the electrolysis temperature of the electrolytic cell is controlled, the decomposition reaction of the tetrapropylammonium hydroxide is prevented, the byproducts are reduced, and the product quality is maintained.
Preferably, the mass concentration of tetrapropylammonium bromide in the feed chamber of the step S1 is not more than 15%.
Through adopting above-mentioned technical scheme, tetrapropyl ammonium bromide aqueous solution concentration in the control raw materials room helps improving the migration rate of tetrapropyl ammonium cation, combines with the concentration technology that this application disclosed, helps improving product production efficiency.
In a second aspect, the present application provides a high-concentration tetrapropylammonium hydroxide, which adopts the following technical scheme:
the high-concentration tetrapropylammonium hydroxide is prepared by the production process of the high-concentration tetrapropylammonium hydroxide.
Through adopting above-mentioned technical scheme, use the production technology production high concentration tetrapropylammonium hydroxide that this application disclosed, help preventing tetrapropylammonium hydroxide and decomposing and form impurity, help improving the product quality, help improving product production efficiency.
In summary, the present application includes at least one of the following beneficial technical effects:
1. according to the method, the crude product is prepared by electrolysis, and then the n-propanol is added for concentration, so that the decomposition reaction of the tetrapropyl ammonium hydroxide is prevented, the concentration temperature can be properly increased, the concentration time is shortened, and the production efficiency is improved; the concentration of products in the crude product can be properly reduced, the reduction of electrolytic voltage is facilitated, the reduction of electrolytic time is facilitated, and the improvement of production efficiency is facilitated; the n-propanol and the water are subjected to azeotropic distillation, and the water is removed along with the n-propanol, so that the concentration efficiency and the production efficiency are improved;
2. according to the method, the concentration is carried out at a higher temperature in the earlier stage, and the concentration temperature is gradually reduced along with the reduction of the n-propanol content in the system, so that the decomposition reaction of the tetrapropyl ammonium hydroxide is prevented, the concentration efficiency is improved on the premise of ensuring the product quality, and the production efficiency is improved; the concentration is carried out in a vacuum state, and the concentration and the normal propyl alcohol and the special concentration temperature condition act together, which is beneficial to improving the production efficiency;
3. the electrolysis is carried out by adopting a four-chamber three-membrane method, so that the corrosion of materials to the electrodes is reduced, and the electrolytic equipment is protected better; this application helps preventing the production of impurity through control electrolysis temperature, helps improving the product quality.
Drawings
FIG. 1 is a schematic view of an electrolytic cell used in the electrolysis step of the present application.
Reference numerals: 1. an anode chamber; 2. a secondary production room; 3. a raw material chamber; 4. a cathode chamber; 5. an anode plate; 6. a cathode plate; 7. a first cationic membrane; 8. an anionic membrane; 9. a second cationic membrane.
Detailed Description
The inventor finds in practice that in the process of producing a high-concentration tetrapropylammonium hydroxide aqueous solution, when the concentration temperature is high, tetrapropylammonium hydroxide is easy to decompose and react to generate impurities, the product quality is affected, concentration is generally required to be carried out at a temperature of not higher than 60 ℃, the concentration efficiency is not high, and the production efficiency of the product is affected to a certain extent. Based on the above technical background, the present application provides a technical solution capable of improving the production efficiency of a high-concentration tetrapropylammonium hydroxide product, which is specifically described in the following detailed description.
The tetrapropyl quaternary ammonium salt in the present application is preferably tetrapropyl ammonium bromide. The mass concentration of tetrapropylammonium bromide in the feed chamber during electrolysis is not more than 15%, preferably 10-15%. In the electrolytic process, titrating the bromide ion concentration in the raw material chamber by using silver nitrate, measuring the tetrapropyl ammonium bromide concentration through conversion, and tracking the tetrapropyl ammonium bromide concentration in the raw material chamber in the electrolytic process; according to the concentration change condition of the tetrapropylammonium bromide in the raw material chamber, about 35% of tetrapropylammonium bromide aqueous solution is supplemented into the raw material chamber in the electrolysis process, so that the mass concentration of the tetrapropylammonium bromide in the raw material chamber is kept at 10-15%. When the concentration of the tetrapropylammonium bromide is too high, on one hand, a small amount of bromide ions enter the cathode chamber to influence the product quality; on the other hand, the concentration of the raw materials is too high, the viscosity is large, the ion migration capability is influenced, and the production efficiency is influenced. When the concentration of the tetrapropylammonium bromide is too low, the concentration of the tetrapropylammonium cations in the raw material chamber is too low, so that the tetrapropylammonium cations are not favorably transferred to the cathode chamber, and the production efficiency is influenced. There are two conventional methods for producing an aqueous solution of tetrapropylammonium hydroxide of about 25 wt.%: one method is to prepare tetrapropyl ammonium hydroxide aqueous solution with the mass concentration of about 15 percent through electrolysis, and then prepare tetrapropyl ammonium hydroxide aqueous solution with the mass concentration of about 25 percent through concentration at the temperature of not higher than 60 ℃, and the concentration efficiency of the method is lower, thus influencing the production efficiency of products; the other method is that tetrapropylammonium bromide is supplemented into a raw material chamber of the electrolytic cell, and tetrapropylammonium hydroxide aqueous solution with the mass concentration of about 25% is directly produced by prolonging the electrolysis time and increasing the electrolysis voltage, the method has overhigh electrolysis voltage or overlong electrolysis time and higher energy consumption, and when the mass concentration of the tetrapropylammonium hydroxide aqueous solution in a cathode chamber approaches 25%, the tetrapropylammonium cation concentration in the cathode chamber is overhigh, so that the tetrapropylammonium cation is not favorably transferred from the raw material chamber to the cathode chamber, and the tetrapropylammonium hydroxide aqueous solution with the mass concentration of more than 25% is inconvenient to produce by the method; with the development of molecular sieve synthesis technology, more and more people adopt a high-solid-content molecular sieve synthesis system, and more people in the market need to use tetrapropylammonium hydroxide aqueous solution with the mass concentration of more than 25%, even the mass concentration reaches 35%. The method is suitable for producing the tetrapropyl ammonium hydroxide aqueous solution with high concentration, and is particularly suitable for producing the tetrapropyl ammonium hydroxide aqueous solution with the mass concentration of about 35 percent.
In the actual production process, tetrapropylammonium hydroxide aqueous solutions with different concentrations can be produced according to the requirements of customers. Parameters such as electrolysis voltage, electrolysis time, n-propanol dosage, concentration temperature condition and the like can be determined according to the required concentration of the tetrapropylammonium hydroxide aqueous solution. The circulating pump of raw materials room material is connected with the surge bin, and the surge bin is provided with the cooling water jacket, controls the electrolysis temperature to be not more than 58 ℃ through letting in cooling water to the surge bin cooling water jacket, and the material in the raw materials room gets into the surge bin through the circulating pump, and the raw materials room is got back to another circulating pump to the rethread, realizes the control to the electrolysis temperature. The same electrolysis apparatus was used in the following examples. In the following examples, the water is deionized water and the conductivity is not greater than 15. mu.s/cm. The power supply for the electrolysis process is a direct current power supply. In the practical application process, the concentration temperature in the step S2 is controlled by program temperature control, and the cooling rate of the natural cooling of the water bath can be faster than the required cooling rate under the general condition; in the actual production process, if the cooling rate of the water bath natural cooling is slower than the required cooling rate, room temperature water can be properly added into the water bath to meet the cooling rate. In the following examples, the anode plate was an iridium-based titanium-based metal oxide anode of Jiangsu Yianteng Special electrode New Material science and technology, Inc., and the cathode plate was a nickel-based cathode plate.
The following application is described in further detail with reference to the accompanying drawings.
Examples
Example 1: a process for producing high-concentration tetrapropylammonium hydroxide by electrolysis using an electrolytic cell comprising, as shown in FIG. 1, an anode chamber 1, a byproduct chamber 2, a raw material chamber 3 and a cathode chamber 4 which are adjacent to each other in this order at the same height; an anode plate 5 is arranged in the anode chamber 1, a cathode plate 6 is arranged in the cathode chamber 4, and the anode plate 5 is connected with the cathode plate 6 through a power supply; the anode chamber 1 is communicated with the byproduct chamber 2 through a first cation membrane 7, the byproduct chamber 2 is communicated with the raw material chamber 3 through an anion membrane 8, and the raw material chamber 3 is communicated with the cathode chamber 4 through a second cation membrane 9; the production process comprises the following steps:
s1 electrolysis: adding water into tetrapropyl ammonium bromide to prepare a tetrapropyl ammonium bromide aqueous solution, adding water into the anode chamber 1, the byproduct chamber 2 and the cathode chamber 4, adding the tetrapropyl ammonium bromide aqueous solution into the raw material chamber 3, controlling the mass concentration of the tetrapropyl ammonium bromide in the raw material chamber to be 10-15%, controlling the electrolysis voltage to be 6V, combining tetrapropyl ammonium cations with hydroxide ions generated by the cathode chamber 4 of the electrolytic cell to form tetrapropyl ammonium hydroxide, and electrolyzing for 24 hours to prepare 3.2kg of a crude tetrapropyl ammonium hydroxide aqueous solution with the mass concentration of 17.4%. Materials in the anode chamber 1, the byproduct chamber 2, the raw material chamber 3 and the cathode chamber 4 are respectively circulated by a circulating pump in the electrolysis process, the circulating flow rates of the materials in the anode chamber 1, the byproduct chamber 2 and the cathode chamber 4 are all 120ml/min, and the circulating flow rate of the material in the raw material chamber 3 is 160 ml/min.
S2 concentration: taking 1.5kg of crude product, adding 150g of n-propanol, and uniformly mixing to obtain a mixed solution. Concentrating the mixed solution by using a rotary evaporator at 80 r/min, vacuumizing to-0.09 MPa, concentrating in 80 ℃ water bath for 15min, selecting a program temperature control evaporator, continuously concentrating, simultaneously cooling the water bath to 60 ℃ at a constant speed for 80min, then continuously concentrating for 30min at 60 ℃ to prepare high-concentration tetrapropylammonium hydroxide, and detecting the mass concentration of the tetrapropylammonium hydroxide to be 30.7%.
Example 2
Example 2 differs from example 1 in that step S2 of example 2 was concentrated in 80 ℃ water bath for 125min without a temperature reduction concentration process, and otherwise the process was identical to example 1.
Examples 3 to 6
Examples 3 to 6 are different from example 1 in that the process parameters of the steps of examples 3 to 6 are different, the circulating flow rates of the materials in the anode chamber, the byproduct chamber and the cathode chamber are 120ml/min, and the others are the same as example 1, and the process parameters of the steps of examples 3 to 6 are shown in Table 1.
TABLE 1 Process parameters for each step of examples 3-6
Comparative example
Comparative example 1
Comparative example 1 differs from example 1 in that comparative example 1 does not have n-propanol added and the concentration temperature conditions are the same as example 1, all other things remaining the same as example 1.
Comparative example 2
The difference between the comparative example 2 and the example 1 is that the comparative example 2 does not add n-propanol, the concentration temperature condition is different from the example 1, the constant temperature concentration is carried out for 125min at 60 ℃, the temperature reduction concentration process is not carried out, and the rest is consistent with the example 1.
Comparative example 3
Comparative example 3 differs from comparative example 2 in that the concentration time of comparative example 3 was extended from 125min to 360min, all else remaining the same as in comparative example 2.
Performance detection
1. Tetrapropylammonium hydroxide concentration: 10mL of product is measured and injected into a 250mL triangular flask with a plug, 10.00mL of 100g/L barium chloride aqueous solution is added, 2-3 drops of 10g/L phenolphthalein indicator are added, and under the stirring of a magnetic stirrer, a hydrochloric acid standard titration solution with the concentration of 0.1000mol/L is used for titration until reddish color is taken as an end point. Record the volume of the consumed standard titration solution as V1. Tetrapropylammonium hydroxide content (X) in mass percent1%) was calculated as follows: x1％＝V1c × 203.36/(m × 10), wherein: v1 is the volume of hydrochloric acid standard solution consumed in the measurement of the sample solution, in ml; c is the molar concentration of the hydrochloric acid standard solution, and the unit mol/L; m is the mass of the sample, in g; 203.36 is the molar mass of tetrapropylammonium hydroxide in g/mol.
2. Determination of content of free tripropylamine: preparing a sample solution: weighing 50g of product into a 100mL volumetric flask, adding 5.00mL of cyclohexane, violently shaking for 5 minutes, adding water until the cyclohexane layer is positioned at the neck of the volumetric flask, standing for 20 minutes, and taking the cyclohexane layer for sample injection chromatography detection. Preparing a solution by a standard addition method: weighing 0.1 g of tripropylamine, adding the tripropylamine into a 10mL volumetric flask, dissolving the tripropylamine with cyclohexane and diluting the tripropylamine to a scale mark to obtain a tertiary amine solution; weighing 50g of product into a 100mL volumetric flask, sucking 1.00mL of the tertiary amine solution prepared in the step A by using a pipette, adding the tertiary amine solution into the volumetric flask, adding 4.00mL of cyclohexane, violently shaking for 5 minutes, adding water until a cyclohexane layer is positioned at the neck position, standing for 20 minutes, and taking the cyclohexane layer for sample injection chromatography detection. The tripropylamine content is in terms of mass ratio X, and the value is expressed in ug/g (equivalent to PPM) and is calculated as follows:
X＝A1m2/(A2m1-A1m3)×10-5(ii) a In the formula: a. the1The area value of the tripropylamine peak of the sample solution is obtained; a. the2The tripropylamine peak area value of the solution of the standard addition method is obtained; m is1The mass value of the sample in grams when the sample solution is prepared; m is2The numerical value of the mass of the tripropylamine in grams when the solution is prepared by a standard addition method; m is3Is a measure of the mass of a sample in grams when formulated in a standard addition solution.
TABLE 2 comparison of properties of tetrapropylammonium hydroxide products prepared by different processes
| Sample numbering | Tetrapropylammonium hydroxide concentration (%) | Tripropylamine content (ug/g) |
| Example 1 | 30.7 | 13.7 |
| Example 2 | 35.8 | 96.1 |
| Example 3 | 32.9 | 7.2 |
| Example 4 | 31.4 | 11.6 |
| Example 5 | 32.1 | 9.4 |
| Example 6 | 28.7 | 26.8 |
| Comparative example 1 | 23.6 | 345.3 |
| Comparative example 2 | 20.9 | 48.5 |
| Comparative example 3 | 26.7 | 83.2 |
Compared with example 1, the concentration step of comparative example 1 has no n-propanol added, the concentration effect is poor, and the product quality is affected because the concentration temperature is higher and the tripropylamine impurity content is higher. Comparative example 2 no n-propanol was added, and compared to comparative example 1, comparative example 2 concentrated at a lower temperature, which significantly reduced the tripropylamine impurity content in the product and contributed to the improvement of product quality, but the concentration effect was not good enough and the concentration of the product obtained was low. Comparative example 3 on the basis of comparative example 2, the concentration time is remarkably prolonged, and the prepared product has higher concentration, but the concentration time is longer, so that the production efficiency of the product is influenced.
Comparing the experimental results of example 1 and comparative examples 1-3, in example 1, n-propanol is added in the concentration step, and specific concentration temperature conditions are used, so that the concentration of the prepared product is higher, the content of tripropylamine impurities in the product is obviously reduced, and the improvement of the product quality is facilitated. Compared with the comparative example 3, the example 1 shortens the concentration time, and is helpful for improving the production efficiency of the product.
In comparison with example 1, example 2, in which concentration was carried out at 80 ℃, does not apply the preferable concentration temperature conditions, and the concentration of the obtained product is significantly increased, but the tripropylamine impurity content is high, so that it is recommended to use the specific concentration temperature conditions disclosed in the present application. Compared with example 1, the process parameters of examples 3-6 are changed, the concentration and impurity content of the prepared product are changed, wherein the n-propanol dosage in example 6 is less, and the impurity content of the tripropylamine in the prepared product is slightly increased. The method disclosed by the application is used for preparing the tetrapropylammonium hydroxide aqueous solution with high concentration, which is beneficial to reducing the impurity content in the product, improving the product quality, shortening the concentration time and improving the production efficiency.
The embodiments of the present invention are preferred embodiments of the present application, and the scope of protection of the present application is not limited by the embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (9)
1. A production process of high-concentration tetrapropylammonium hydroxide is characterized by comprising the following steps:
s1 electrolysis: adding water into tetrapropyl quaternary ammonium salt to prepare tetrapropyl quaternary ammonium salt water solution, and combining tetrapropyl ammonium cations with hydroxide ions generated by electrolysis by an electrolysis method to form tetrapropyl ammonium hydroxide to prepare a crude product;
s2 concentration: adding n-propanol 0.05-0.2 times the weight of the crude product into the crude product, mixing well to obtain a mixed solution, heating the mixed solution to 60-80 deg.C, and concentrating for not less than 60min to obtain high-concentration tetrapropylammonium hydroxide.
2. The process according to claim 1, wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of: the tetrapropyl quaternary ammonium salt is tetrapropyl ammonium bromide.
3. The process according to claim 2, wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of: the step S1 is an electrolysis step using an electrolytic cell comprising an anode chamber (1), a byproduct chamber (2), a raw material chamber (3) and a cathode chamber (4) which are adjacent in sequence; an anode plate (5) is arranged in the anode chamber (1), a cathode plate (6) is arranged in the cathode chamber (4), and the anode plate (5) is connected with the cathode plate (6) through a power supply; the anode chamber (1) is communicated with the byproduct chamber (2) through a first cationic membrane (7), the byproduct chamber (2) is communicated with the raw material chamber (3) through an anionic membrane (8), and the raw material chamber (3) is communicated with the cathode chamber (4) through a second cationic membrane (9); in the step S1, water is added to the anode chamber (1), the byproduct chamber (2) and the cathode chamber (4), and in the step S1, the tetrapropyl quaternary ammonium salt water solution is added to the raw material chamber (3) and then electrolysis is carried out.
4. The process according to claim 1, wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of: the step S2 is performed in a vacuum state at a pressure of-0.095 to-0.08 MPa.
5. The process according to claim 4, wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of: and step S2, carrying out vacuum-pumping concentration on the mixed solution in a water bath at the temperature of 80 ℃ for 10-20min, continuously concentrating, simultaneously cooling the water bath to 60 ℃ at a constant speed for 60-90min, and then continuously concentrating at the temperature of 60 ℃ for not less than 30min to obtain the high-concentration tetrapropylammonium hydroxide.
6. The process according to claim 3, wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of: materials in the anode chamber (1), the byproduct chamber (2), the raw material chamber (3) and the cathode chamber (4) are respectively circulated by a circulating pump in the electrolysis process of the step S1, the circulating flow rates of the materials in the anode chamber (1) and the byproduct chamber (2) are the same as the circulating flow rate of the materials in the cathode chamber (4), and the circulating flow rate of the materials in the raw material chamber (3) is 1.2-1.5 times of the circulating flow rate of the materials in the anode chamber (1).
7. The process according to claim 1, wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of: the electrolysis temperature of the step S1 is not more than 58 ℃.
8. The process according to claim 3, wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of: and the mass concentration of the tetrapropyl ammonium bromide in the material chamber of the step S1 is not more than 15%.
9. A high-concentration tetrapropylammonium hydroxide, characterized in that: is prepared by the production process of the high-concentration tetrapropylammonium hydroxide according to any one of claims 1 to 8.
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