CN114318376A - Preparation method of tetrapropylammonium hydroxide and quaternary ammonium alkaline water solution prepared by same - Google Patents
Preparation method of tetrapropylammonium hydroxide and quaternary ammonium alkaline water solution prepared by same Download PDFInfo
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Abstract
The application discloses a preparation method of tetrapropyl ammonium hydroxide and a quaternary ammonium base aqueous solution prepared by the same, and relates to the technical field of molecular sieve quaternary ammonium base template agent production. The preparation method of tetrapropylammonium hydroxide comprises the following steps: quaternization of S1: taking tri-n-propylamine and bromopropane, taking acetonitrile as a reaction solvent, adding a nickel-titanium catalyst, stirring, and carrying out reflux reaction to obtain a quaternary ammonium compound; s2 base formation: preparing a quaternary ammonium alkali aqueous solution from a quaternary ammonium compound by an ion exchange method or an electrolytic method; the mass ratio of tri-n-propylamine to bromopropane to acetonitrile in the step S1 is 1: (1-1.1): (3-8); the mass ratio of the tri-n-propylamine to the nickel titanium catalyst in the step S1 is 100: (1-5); the nickel-titanium catalyst is mainly prepared from the following raw materials in parts by weight: 8-15 parts of soluble nickel salt and 50 parts of nano titanium oxide. The preparation method of tetrapropylammonium hydroxide has the advantage of low energy consumption.
Description
Technical Field
The application relates to the technical field of molecular sieve quaternary ammonium hydroxide template agent production, in particular to a preparation method of tetrapropyl ammonium hydroxide and a quaternary ammonium hydroxide aqueous solution prepared by the same.
Background
Propylene oxide is an important raw material for producing chemical products such as polyether, propylene glycol, polyurethane, nonionic surfactant, oil field demulsifier and the like, and is widely applied to the field of fine chemical engineering. The process for preparing propylene oxide by using chlorohydrin faces serious environmental protection problems, and with the increasing social requirements on environmental protection, people gradually abandon the synthesis process for preparing propylene oxide by using chlorohydrin and gradually select an HPPO process using hydrogen peroxide as an oxidant. The core of the HPPO process is a TS-1 molecular sieve catalyst, and the TS-1 molecular sieve is generally synthesized by using tetrapropylammonium hydroxide as a template agent.
The currently common production process of tetrapropylammonium hydroxide is to react tripropylamine with bromopropane to generate tetrapropylammonium bromide, and then prepare tetrapropylammonium hydroxide by ion exchange or electrolysis and other methods.
In view of the above-mentioned related technologies, the inventors believe that, in the reaction process of tripropylamine and bromopropane, the reaction activity between tripropylamine and bromopropane is not high, the reaction yield is low, and the reaction time is more than 50 hours to achieve a yield of more than 80%, which increases the energy consumption of the tetrapropylammonium hydroxide production process.
Disclosure of Invention
In order to reduce the energy consumption of tetrapropylammonium hydroxide, the application provides a preparation method of tetrapropylammonium hydroxide and a quaternary ammonium alkali aqueous solution prepared by the preparation method.
In a first aspect, the present application provides a preparation method of tetrapropylammonium hydroxide, which adopts the following technical scheme:
a preparation method of tetrapropylammonium hydroxide comprises the following steps:
quaternization of S1: taking tri-n-propylamine and bromopropane, taking acetonitrile as a reaction solvent, adding a nickel-titanium catalyst, stirring, heating until reflux reaction is carried out for 8-20h to form quaternary ammonium salt, and recovering a product to obtain a quaternary ammonium compound;
s2 base formation: preparing a quaternary ammonium alkali aqueous solution from a quaternary ammonium compound by an ion exchange method or an electrolytic method;
the mass ratio of tri-n-propylamine to bromopropane to acetonitrile in the step S1 is 1: (1-1.1): (3-8); the mass ratio of the tri-n-propylamine to the nickel titanium catalyst in the step S1 is 100: (1-5); the nickel-titanium catalyst is mainly prepared from the following raw materials in parts by weight: 8-15 parts of soluble nickel salt and 50 parts of nano titanium oxide.
By adopting the technical scheme, in the step S1, acetonitrile is used as a reaction solvent, is a polar aprotic solvent, has certain dissolving capacity on nickel ions and titanium ions under a high-temperature reflux state, and has certain activation effect on the nickel ions and the titanium ions; the nickel-titanium catalyst contains nickel ions and titanium ions, and after being activated by acetonitrile at high temperature, the nickel-titanium catalyst has a remarkable catalytic effect on the quaternization reaction between bromopropane and tri-n-propylamine, so that the quaternization reaction is accelerated, the reaction conversion rate is improved, the reaction time of the quaternization reaction is remarkably shortened, and the production energy consumption of tetrapropylammonium hydroxide products is reduced.
Preferably, the mass ratio of tri-n-propylamine to bromopropane to acetonitrile in step S1 is 1: (1.02-1.04): (3.5-5); the mass ratio of the tri-n-propylamine to the nickel titanium catalyst in the step S1 is 100: (2.5-3.5).
By adopting the technical scheme, the better raw material feeding ratio is used, the reaction yield is improved, and the production cost of the tetrapropyl ammonium hydroxide is reduced.
Preferably, the reflux reaction time of the step S1 is 12-20 h.
By adopting the technical scheme, better reflux reaction time is selected, the reaction yield is improved, and the production cost of the tetrapropylammonium hydroxide is reduced.
Preferably, after the reflux reaction in the step S1 is completed, the temperature is reduced to not higher than 35 ℃, the filtration is performed for the first time, and the filter cake is washed with acetonitrile for the first time; adding the primary filter cake into water with a weight not less than 4 times of that of tri-n-propylamine, stirring for not less than 30min, carrying out secondary filtration, washing the secondary filter cake with water, and taking secondary filtrate to obtain the quaternary ammonium compound.
By adopting the technical scheme, after the reflux reaction in the step S1 is finished, the tetrapropyl ammonium bromide is separated out from the acetonitrile, and the tetrapropyl ammonium bromide and the nickel-titanium catalyst are in a filter cake, and the acetonitrile and the unreacted raw materials are in primary mother liquor through primary filtration, so that the acetonitrile and the unreacted raw materials are convenient to recover; dissolving the primary filter cake in water, dissolving tetrapropyl ammonium bromide in water, and recycling the tetrapropyl ammonium bromide by secondary filtration, wherein the tetrapropyl ammonium bromide is in secondary mother liquor, and the nickel-titanium catalyst is in a secondary filter cake; the secondary mother liquor can be directly subjected to ion exchange or electrolysis in the next step to generate tetrapropylammonium hydroxide; the nickel titanium catalyst of the secondary filter cake can be recycled, which is beneficial to reducing the production cost.
Preferably, the step S1 further includes the steps of: and drying the secondary filter cake to complete the recovery of the nickel-titanium catalyst.
By adopting the technical scheme, the nickel-titanium catalyst is recycled, the material waste is reduced, and the production cost is reduced.
Preferably, the preparation method of the nickel titanium catalyst comprises the following steps: adding water into soluble nickel salt to prepare a nickel salt aqueous solution with the concentration of 4-8%, adding nano titanium oxide, uniformly mixing, soaking for not less than 120min, drying, and roasting at the temperature of 250-350 ℃ for not less than 2h to prepare the nickel-titanium catalyst; the soluble nickel salt is nickel chloride; the weight ratio of the nickel chloride to the nano titanium oxide is (10-12): 50.
by adopting the technical scheme, the nano titanium oxide is used as a carrier, nickel chloride is dissolved in water and then is soaked on the surface of the nano titanium oxide, and nickel ions are attached to the surface of the nano titanium oxide in the form of nickel oxide or nickel simple substance by roasting, so that the synergistic effect of the nickel ions and the titanium ions is favorably exerted, and the quaternization reaction is better catalyzed; on the other hand, the method is beneficial to separating the tetrapropylammonium bromide and the nickel titanium catalyst through secondary filtration, and better recovery of products is facilitated.
Preferably, the specific surface area of the nano titanium oxide is not less than 120 square meters per gram.
By adopting the technical scheme, the nano titanium oxide with high specific surface area is used, so that nickel ions are favorably dispersed on the surface of the nano titanium oxide, bromopropane is favorably acted with a nickel-titanium catalyst, the reaction rate is favorably accelerated, the reaction yield is improved, and the cost is reduced.
Preferably, the step S2 is to perform alkali formation by an electrolytic method using an electrolytic cell, wherein the electrolytic cell comprises an anode chamber, a transition 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 transition chamber through a first cation membrane, the transition chamber is communicated with the raw material chamber through an anion membrane, and the raw material chamber is communicated with the cathode chamber through a second cation membrane; the step S2 includes the steps of: and adding the quaternary ammonium compound aqueous solution into the raw material chamber, starting a power supply, enabling tetrapropyl ammonium cations to enter the cathode chamber through the second cationic membrane, and combining the tetrapropyl ammonium cations with hydroxide ions generated by the cathode chamber to form tetrapropyl ammonium hydroxide to prepare the quaternary ammonium aqueous alkali solution.
By adopting the technical scheme, the electrolysis method is used in the alkali forming step, which is beneficial to improving the product purity of the quaternary ammonium alkali aqueous solution and reducing impurities; the method is favorable for improving the specific surface area of the downstream molecular sieve product and the catalytic performance of the downstream molecular sieve product.
In a second aspect, the present application provides an aqueous alkaline quaternary ammonium solution, which adopts the following technical scheme:
a quaternary ammonium aqueous alkali solution is prepared by the preparation method of the tetrapropylammonium hydroxide.
By adopting the technical scheme, the method disclosed by the application is used for preparing the aqueous solution of the quaternary ammonium base, so that the energy consumption is reduced, and the product purity is improved.
In summary, the present application includes at least one of the following beneficial technical effects:
1. in the process of carrying out quaternization reaction on tripropylamine and bromopropane, acetonitrile is used as a reaction solvent, a nickel-titanium catalyst containing nickel ions and titanium ions, the acetonitrile, the nickel ions and the nano titanium oxide are added, and the three components act together, so that the reaction activity between the bromopropane and the tripropylamine is remarkably improved, the reaction yield is improved, the quaternization reaction time is shortened, and the energy consumption of a tetrapropylammonium hydroxide production process is reduced;
2. by selecting a proper nickel-titanium catalyst preparation method, the preparation method is beneficial to better exerting the synergistic effect of nickel ions, nano titanium oxide and acetonitrile, is beneficial to improving the reaction yield, and is beneficial to reducing the production cost of tetrapropyl ammonium hydroxide;
3. by selecting a proper post-treatment process in the step S1, the nickel-titanium catalyst, the reaction product, the solvent and the raw materials are better separated, the catalyst, the acetonitrile and other materials are better recovered, and the production cost of the tetrapropylammonium hydroxide is reduced.
Drawings
FIG. 1 is a schematic view of the cell structure used in the present application.
Reference numerals: 1. an anode chamber; 2. a transition chamber; 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 production process of tetrapropylammonium hydroxide generally comprises the steps of reacting tripropylamine with bromopropane to generate tetrapropylammonium bromide, and then preparing the tetrapropylammonium hydroxide by methods such as ion exchange or electrolysis. The inventor finds that the reaction activity between tripropylamine and bromopropane is not high, the reaction yield of quaternization is not high, if the reaction yield of quaternization is more than 80%, the reflux reaction needs to be carried out for more than 50 hours, and the energy consumption is high. Based on the above technical background, the present application provides a technical solution for reducing the production energy consumption of tetrapropylammonium hydroxide products, which is specifically described in the following detailed description.
Tripropylamine is tri-n-propylamine and bromopropane is 1-bromopropane in this application. In the post-treatment process of the step S1, the water amount for dissolving the primary filter cake and washing the secondary filter cake can be adjusted according to actual production requirements, so that the concentration of the tetrapropylammonium bromide is matched with the raw material concentration required in the step S2 for forming alkali. In the actual production process, the secondary mother liquor can be concentrated and dried as required to obtain a dry tetrapropyl ammonium bromide intermediate product. In the actual production process, because a small amount of tetrapropylammonium bromide is dissolved in acetonitrile, the mother liquor once filtered in the step S1 can be recycled, and the product loss is reduced; the mother liquor once filtered in step S1 may be concentrated to recover tetrapropylammonium bromide in the mother liquor once. 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. The mass concentration of tetrapropylammonium bromide in the feed chamber during electrolysis is not more than 14%, preferably 12-14%. 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, the 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 between 12 and 14 percent.
The following examples use the same set of electrolysis equipment. The raw materials are all commercially available, and the nano titanium oxide is provided by Hangzhou Hengge nano science and technology limited company, model number HN-T30D, average particle size is 18nm, specific surface area is 185m2/g。
The detection method of the concentration of tetrapropylammonium hydroxide comprises the following steps: 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.
The present application is described in further detail below with reference to the attached drawings.
Preparation example
Preparation example 1:
the preparation method of the nickel-titanium catalyst comprises the following steps: 1kg of nickel chloride (anhydrous nickel chloride, industrial grade, and chemical Limited of Jinan element) is added with water to prepare 6% nickel chloride aqueous solution, 5kg of nano titanium oxide is added, the mixture is uniformly mixed, dipped for 120min, dried and roasted for 2h at 350 ℃ to prepare the nickel-titanium catalyst.
Examples
Example 1: the preparation method of tetrapropylammonium hydroxide comprises the following steps: quaternization of S1: 1.43kg of tri-n-propylamine and 1kg of bromopropane were taken, 3.28kg of acetonitrile was added as a reaction solvent, 15g of nickel titanium catalyst (prepared in preparation example 1) was added, stirring was carried out at a rotation speed of 100 rpm, and heating was carried out until reflux reaction was carried out for 8 hours. Cooling to 35 ℃, filtering for the first time, and washing a filter cake for the first time by 200ml of acetonitrile; adding the primary filter cake into 5.8kg of water, stirring at the rotating speed of 200 r/min for 30min, filtering for the second time, washing the secondary filter cake with 500ml of water, and taking the secondary filtrate to obtain the quaternary ammonium compound.
S2 base formation: electrolyzing a quaternary ammonium compound by an electrolytic method by using an electrolytic cell, wherein the electrolytic cell comprises an anode chamber 1, a transition chamber 2, a raw material chamber 3 and a cathode chamber 4 which are adjacent in sequence and are at the same height; an anode plate 5 (iridium tantalum plate and titanium substrate) is arranged in the anode chamber 1, a cathode plate 6 (the size and shape of the cathode plate 6 are consistent with those of the anode plate 5, a nickel electrode is adopted) 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 transition chamber 2 through a first cation membrane 7, the transition 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 preparation method comprises the following steps: taking the quaternary ammonium compound tetrapropyl ammonium bromide aqueous solution prepared in the step S1, adding water into the anode chamber 1, the transition chamber 2 and the cathode chamber 4, adding the tetrapropyl ammonium bromide aqueous solution into the raw material chamber 3, adding water to control the initial mass concentration of the tetrapropyl ammonium bromide aqueous solution in the raw material chamber 3 to be 14%, controlling the electrolysis process to be 12-14%, controlling the electrolysis voltage to be 6V, combining tetrapropyl ammonium cations with hydroxyl ions generated by the cathode chamber 4 of the electrolytic cell to form tetrapropyl ammonium hydroxide, circulating the materials in the anode chamber 1, the transition chamber 2, the raw material chamber 3 and the cathode chamber 4 in the electrolysis process by using a circulating pump, wherein the circulating flow of the materials in the anode chamber 1, the transition chamber 2 and the cathode chamber 4 is 150ml/min, and the circulating flow of the material in the raw material chamber 3 is 180 ml/min. According to the concentration change of the tetrapropylammonium bromide in the raw material chamber 3, the tetrapropylammonium bromide aqueous solution prepared in the step S1 is supplemented into the raw material chamber 3 in the electrolysis process, so that the mass concentration of the tetrapropylammonium bromide in the raw material chamber 3 is kept between 12 and 14 percent. After 30 hours of electrolysis, 2.5kg of 23.4% strength by mass aqueous tetrapropylammonium hydroxide solution was obtained.
Example 2
Example 2 differs from example 1 in that tri-n-propylamine in step S1 of example 2: bromopropane: the mass ratio of acetonitrile is 1: 1.04: 3.5, the rest remaining in accordance with example 1.
Example 3
Example 3 differs from example 2 in that step S1 of example 3 extended the reflux reaction time from 8h to 12h, all else remaining the same as example 2.
Example 4
Example 4 differs from example 3 in that step S1 of example 4 extended the reflux reaction time from 12h to 20h, all else remaining the same as example 3.
Examples 5 to 8
Examples 5 to 8 were different from example 3 in the amounts of the respective raw materials added in step S1 in examples 5 to 8, but were identical to example 3, and the amounts of the respective raw materials added in examples 5 to 8 were shown in Table 1.
TABLE 1 addition amount of each raw material of examples 5 to 8
Example 9
Example 9 differs from example 6 in that example 9 uses the recovered nickel titanium catalyst of examples 5-8 instead of fresh nickel titanium catalyst (the second cake of step S1 was washed with water and dried at 100 c for 180min to complete the recovery of nickel titanium catalyst), all otherwise in accordance with example 6.
Comparative example
Comparative example 1
Comparative example 1 differs from example 1 in that no nickel titanium catalyst was added in step S1 of comparative example 1, and otherwise remains the same as example 1.
Comparative example 2
Comparative example 2 differs from comparative example 1 in that comparative example 2 extended the heat reflux time of step S1 from 8h to 60h, all else being consistent with comparative example 1.
Comparative example 3
Comparative example 3 differs from example 1 in that the nickel titanium catalyst was not added in step S1 of comparative example 3, but 15g of nano titanium oxide was added, and the rest was identical to example 1.
Comparative example 4
Comparative example 4 differs from example 1 in that the nickel titanium catalyst was not added in step S1 of comparative example 4, but 1.5g of nickel chloride was added, all of which were otherwise identical to example 1.
Performance detection
1. Calculation of quaternization yield in step S1: and (3) taking 100g of the quaternary ammonium compound aqueous solution prepared in the step S1, carrying out rotary evaporation drying at-0.09 MPa and 80 ℃ for 300min, weighing the dried solid, and calculating the content of tetrapropylammonium bromide in the quaternary ammonium compound aqueous solution prepared in the step S1. Concentrating the primary mother liquor obtained by primary filtration in the step S1 at-0.09 MPa and 80 ℃ to constant weight to obtain a mother liquor concentrate, and detecting the content of bromide ions in the mother liquor concentrate by using a silver quantity method; the specific method comprises the following steps: weighing a mother liquor concentrate sample (accurate to 0.0002g) with the mass of about 0.80g, dissolving the mother liquor concentrate sample in 50ml of ethanol, adding 25ml of distilled water, adding 0.1g of calcium carbonate and 8 drops of a fluorescent yellow ethanol solution, and titrating the mixture by using a 0.1mol/L silver nitrate standard solution until the turbid solution is suddenly changed into pink, namely an end point; the amount of tetrapropylammonium bromide in the mother liquor concentrate was calculated. The content of tetrapropylammonium bromide in the mother liquor concentrate and the content of tetrapropylammonium bromide in the aqueous solution of the quaternary ammonium compound were combined, and the yield of step S1 was calculated. The results are shown in Table 2.
TABLE 3 comparison of quaternization yields in the different process steps S1
Comparative example 1 the reaction yield of the quaternization reaction was lower without the addition of a nickel titanium catalyst; comparative examples 3-4 were all high in yield by adding nano titanium oxide and nickel chloride separately. Comparative example 2 the yield was improved by extending the reaction time to 60h, but the reaction time was too long and the energy consumption was high. Comparing example 1 with comparative examples 1-4, the reaction yield of quaternization reaction is obviously improved, the reaction time is shortened and the energy consumption is reduced by adding the nickel titanium catalyst in example 1.
Comparing example 2 with example 1, example 2 selects more suitable charging ratio, and the yield is slightly improved. Comparing examples 3-4 with example 2, the quaternization reaction time of examples 3-4 is longer and the yield is higher. Examples 5-8 are comparative experiments with different amounts of nickel titanium catalyst, and the reaction yield of the quaternization reaction increases with increasing amounts of nickel titanium catalyst, but does not increase further when the amount is too large. Example 9 is a high reaction yield with a recycled nickel titanium catalyst.
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 preparation method of tetrapropylammonium hydroxide is characterized by comprising the following steps:
quaternization of S1: taking tri-n-propylamine and bromopropane, taking acetonitrile as a reaction solvent, adding a nickel-titanium catalyst, stirring, heating until reflux reaction is carried out for 8-20h to form quaternary ammonium salt, and recovering a product to obtain a quaternary ammonium compound;
s2 base formation: preparing a quaternary ammonium alkali aqueous solution from a quaternary ammonium compound by an ion exchange method or an electrolytic method;
the mass ratio of tri-n-propylamine to bromopropane to acetonitrile in the step S1 is 1: (1-1.1): (3-8); the mass ratio of the tri-n-propylamine to the nickel titanium catalyst in the step S1 is 100: (1-5); the nickel-titanium catalyst is mainly prepared from the following raw materials in parts by weight: 8-15 parts of soluble nickel salt and 50 parts of nano titanium oxide.
2. The method according to claim 1, wherein the method comprises the following steps: the mass ratio of tri-n-propylamine to bromopropane to acetonitrile in the step S1 is 1: (1.02-1.04): (3.5-5); the mass ratio of the tri-n-propylamine to the nickel titanium catalyst in the step S1 is 100: (2.5-3.5).
3. The method according to claim 1, wherein the method comprises the following steps: the reflux reaction time of the step S1 is 12-20 h.
4. The method according to claim 1, wherein the method comprises the following steps: after the reflux reaction in the step S1 is finished, cooling to a temperature not higher than 35 ℃, carrying out primary filtration, and washing a primary filter cake with acetonitrile; adding the primary filter cake into water with a weight not less than 4 times of that of tri-n-propylamine, stirring for not less than 30min, carrying out secondary filtration, washing the secondary filter cake with water, and taking secondary filtrate to obtain the quaternary ammonium compound.
5. The method according to claim 4, wherein the step S1 further comprises the steps of: and drying the secondary filter cake to complete the recovery of the nickel-titanium catalyst.
6. The method of claim 1, wherein the nickel titanium catalyst is prepared by the steps of: adding water into soluble nickel salt to prepare a nickel salt aqueous solution with the concentration of 4-8%, adding nano titanium oxide, uniformly mixing, soaking for not less than 120min, drying, and roasting at the temperature of 250-350 ℃ for not less than 2h to prepare the nickel-titanium catalyst; the soluble nickel salt is nickel chloride; the weight ratio of the nickel chloride to the nano titanium oxide is (10-12): 50.
7. the method according to claim 6, wherein the method comprises the following steps: the specific surface area of the nano titanium oxide is not less than 120 square meters per gram.
8. The method according to claim 1, wherein the method comprises the following steps: the step S2 is to perform alkali formation by an electrolytic method by using an electrolytic cell, wherein the electrolytic cell comprises an anode chamber (1), a transition 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 transition chamber (2) through a first cationic membrane (7), the transition 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); the step S2 includes the steps of: and adding the quaternary ammonium compound aqueous solution into the raw material chamber (3), starting a power supply, enabling tetrapropylammonium cations to enter the cathode chamber (4) through the second cationic membrane (9), and combining the tetrapropylammonium cations with hydroxide ions generated by the cathode chamber (4) to form tetrapropylammonium hydroxide to prepare the quaternary ammonium alkali aqueous solution.
9. An aqueous alkaline quaternary ammonium salt solution characterized by: prepared by the process for the preparation of tetrapropylammonium hydroxide according to any one of claims 1 to 8.
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| CN116162943A (en) * | 2023-02-13 | 2023-05-26 | 肯特催化材料股份有限公司 | Preparation method of trimethyl ethyl ammonium hydroxide and quaternary ammonium base aqueous solution prepared by preparation method |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0100477A2 (en) * | 1982-07-31 | 1984-02-15 | Bayer Ag | 4-Trifluoromethyl-benzyl ammonium salts |
| US5393386A (en) * | 1992-12-28 | 1995-02-28 | Mitsubishi Gas Chemical Company, Inc. | Method for preparing aqueous quaternary ammonium hydroxide solution |
| US20040126308A1 (en) * | 2002-12-16 | 2004-07-01 | Council Of Scientific And Industrial Research | Process for preparing quaternary ammonium tribromides |
| CN1948268A (en) * | 2005-10-10 | 2007-04-18 | 浙江师范大学 | Synthesis method of quaternary ammonium salt |
| CN101148411A (en) * | 2007-11-06 | 2008-03-26 | 华东理工大学 | Method for preparing tetrapropylammonium bromide and horizontal autoclave |
| CN102020570A (en) * | 2009-09-23 | 2011-04-20 | 天津市化学试剂研究所 | Preparation method for tetrapropyl ammonium bromide |
| CN109053459A (en) * | 2018-09-20 | 2018-12-21 | 中国矿业大学(北京) | A kind of preparation method of four N-propyl bromides |
| CN109651175A (en) * | 2018-12-05 | 2019-04-19 | 江西肯特化学有限公司 | A method of preparing high-purity 4-propyl bromide |
| CN110711582A (en) * | 2019-09-18 | 2020-01-21 | 郑州大学 | Catalyst, preparation method and application thereof |
| CN111960948A (en) * | 2020-09-16 | 2020-11-20 | 肯特催化材料股份有限公司 | Synthesis process of tetrabutylammonium bromide |
| CN113235117A (en) * | 2021-05-12 | 2021-08-10 | 肯特催化材料股份有限公司 | Production process of high-concentration tetrapropylammonium hydroxide and high-concentration tetrapropylammonium hydroxide prepared by same |
| CN113265683A (en) * | 2021-05-12 | 2021-08-17 | 肯特催化材料股份有限公司 | High-efficiency production process of tetrapropylammonium hydroxide and tetrapropylammonium hydroxide aqueous solution prepared by high-efficiency production process |
| CN113463118A (en) * | 2021-05-12 | 2021-10-01 | 肯特催化材料股份有限公司 | Energy-saving production process of tetrapropylammonium hydroxide and tetrapropylammonium hydroxide aqueous solution prepared by same |
| CN113620810A (en) * | 2021-08-05 | 2021-11-09 | 肯特催化材料股份有限公司 | Preparation method of quaternary ammonium salt and method for preparing quaternary ammonium base by using quaternary ammonium salt |
-
2022
- 2022-01-26 CN CN202210090791.6A patent/CN114318376B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0100477A2 (en) * | 1982-07-31 | 1984-02-15 | Bayer Ag | 4-Trifluoromethyl-benzyl ammonium salts |
| US5393386A (en) * | 1992-12-28 | 1995-02-28 | Mitsubishi Gas Chemical Company, Inc. | Method for preparing aqueous quaternary ammonium hydroxide solution |
| US20040126308A1 (en) * | 2002-12-16 | 2004-07-01 | Council Of Scientific And Industrial Research | Process for preparing quaternary ammonium tribromides |
| CN1948268A (en) * | 2005-10-10 | 2007-04-18 | 浙江师范大学 | Synthesis method of quaternary ammonium salt |
| CN101148411A (en) * | 2007-11-06 | 2008-03-26 | 华东理工大学 | Method for preparing tetrapropylammonium bromide and horizontal autoclave |
| CN102020570A (en) * | 2009-09-23 | 2011-04-20 | 天津市化学试剂研究所 | Preparation method for tetrapropyl ammonium bromide |
| CN109053459A (en) * | 2018-09-20 | 2018-12-21 | 中国矿业大学(北京) | A kind of preparation method of four N-propyl bromides |
| CN109651175A (en) * | 2018-12-05 | 2019-04-19 | 江西肯特化学有限公司 | A method of preparing high-purity 4-propyl bromide |
| CN110711582A (en) * | 2019-09-18 | 2020-01-21 | 郑州大学 | Catalyst, preparation method and application thereof |
| CN111960948A (en) * | 2020-09-16 | 2020-11-20 | 肯特催化材料股份有限公司 | Synthesis process of tetrabutylammonium bromide |
| CN113235117A (en) * | 2021-05-12 | 2021-08-10 | 肯特催化材料股份有限公司 | Production process of high-concentration tetrapropylammonium hydroxide and high-concentration tetrapropylammonium hydroxide prepared by same |
| CN113265683A (en) * | 2021-05-12 | 2021-08-17 | 肯特催化材料股份有限公司 | High-efficiency production process of tetrapropylammonium hydroxide and tetrapropylammonium hydroxide aqueous solution prepared by high-efficiency production process |
| CN113463118A (en) * | 2021-05-12 | 2021-10-01 | 肯特催化材料股份有限公司 | Energy-saving production process of tetrapropylammonium hydroxide and tetrapropylammonium hydroxide aqueous solution prepared by same |
| CN113620810A (en) * | 2021-08-05 | 2021-11-09 | 肯特催化材料股份有限公司 | Preparation method of quaternary ammonium salt and method for preparing quaternary ammonium base by using quaternary ammonium salt |
Non-Patent Citations (2)
| Title |
|---|
| 孙斌等: "四丙基氢氧化铵合成工艺技术的研究", 《石油炼制与化工》 * |
| 苏晓明等: "三甲氧基硅烷季铵盐的合成工艺研究", 《化工技术与开发》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116162943A (en) * | 2023-02-13 | 2023-05-26 | 肯特催化材料股份有限公司 | Preparation method of trimethyl ethyl ammonium hydroxide and quaternary ammonium base aqueous solution prepared by preparation method |
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