CN111377875A - Preparation method and application of 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution - Google Patents
Preparation method and application of 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution Download PDFInfo
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- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
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Abstract
The invention relates to the field of environmental protection, and in particular relates to a preparation method and application of a2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution. The preparation method of the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution comprises the following steps: adding cyanuric chloride and a sodium sulfide aqueous solution into a sodium hydrosulfide aqueous solution, and controlling the speed of adding the cyanuric chloride and the sodium sulfide aqueous solution to obtain a mixed solution with the pH value of 10-12; the temperature of the mixed solution is controlled to be 0-20 ℃; and heating the mixed solution to enable sodium hydrosulfide and sodium sulfide to react with cyanuric chloride, and after the reaction is finished, sequentially cooling and filtering to obtain the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution. The invention avoids using alkali to control the pH value of a reaction system and furthest inhibits the occurrence of hydrolysis reaction by changing the molar ratio of the sodium hydrosulfide to the sodium sulfide, thereby ensuring the purity and the yield of the 2, 4, 6-trimercapto-s-triazine disodium salt.
Description
Technical Field
The invention relates to the field of environmental protection, and in particular relates to a preparation method and application of a2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution.
Background
2, 4, 6-trimercapto-s-triazine has a wide range of applications in various fields because of having three mercapto groups (SH). For example: the rubber is used as a vulcanizing agent to modify a polymer, is used as a bonding agent for bonding rubber and metal, is used for forming a secondary battery, and is used for recovering metal or treating heavy metal pollutants in an environmental medium.
The preparation method of 2, 4, 6-trimercapto-s-triazine or salt thereof has been related to a plurality of documents and patents.
U.S. Pat. No. 4,4849517 discloses 2, 4, 6-trimercapto-s-triazine trisodium salt nonahydrate (TMT-Na)39H2O) preparation method. By cyanuric chloride with NaHS + NaOH or NaHS + Na2S + NaOH reacts in aqueous solution for preparation, and then the product is cooled to 0-20 ℃ for crystallization and is filtered to obtain TMT-Na39H2Crystal of O (yield 79.3%), TMT-Na in filtrate3It is converted to TMT-H by acidification to pH 2-4 with mineral acid3Precipitated out (yield 16.2%).
Chinese patent application (CN101591303A) for reducing TMT-Na in recovered filtrate3The use amount of acid and alkali in the process is reduced to 6-8 from 12, and 2, 4, 6-trimercapto-s-triazine monosodium salt (TMT-Na) is separated out through precipitation, so that the economical efficiency of the process is improved.
Liu ' an Chang et al reported a trisodium salt (TMT-Na) for preparing 2, 4, 6-trimercapto-s-triazine in 2015, 27 vol.4, pages 8-10 of the book ' Wuhan chemical institute ' journal3) The method of (1). The method is to add hydrochloric acid directly into the reaction product for acidification and precipitate TMT-H3And then recrystallizing and purifying the obtained TMT-H by using methanol3And (4) crystals. Then adding TMT-H3Dissolving in NaOH water solution (pH 12-12.5)) To obtain TMT-Na3Aqueous solution (concentration is more than or equal to 15wt percent).
Yan et al in Ind.Eng.chem.Res.2008,47,5318-5322 report that cyanuric chloride undergoes a hydrolysis reaction in aqueous solution according to the following equation (1). And when the pH of the aqueous solution is>At 7, the rate of hydrolysis is faster [ as in equation (2) ]. Thus, cyanuric chloride is reacted with NaHS or Na in aqueous solution2In the process of synthesizing 2, 4, 6-trimercapto-S-triazine by S reaction, the side reaction (as shown in equation (2)) promoted by adding NaOH is avoided as much as possible.
The method for synthesizing 2, 4, 6-trimercapto-s-triazine or salt thereof disclosed above directly combines the raw material cyanuric chloride with a sulfhydrylation reagent (NaHS or Na) without considering the water insolubility of the raw material cyanuric chloride2S) and a base are rapidly mixed to react, which results in a large amount of solids in the reaction system, thereby causing local reaction conditions such as pH and temperature to deviate from ideal reaction conditions. Furthermore, it involves adding a base to the reaction system to maintain the pH of the reaction in the alkaline range. Thus, the products all undergo hydrolysis to varying degrees. In addition, these synthetic methods involve a step of separating and purifying the synthesized product, so that the actual synthetic process becomes complicated and the yield of the product is also reduced.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method and application of a2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution, which can reduce or even avoid using alkali to adjust the pH value of a reaction solution, thereby inhibiting the occurrence of hydrolysis side reaction and improving the purity and yield of the 2, 4, 6-trimercapto-s-triazine disodium salt.
The invention provides a preparation method of a2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution, which comprises the following steps:
adding cyanuric chloride and a sodium sulfide aqueous solution into a sodium hydrosulfide aqueous solution, and controlling the speed of adding the cyanuric chloride and the sodium sulfide aqueous solution to obtain a mixed solution with the pH value of 10-12; the temperature of the mixed solution is controlled to be 0-20 ℃;
and heating the mixed solution to enable sodium hydrosulfide and sodium sulfide to react with cyanuric chloride, and after the reaction is finished, sequentially cooling and filtering to obtain the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution.
Preferably, the molar ratio of the sodium hydrosulfide to the cyanuric chloride is 1.1-1.5: 1, the molar ratio of the sodium sulfide to the cyanuric chloride is 2.2-3.0: 1.
preferably, the concentration of the sodium hydrosulfide aqueous solution is 1-5 mol/L, and the concentration of the sodium sulfide aqueous solution is 1-5 mol/L.
Preferably, the molar ratio of sodium sulfide to sodium hydrosulfide is greater than or equal to 2 and less than 3.
Preferably, during the temperature raising treatment, the pH value of the mixed solution is kept at 10-12, and the temperature is raised to 40-60 ℃.
Preferably, the reaction time is 1-5 hours.
Preferably, the temperature is controlled to be 45-55 ℃ during the reaction, and the reaction time is 2-4 hours.
The invention provides a preparation method of 2, 4, 6-trimercapto-s-triazine and salt thereof, which comprises the following steps:
the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution prepared by the method of the technical scheme is subjected to derivatization and/or crystallization purification treatment to obtain 2, 4, 6-trimercapto-s-triazine and salt thereof.
Preferably, the method specifically comprises the following steps:
adjusting the pH value of the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution prepared by the method in the technical scheme to be more than 12, and cooling to separate out 2, 4, 6-trimercapto-s-triazine trisodium salt crystals; or
Adjusting the pH value of the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution prepared by the method in the technical scheme to 5-7, and precipitating 2, 4, 6-trimercapto-s-triazine monosodium salt crystals; or
The pH value of the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution prepared by the method of the technical scheme is adjusted to be less than 2, and 2, 4, 6-trimercapto-s-triazine crystals are precipitated.
The invention also provides a heavy metal trapping agent which comprises the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution prepared by the method in the technical scheme or the 2, 4, 6-trimercapto-s-triazine and salt thereof prepared by the method in the technical scheme.
Compared with the prior art, the preparation method of the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution comprises the following steps: adding cyanuric chloride and a sodium sulfide aqueous solution into a sodium hydrosulfide aqueous solution, and controlling the speed of adding the cyanuric chloride and the sodium sulfide aqueous solution to obtain a mixed solution with the pH value of 10-12; the temperature of the mixed solution is controlled to be 0-20 ℃; and heating the mixed solution to enable sodium hydrosulfide and sodium sulfide to react with cyanuric chloride, and after the reaction is finished, sequentially cooling and filtering to obtain the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution.
The invention avoids using alkali to control the pH value of a reaction system and furthest inhibits the occurrence of hydrolysis reaction by changing the molar ratio of the sodium hydrosulfide to the sodium sulfide, thereby ensuring the purity and the yield of the 2, 4, 6-trimercapto-s-triazine disodium salt. In addition, in the process of mixing reactants, the temperature in the reaction system is controlled below 20 ℃ by controlling the adding speed of cyanuric chloride, and the pH value of the reaction system is always 10-12 by controlling the adding speed of a sodium sulfide aqueous solution, so that the 2, 4, 6-trimercapto-s-triazine disodium salt is ensured to be in a main existing form, and the generation and precipitation of the 2, 4, 6-trimercapto-s-triazine monosodium salt with low solubility are avoided, thereby further improving the yield of the 2, 4, 6-trimercapto-s-triazine disodium salt. The disodium salt of 2, 4, 6-trimercapto-s-triazine is an intermediate product of 2, 4, 6-trimercapto-s-triazine and trisodium salt thereof. The 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution prepared by the method can be subjected to derivatization and crystallization purification treatment to obtain 2, 4, 6-trimercapto-s-triazine and salt thereof.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention in conjunction with the following examples, but it will be understood that the description is intended to illustrate the features and advantages of the invention further, and not to limit the invention.
The embodiment of the invention discloses a preparation method of a2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution, which comprises the following steps:
adding cyanuric chloride and a sodium sulfide aqueous solution into a sodium hydrosulfide aqueous solution, and controlling the speed of adding the cyanuric chloride and the sodium sulfide aqueous solution to obtain a mixed solution with the pH value of 10-12; the temperature of the mixed solution is controlled to be 0-20 ℃;
and heating the mixed solution to enable sodium hydrosulfide and sodium sulfide to react with cyanuric chloride, and after the reaction is finished, sequentially cooling and filtering to obtain the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution.
TMT-Na39H2O has a pKa1 of 5.71, a pKa2 of 8.36, and a pKa3 of 11.38. In solutions of different pH, TMT-HxNa3-xThe form of presence and solubility of (x ═ 0, 1, 2, or 3) also varied (table-1). As can be seen from Table-1, TMT-HNa is present in all TMT derivatives2Solubility in water is the greatest.
TABLE 1 pH range and solubility of TMT-related derivatives in aqueous solution
Therefore, the invention prepares the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution, and obtains the 2, 4, 6-trimercapto-s-triazine disodium salt with high purity and high yield. The disodium salt of 2, 4, 6-trimercapto-s-triazine may be further converted into 2, 4, 6-trimercapto-s-triazine, 2, 4, 6-trimercapto-s-triazine monosodium salt, or 2, 4, 6-trimercapto-s-triazine trisodium salt.
The following method for preparing the aqueous solution of disodium salt of 2, 4, 6-trimercapto-s-triazine is described in detail according to the specific steps:
the method comprises the following steps: adding cyanuric chloride and a sodium sulfide aqueous solution into a sodium hydrosulfide aqueous solution, and controlling the speed of adding the cyanuric chloride and the sodium sulfide aqueous solution to obtain a mixed solution with the pH value of 10-12; the temperature of the mixed solution is controlled to be 0-20 ℃.
The reactants selected by the invention are sodium sulfide, sodium hydrosulfide and cyanuric chloride.
The concentration of the sodium hydrosulfide aqueous solution is preferably 1-5 mol/L, and more preferably 2-4 mol/L.
The concentration of the sodium hydrosulfide aqueous solution is too low, so that the water amount in a reaction system is increased, the concentration of the 2, 4, 6-trimercapto-s-triazine disodium salt is low, and the inventory volume and the transportation cost are increased; the concentration of the sodium hydrosulfide is too high, so that the subsequent full and uniform mixing with the solid cyanuric chloride is not facilitated.
The temperature of the sodium hydrosulfide aqueous solution is preferably 0-20 ℃, and preferably 5-15 ℃. The sodium hydrosulfide aqueous solution is frozen to be unfavorable for being uniformly mixed with the solid cyanuric chloride at a low temperature, and the cyanuric chloride is hydrolyzed at an accelerated speed at a high temperature, so that the purity and the yield of the product are reduced.
When cyanuric chloride is added to an aqueous sodium hydrosulfide solution, the addition rate is preferably such that a large amount of solids do not remain in the mixed solution and the temperature and pH of the mixed solution rapidly change.
In the addition process of the cyanuric chloride, the pH value of the mixed solution can be controlled within the control range of 10-12 by controlling the addition speed of the sodium sulfide aqueous solution. The pH value of the mixed solution cannot be lower than 10, otherwise, TMT-Na with low solubility can be separated out and wrap unreacted cyanuric chloride; on the other hand, the pH of the mixture cannot be higher than 12, otherwise the hydrolysis of cyanuric chloride is accelerated. The concentration of the sodium sulfide water solution is preferably 1-5 mol/L, and more preferably 2-4 mol/L. Likewise, too low a concentration of aqueous sodium sulfide solution increases the amount of water in the mixture, resulting in a lower concentration of active ingredient in the final product; too high a concentration may not avoid a local pH of the mixture above 12.
In order to control the pH value of the system without alkali, the sodium sulfide and the hydrogen sulfideThe molar ratio of sodium oxide is preferably 2 or more and less than 3. If the molar ratio of the sodium sulfide to the sodium hydrosulfide is less than 2, an additional alkali is required to control the pH of the system to be not lower than 10; on the contrary, the molar ratio of sodium sulfide to sodium hydrosulfide is greater than or equal to 3, and the product is mainly TMT-Na3。
In order to increase the conversion of cyanuric chloride, the ratio of the number of moles of sulfide ions and hydrogensulfate ions to the number of moles of cyanuric chloride is preferably greater than 3 and not greater than 5. More preferably, the molar ratio is not less than 3.2 and not more than 4.0. The ratio of the mole number of the sulfide ions and the sulfhydryl ions to the mole number of the cyanuric chloride is less than or equal to 3, partial cyanuric chloride cannot be sulfhydrylated; if the ratio of the number of moles of sulfide ions and hydrogensulfide ions to the number of moles of cyanuric chloride is greater than 5, a large amount of unreacted sodium hydrogensulfide and sodium sulfide may remain in the reaction system. The content of the sodium sulfide and the sodium hydrosulfide is converted, namely, the molar ratio of the sodium hydrosulfide to the cyanuric chloride is 1.1-1.5: 1, the molar ratio of the sodium sulfide to the cyanuric chloride is 2.2-3.0: 1.
according to the invention, step two: and heating the mixed solution to enable sodium hydrosulfide and sodium sulfide to react with cyanuric chloride, and after the reaction is finished, sequentially cooling and filtering to obtain the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution.
After the reactants cyanuric chloride and the sodium sulfide aqueous solution are completely added, the obtained mixed solution is heated to react the sodium hydrosulfide and the sodium sulfide with the cyanuric chloride.
Preferably, during the temperature raising treatment, the pH value of the mixed solution is kept at 10-12, and the temperature is raised to 40-60 ℃. . During the reaction, the temperature is preferably controlled to be 45-55 ℃, and the reaction time is preferably 1-5 hours, and more preferably 2-4 hours.
The reaction temperature is low or the reaction time is too short, so that the reaction is insufficient; conversely, too high a temperature or too long a time will increase the energy consumption and cost of the synthesis process. After the reaction was complete, the system became a clear solution.
According to the invention, after the reaction is finished, the temperature is reduced and the filtration is carried out in sequence to obtain the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution. And after the reaction is finished, cooling to room temperature.
The pH value of the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution at 25 ℃ meets the condition that the pH value is more than or equal to 10 and less than or equal to 12, and the concentration of 2, 4, 6-trimercapto-s-triazine ring in the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution at the temperature range of-10 to 40 ℃ is more than the saturation concentration of 2, 4, 6-trimercapto-s-triazine trisodium salt at the corresponding temperature.
The experiment proves that in the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution prepared by the method, the content of the 2, 4, 6-trimercapto-s-triazine disodium salt is higher than 13%, the purity is higher than 99%, and the recovery rate is higher than 95%.
The embodiment of the invention discloses a preparation method of 2, 4, 6-trimercapto-s-triazine and salt thereof, which comprises the following steps:
the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution in the technical scheme is subjected to derivatization and/or crystallization purification treatment to obtain 2, 4, 6-trimercapto-s-triazine and salt thereof.
An aqueous solution of disodium salt of 2, 4, 6-trimercapto-s-triazine as an intermediate product may be converted into 2, 4, 6-trimercapto-s-triazine, monosodium salt of 2, 4, 6-trimercapto-s-triazine, or trisodium salt of 2, 4, 6-trimercapto-s-triazine.
According to the invention, the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution in the technical scheme is subjected to derivatization and/or crystallization purification treatment to obtain 2, 4, 6-trimercapto-s-triazine and salt thereof.
Preferably, the method specifically comprises the following steps:
adjusting the pH value of the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution to be more than 12, cooling, preferably to 5-15 ℃, and precipitating 2, 4, 6-trimercapto-s-triazine trisodium salt crystals; or
Adjusting the pH value of the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution in the technical scheme to 5-7, and separating out 2, 4, 6-trimercapto-s-triazine monosodium salt crystals; or
The pH value of the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution is adjusted to be less than 2, and 2, 4, 6-trimercapto-s-triazine crystals are precipitated.
The embodiment of the invention also discloses a heavy metal trapping agent which comprises the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution prepared by the method in the technical scheme or the 2, 4, 6-trimercapto-s-triazine and salt thereof prepared by the method in the technical scheme. The 2, 4, 6-trimercapto-s-triazine and its salt may be 4, 6-trimercapto-s-triazine trisodium salt crystal, 2, 4, 6-trimercapto-s-triazine monosodium salt crystal or 2, 4, 6-trimercapto-s-triazine crystal.
According to the invention, the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution prepared by the method in the technical scheme can be directly used for recovering or removing heavy metal ions.
For further understanding of the present invention, the following examples are provided to illustrate the preparation method and application of the aqueous solution of disodium salt of 2, 4, 6-trimercapto-s-triazine provided by the present invention, and the scope of the present invention is not limited by the following examples.
Example 1
(1) An aqueous sodium sulfide solution was prepared in advance. 1600g (6.5mol) of industrial-grade sodium sulfide nonahydrate (98%) is weighed and dissolved in 1800g of water, stirred, heated to 40-45 ℃ in water bath and slowly dissolved into light grey green slightly turbid liquid for standby, Na2The S concentration is 2.2 mol/L.
(2) Preparing sodium hydrosulfide aqueous solution. 288g (3.6mol) of NaHS (70%) is weighed out and dissolved in 1000g of water, and the mixture is heated in a water bath to 40-45 ℃ while stirring to be dissolved into brown and brown turbid liquid (the NaHS concentration is 3 mol/L).
(3) And pouring the NaHS aqueous solution into a 10L glass reaction kettle, stirring for 200r/min, starting cold water circulation, and cooling to ensure that the temperature of reactants is 12.0 ℃ and the pH value is about 14.0. The slow addition of cyanuric chloride was started. Cyanuric chloride was added in an amount of about 41g (7% total) and the pH was lowered to about 10. Na was initially slowly added dropwise2S aqueous solution, light yellow turbid solution of reaction liquid. The pH of the reaction solution is maintained at about 10.5-11.5, and the temperature is maintained at 15-20 ℃. About 150min of addition of 560g of cyanuric chloride (3mol, average rate of addition 3.5-4 was completed.0 g/min). Na addition completed in about 150min2About 2L of S solution (average dropping speed 13.3 ml/min; Na)2Total of about 3L S solution). With the remaining about 1L Na2And washing the kettle wall with the S water solution, wherein the reaction solution is light yellow green turbid solution.
(4) Heating, keeping the temperature of the reactant at 50-51 ℃, and reacting for 4h at the pH value of 10.2-10.6 to obtain a grey green turbid liquid. Cooling to 35 deg.c and pH 10.7; and (4) carrying out suction filtration, obtaining a yellow clear liquid from the filtrate, and washing a little of the filter residue with 50ml of water, and then discarding the filter residue. TMT-Na in the product solution2The content is about 13%.
(5) Taking the product solution, and quantitatively analyzing the TMT-Na content by HPLC213% of TMT-Na2The recovery of (a) was 96%.
Example 2
(1) An aqueous sodium sulfide solution was prepared in advance. 1600g (6.5mol) of industrial-grade sodium sulfide nonahydrate (98%) is weighed and dissolved in 1800g of water, stirred, heated to 40-45 ℃ in water bath and slowly dissolved into light grey green slightly turbid liquid for standby, Na2The S concentration is 2.2 mol/L.
(2) Preparing sodium hydrosulfide aqueous solution. 616g (7.7mol) of NaHS (70%) is weighed out and dissolved in 1000g of water, and the mixture is heated in a water bath to 40-45 ℃ with stirring to be dissolved into brown and brown turbid liquid (the NaHS concentration is 7.7 mol/L).
(3) And pouring the NaHS aqueous solution into a 10L glass reaction kettle, stirring for 200r/min, starting cold water circulation, and cooling to ensure that the temperature of reactants is 12.0 ℃ and the pH value is about 14.0. The slow addition of cyanuric chloride was started. Cyanuric chloride is added in about 41g (total 7%), the pH is reduced to about 10, and Na is slowly added dropwise2S aqueous solution, light yellow turbid solution of reaction liquid. About 150min, 560g of cyanuric chloride (3mol, average feed rate 3.5-4.0g/min) was added. Na addition completed in about 150min2About 2L of S solution (average dropping speed 13.3 ml/min; Na)2Total of about 3L S solution). With a remaining of about 1LNa2And washing the kettle wall with the S water solution, wherein the reaction solution is light yellow green turbid solution.
(4) Heating, keeping the temperature of the reactant at 55 ℃, and reacting for 4h when the pH value is 8.5-9.0, wherein the reactant is a grey green turbid liquid. Cooling to 25 deg.c and pH 9.2; and (4) carrying out suction filtration, obtaining a yellow clear liquid from the filtrate, and washing a little of the filter residue with 50ml of water, and then discarding the filter residue. The total TMT-Na salt content of the resulting product solution was about 14%.
(5) Taking the product solution, and quantitatively analyzing the TMT-Na content by HPLC28% of TMT-Na, 6% of TMT-Na2The recovery of (a) was 58%.
Example 3
(1) An aqueous sodium sulfide solution was prepared in advance. 1600g (6.5mol) of industrial-grade sodium sulfide nonahydrate (98%) is weighed and dissolved in 1800g of water, stirred, heated to 40-45 ℃ in water bath and slowly dissolved into light grey green slightly turbid liquid for standby, Na2The S concentration is 2.2 mol/L.
(2) Preparing sodium hydrosulfide aqueous solution. 288g (3.6mol) of NaHS (70%) is weighed out and dissolved in 1000g of water, and the mixture is heated in a water bath to 40-45 ℃ while stirring to be dissolved into brown and brown turbid liquid (the NaHS concentration is 3 mol/L).
(3) And pouring the NaHS aqueous solution into a 10L glass reaction kettle, stirring for 200r/min, starting cold water circulation, and cooling to ensure that the temperature of reactants is 12.0 ℃ and the pH value is about 14.0. The slow addition of cyanuric chloride was started. Cyanuric chloride was added in an amount of about 41g (7% total) and the pH was lowered to about 10. Na was initially slowly added dropwise2S aqueous solution, light yellow turbid solution of reaction liquid. The pH of the reaction solution is maintained at about 10.5-11.5, and the temperature is maintained at 10-15 ℃. About 150min, 560g of cyanuric chloride (3mol, average feed rate 3.5-4.0g/min) was added. Na addition completed in about 150min2About 2L of S solution (average dropping speed 13.3 ml/min; Na)2Total of about 3L S solution). With a remaining of about 1LNa2And washing the kettle wall with the S water solution, wherein the reaction solution is light yellow green turbid solution.
(4) Heating, keeping the temperature of the reactant at 80 ℃, and reacting for 4h at the pH value of 10.2-10.6 to obtain yellow clear liquid. Cooling to 25 deg.c and pH 10.5; and (4) carrying out suction filtration, obtaining a yellow clear solution of the filtrate, and washing a little suspended substance 50ml of water in the filter residue and then discarding the filter residue. The total TMT-Na salt content of the resulting product solution was about 13%.
(5) Taking the product solution, and quantitatively analyzing the TMT-Na content by HPLC210% of TMT-Na33% of TMT-Na2The recovery of (D) was 73%.
Example 4
Preparation of a composition containing TMT-Na as in example 12After the aqueous solution, 45% aqueous sodium hydroxide solution was added to adjustThe pH value is 12.5-13.0, then the temperature is reduced to 5 ℃, the pH value is about 13.0, and a large amount of yellow needle-shaped crystals are separated out in the reaction kettle. Keeping the temperature at 5 ℃ for 1h, then carrying out suction filtration, and finally obtaining light yellow solid after being dried for 3-4 h. Drying at 40 ℃ for 16h, and recovering 1990g of the dried product. Determination of TMT-Na in the product by HPLC analysis3The purity of (2) was 99.5%, and the yield was 96%.
Example 5
Preparation of a composition containing TMT-Na as in example 12Slowly dripping concentrated hydrochloric acid after the aqueous solution is dissolved, adjusting the pH by stages, consuming 280-300g of concentrated hydrochloric acid and keeping the pH at 8-9.5; the pH was maintained at 4.5-6 by the continued addition of 300g of concentrated hydrochloric acid. Acidification for 1h consumed 645g of concentrated hydrochloric acid and the pH dropped to 1.89. Suction filtration and rinsing with 2.5L of pure water to obtain yellow solid. Analysis of TMT-H by HPLC3The product purity was 95.3% and the yield was 95.4%.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution comprises the following steps:
adding cyanuric chloride and a sodium sulfide aqueous solution into a sodium hydrosulfide aqueous solution, and controlling the speed of adding the cyanuric chloride and the sodium sulfide aqueous solution to obtain a mixed solution with the pH value of 10-12; the temperature of the mixed solution is controlled to be 0-20 ℃;
and heating the mixed solution to enable sodium hydrosulfide and sodium sulfide to react with cyanuric chloride, and after the reaction is finished, sequentially cooling and filtering to obtain the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution.
2. The preparation method according to claim 1, wherein the molar ratio of the sodium hydrosulfide to the cyanuric chloride is 1.1-1.5: 1, the molar ratio of the sodium sulfide to the cyanuric chloride is 2.2-3.0: 1.
3. the method according to claim 2, wherein the concentration of the aqueous solution of sodium hydrosulfide is 1 to 5mol/L, and the concentration of the aqueous solution of sodium sulfide is 1 to 5 mol/L.
4. The method according to any one of claims 1 to 3, wherein the molar ratio of sodium sulfide to sodium hydrosulfide is 2 or more and less than 3.
5. The method according to claim 1, wherein the pH of the mixed solution is maintained at 10 to 12 during the temperature-raising treatment, and the temperature is raised to 40 to 60 ℃.
6. The method according to claim 1, wherein the reaction time is 1 to 5 hours.
7. The preparation method according to claim 6, wherein the reaction temperature is controlled to 45-55 ℃ and the reaction time is 2-4 hours.
8. A preparation method of 2, 4, 6-trimercapto-s-triazine and salt thereof is characterized by comprising the following steps:
the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution prepared by the method of any one of claims 1 to 7 is subjected to derivatization and/or crystallization purification treatment to obtain 2, 4, 6-trimercapto-s-triazine and salt thereof.
9. The preparation method according to claim 8, comprising the following steps:
adjusting the pH value of the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution prepared by the method of any one of claims 1 to 7 to be more than 12, and cooling to separate out 2, 4, 6-trimercapto-s-triazine trisodium salt crystals; or
Adjusting the pH value of the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution prepared by the method of any one of claims 1 to 7 to 5 to 7, and precipitating 2, 4, 6-trimercapto-s-triazine monosodium salt crystals; or
Adjusting the pH value of the 2, 4, 6-trimercapto-s-triazine disodium salt aqueous solution prepared by the method of any one of claims 1 to 7 to be less than 2, and precipitating 2, 4, 6-trimercapto-s-triazine crystals.
10. A heavy metal trapping agent comprising the aqueous solution of disodium salt of 2, 4, 6-trimercapto-s-triazine prepared by the method according to any one of claims 1 to 8 or the 2, 4, 6-trimercapto-s-triazine and the salt thereof prepared by the method according to claim 9.
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