Preparation method of high-purity tetraammineplatinum nitrate

Abstract

The invention belongs to the technical field of noble metal catalyst preparation, and particularly relates to a preparation method of high-purity tetraammineplatinum nitrate. According to the method, potassium tetranitroplatinate is prepared from chloroplatinic acid and potassium nitrite, then potassium hexanitroplatinate is prepared, and finally platinum nitrate tetraammine is prepared, so that the method uses fewer types of raw materials, does not use expensive reagents, has fewer steps, is simple and convenient to operate, is easy to realize large-scale production, and is suitable for industrial production. The yield of the prepared platinum tetraamminenitrate is greater than or equal to 94.1%, the purity of the platinum tetraamminenitrate is greater than or equal to 99.3%, and the platinum content is greater than or equal to 41.9%.

Description

Technical Field

[0001] The invention belongs to the technical field of precious metal catalyst preparation, and specifically relates to a method for preparing high-purity tetraammine platinum nitrate. Background Art

[0002] Tetraammineplatinum nitrate, also known as tetraammineplatinum nitrate and tetraammineplatinum nitrate, is a white crystal. Tetraammineplatinum nitrate is widely used in the medical field as an important anticancer drug. It can also be used to repair DNA damage, reduce the number of white blood cells and platelets, and thus reduce the side effects of chemotherapy. In addition, due to its excellent catalytic activity and selectivity, it has become an ideal catalyst for many industrial catalytic reactions.

[0003] Currently, the main methods for synthesizing tetraammineplatinum nitrate include direct synthesis, ion exchange and ligand replacement. However, these synthesis methods all have shortcomings. For example, the direct synthesis method uses expensive silver nitrate, the raw materials used in the ion exchange method are relatively complex, and the ligand replacement method requires a series of replacement reactions, which is not easy to operate.

[0004] Therefore, it is necessary to develop a new preparation method that can conveniently and efficiently synthesize high-purity tetraammineplatinum nitrate. Summary of the invention

[0005] The present invention aims to solve the problems existing in the prior art and provides a method for preparing high-purity tetraammine platinum nitrate. The method uses fewer types of raw materials, is low in price, has fewer steps and is easy to operate, and is easy to achieve large-scale production.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions.

[0007] A method for preparing high-purity tetraammine platinum nitrate comprises the following steps:

[0008] Step 1, preparation of potassium tetranitrosoplatinate solution:

[0009] Weigh chloroplatinic acid and add deionized water, stir thoroughly to completely dissolve the chloroplatinic acid solid, then heat and stir, slowly dropwise add saturated potassium nitrite solution during stirring until the solution completely changes from orange-yellow to rose red to obtain potassium tetranitrosoplatinate solution;

[0010] Step 2, preparation of potassium hexanitroplatinate solution:

[0011] Add an oxidant to the potassium tetranitrosoplatinate solution obtained in step 1 and stir evenly, then subject the solution to a high pressure reaction, and after the reaction is completed, take out and cool to obtain a potassium hexanitroplatinate solution;

[0012] Step 3, preparation of tetraammine platinum nitrate:

[0013] The potassium hexanitroplatinate solution obtained in step 2 is passed through a cation exchange resin to react to obtain a hexanitroplatinic acid solution; ammonia water is slowly added dropwise to the obtained hexanitroplatinic acid solution until no precipitate is generated; the obtained precipitate is filtered, washed, and dried to obtain tetraammineplatinum nitrate.

[0014] Furthermore, the step 1 is specifically as follows: weigh 50-100 g of chloroplatinic acid solid and place it in a beaker, add 200 mL-300 mL of deionized water, stir thoroughly to completely dissolve the chloroplatinic acid solid, then transfer the beaker to a magnetic stirrer with a heating function, heat at 70-100 ° C and slowly add potassium nitrite solution under magnetic stirring until the solution completely changes from orange-yellow to rose red to obtain potassium tetranitrosoplatinate solution.

[0015] Furthermore, the step 2 is specifically as follows: adding a certain amount of oxidant to the potassium tetranitrosoplatinate solution obtained in step 1 and stirring evenly, then transferring the solution to a reactor liner with a polytetrafluoroethylene liner, placing it in a stainless steel high-pressure reactor, reacting it in a digital display forced air drying oven at 70-90° C. for 1-2 hours, taking it out after the reaction is completed, cooling it, and pouring out the liquid in the liner to obtain a potassium hexanitroplatinate solution.

[0016] Furthermore, the oxidant is NaClO.

[0017] Furthermore, the molar ratio of platinum to the oxidant in the potassium tetranitrosoplatinate solution is 1:7.

[0018] Furthermore, the step 3 is specifically as follows: the potassium hexanitroplatinate solution obtained in step 2 is passed through a cation exchange resin and reacted for 30-60 minutes to exchange the potassium ions therein with the hydrogen ions in the resin to obtain a hexanitroplatinic acid solution; the obtained hexanitroplatinic acid solution is transferred to a beaker, and ammonia water is slowly added thereto under magnetic stirring until no precipitate is generated; the obtained precipitate is filtered, washed, and dried to obtain tetraammineplatinum nitrate.

[0019] Furthermore, the cation exchange resin is a 732 type cation exchange resin.

[0020] The reaction scheme of the present invention is as follows:

[0021]

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows.

[0023] The present invention uses fewer types of raw materials, does not use expensive reagents, has fewer steps and is easy to operate, and is easy to achieve large-scale production; after testing, the yield, purity and platinum content of tetraammine platinum nitrate of the present invention are as follows:

[0024] The yield of tetraammine platinum nitrate is ≥94.1%, while the yield of the prior art is about 90%;

[0025] The purity of tetraammine platinum nitrate is ≥99.3%, while the existing technology is about 99%;

[0026] The platinum content is ≥41.9%, while the existing technology is about 39%. DETAILED DESCRIPTION

[0027] The technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0028] A method for preparing high-purity tetraammine platinum nitrate comprises the following steps:

[0029] Step 1, preparation of potassium tetranitrosoplatinate solution:

[0030] Weigh 50-100 g of chloroplatinic acid solid and place it in a beaker, add 200 mL-300 mL of deionized water, stir thoroughly to completely dissolve the chloroplatinic acid solid, then transfer the beaker to a magnetic stirrer with a heating function, heat at 70-100 ° C and slowly add potassium nitrite solution under magnetic stirring until the solution completely changes from orange-yellow to rose red to obtain potassium tetranitrosoplatinate solution;

[0031] Step 2, preparation of potassium hexanitroplatinate solution:

[0032] A certain amount of oxidant NaClO is added to the potassium tetranitrosoplatinate solution obtained in step 1 and stirred evenly, and then the solution is transferred to a reactor liner with a polytetrafluoroethylene liner, placed in a stainless steel high-pressure reactor, and reacted at 70-90° C. in a digital display air drying oven for 1-2 hours. After the reaction is completed, the reaction is taken out, cooled, and the liquid in the liner is poured out to obtain a potassium hexanitroplatinate solution;

[0033] Step 3, preparation of tetraammine platinum nitrate:

[0034] The potassium hexanitroplatinate solution obtained in step 2 is passed through a 732 type cation exchange resin and reacted for 30-60 minutes to exchange the potassium ions therein with the hydrogen ions in the resin to obtain a hexanitroplatinic acid solution; the obtained hexanitroplatinic acid solution is transferred to a beaker, and ammonia water is slowly added dropwise thereto under magnetic stirring until no precipitate is generated; the obtained precipitate is filtered, washed, and dried to obtain tetraammineplatinum nitrate.

[0035] Furthermore, the molar ratio of platinum to the oxidant in the potassium tetranitrosoplatinate solution is 1:7.

[0036] Example 1.

[0037] Dissolve 50g of chloroplatinic acid solid in 200mL of deionized water and place it on a magnetic stirrer with heating function, heat at 80℃ and stir for 10min to completely dissolve chloroplatinic acid; keep heating and stirring conditions, slowly add potassium nitrite solution until the solution completely changes from orange-yellow to rose red; transfer the potassium tetranitrosoplatinate solution to a beaker, add a certain amount of NaClO (n(Pt):n(NaClO)=1:7) and stir evenly; transfer the resulting solution to a reactor liner with polytetrafluoroethylene lining, put it into a stainless steel high-pressure reactor; react for 1.5h in a digital display blast drying oven at 80℃, take out after the reaction, cool and pour out the liquid in the liner, and perform cation exchange for 50min through a 732 type cation exchange resin; transfer the resulting hexanitroplatinic acid solution to a beaker, slowly add ammonia water to it under magnetic stirring conditions until no precipitate is generated. The resulting precipitate is tetraammine platinum nitrate after filtering, washing and drying.

[0038] The yield of tetraammineplatinum nitrate in Example 1 is 94.1%, the purity is 99.3%, and the platinum content is 41.9%.

[0039] Comparative example 1.

[0040] Dissolve 50 g of chloroplatinic acid solid in 200 mL of deionized water and place on a magnetic stirrer with heating function, heat at 80 ° C and stir for 10 min to completely dissolve the chloroplatinic acid, keep heating and stirring, slowly add potassium nitrite solution until the solution completely changes from orange to rose red, transfer the potassium tetranitrosoplatinate solution to a beaker, add a certain amount of H (n (Pt): n (oxidant) = 1:7) 2 O 2 、Na 2 O and stir evenly, transfer the resulting solution to a reactor liner with a polytetrafluoroethylene liner, place it in a stainless steel high-pressure reactor, and react at 80°C in a digital display air drying oven for 1.5 hours. After the reaction is completed, take it out, cool it, pour out the liquid in the liner, and perform cation exchange for 50 minutes through a 732 type cation exchange resin. Transfer the resulting hexanitroplatinic acid solution to a beaker, and slowly add ammonia water to it under magnetic stirring until no precipitation is generated. The resulting precipitate is filtered, washed, and dried to obtain tetraammine platinum nitrate.

[0041] Table 1 Analysis and detection results of tetraammine platinum nitrate of comparative example 1

[0042] Oxidants Yield purity Pt content <![CDATA[H 2 THE 2 ]]> 92.9％ 99.1％ 40.9％ <![CDATA[Na 2 The]]> 94.0％ 99.0％ 41.8％

[0043] Comparative example 2.

[0044] Dissolve 50g of chloroplatinic acid solid in 200mL of deionized water and place it on a magnetic stirrer with heating function, heat at 80℃ and stir for 10min to completely dissolve chloroplatinic acid, keep heating and stirring conditions, slowly add potassium nitrite solution until the solution completely changes from orange-yellow to rose red, transfer the potassium tetranitrosoplatinate solution to a beaker, add a certain amount of NaClO, n(Pt):n(NaClO) is 1:6, 1:8 respectively and stir evenly, transfer the resulting solution to the reactor liner with polytetrafluoroethylene lining, put it into a stainless steel high-pressure reactor. React at 80℃ for 1.5h in a digital display blast drying oven. After the reaction is completed, take it out, cool it down, pour out the liquid in the liner, perform cation exchange with 732 type cation exchange resin for 50min, transfer the obtained hexanitroplatinic acid solution to a beaker, slowly add ammonia water to it under magnetic stirring conditions until no precipitation is generated. The obtained precipitate is tetraammine platinum nitrate after filtration, washing and drying.

[0045] Table 2 Analysis and detection results of tetraammine platinum nitrate in comparative example 2

[0046] Oxidant dosage Yield purity Pt content 1：6 93.2％ 98.3％ 40.9％ 1：8 94.2％ 99.0％ 41.1％

[0047] Comparative example 3.

[0048] 50 g of chloroplatinic acid solid was dissolved in 200 mL of deionized water and placed on a magnetic stirrer with a heating function. The mixture was heated at 80° C. and stirred for 10 min to completely dissolve the chloroplatinic acid. The potassium nitrite solution was slowly added dropwise while maintaining the heating and stirring conditions until the solution completely changed from orange-yellow to rose red. The obtained potassium tetranitrosoplatinate solution was transferred to a beaker, and a certain amount of NaClO (n(Pt):n(NaClO)=1:7) was added and stirred evenly. The obtained solution was transferred to a reactor liner with a polytetrafluoroethylene liner and placed in a stainless steel high-pressure reactor. The reaction was carried out in a digital display forced air drying oven at 70°C and 90°C for 1.5 hours respectively. After the reaction was completed, the mixture was taken out and cooled, and the liquid in the inner tank was poured out. The cation exchange was carried out through a 732 type cation exchange resin for 50 minutes. The obtained hexanitroplatinic acid solution was transferred to a beaker. Under the condition of magnetic stirring, ammonia water was slowly added dropwise until no precipitate was generated. The obtained precipitate was filtered, washed and dried to obtain tetraammineplatinum nitrate.

[0049] Table 3 Analysis and detection results of tetraammine platinum nitrate of comparative example 3

[0050] Reaction temperature Yield purity Pt content 70℃ 93.8％ 99.0％ 41.2％ 90℃ 94.0％ 99.3％ 41.8％

[0051] Comparative example 4.

[0052] Dissolve 50g of chloroplatinic acid solid in 200mL of deionized water and place it on a magnetic stirrer with heating function, heat at 80℃ and stir for 10min to completely dissolve chloroplatinic acid, keep heating and stirring conditions, slowly add potassium nitrite solution until the solution completely changes from orange-yellow to rose red, transfer the tetranitrosoplatinic acid potassium solution to a beaker, add a certain amount of NaClO (n(Pt):n(NaClO)=1:7) and stir evenly, transfer the resulting solution to a reactor liner with polytetrafluoroethylene lining, put it into a stainless steel high-pressure reactor, react at 80℃ in a digital display blast drying oven for 1h and 2h respectively, take it out after the reaction is completed, pour out the liquid in the liner after cooling, perform cation exchange for 50min through 732 type cation exchange resin, transfer the resulting hexanitroplatinic acid solution to a beaker, slowly add ammonia water under magnetic stirring conditions until no precipitation is generated. The resulting precipitate is tetraammine platinum nitrate after filtering, washing and drying.

[0053] Table 4 Analysis and detection results of tetraammine platinum nitrate of comparative example 4

[0054] Reaction time Yield purity Pt content 1h 91.7％ 97.2％ 39.8％ 2h 94.2％ 99.0％ 41.7％

[0055] Comparative Example 5.

[0056] Dissolve 50g of chloroplatinic acid solid in 200mL of deionized water and place on a magnetic stirrer with heating function, heat at 80℃ and stir for 10min to completely dissolve chloroplatinic acid, keep heating and stirring conditions, slowly add potassium nitrite solution until the solution completely changes from orange-yellow to rose red, transfer the potassium tetranitrosoplatinate solution to a beaker, add a certain amount of NaClO (n(Pt):n(NaClO)=1:7) and stir evenly, transfer the resulting solution to a reactor liner with polytetrafluoroethylene lining, put it into a stainless steel high-pressure reactor, react at 80℃ in a digital display blast drying oven for 1.5h, take it out after the reaction, pour out the liquid in the liner after cooling, and perform cation exchange for 40min and 60min through 732 type cation exchange resin, transfer the resulting hexanitroplatinic acid solution to a beaker, slowly add ammonia water under magnetic stirring until no precipitation is generated. The resulting precipitate is tetraammine platinum nitrate after filtering, washing and drying.

[0057] Table 5 Analysis and detection results of tetraammine platinum nitrate of comparative example 5

[0058] Cation exchange time Yield purity Pt content 40min 92.8％ 97.6％ 38.3％ 60min 93.9％ 99.2％ 41.7％

Claims

1. A method for preparing high-purity tetraammine platinum nitrate, characterized in that: The following steps are involved: Step 1, preparation of potassium tetranitrosoplatinate solution: Weigh chloroplatinic acid and add deionized water, stir thoroughly to completely dissolve the chloroplatinic acid solid, then heat and stir, slowly dropwise add saturated potassium nitrite solution during stirring until the solution completely changes from orange-yellow to rose red to obtain potassium tetranitrosoplatinate solution; Step 2, preparation of potassium hexanitroplatinate solution: Add an oxidant to the potassium tetranitrosoplatinate solution obtained in step 1 and stir evenly, then subject the solution to a high pressure reaction, and after the reaction is completed, take out and cool to obtain a potassium hexanitroplatinate solution; Step 3, preparation of tetraammine platinum nitrate: The potassium hexanitroplatinate solution obtained in step 2 is passed through a cation exchange resin to react to obtain a hexanitroplatinic acid solution; ammonia water is slowly added dropwise to the obtained hexanitroplatinic acid solution until no precipitate is generated; the obtained precipitate is filtered, washed, and dried to obtain tetraammineplatinum nitrate.

2. The method for preparing high-purity tetraammine platinum nitrate according to claim 1, wherein The step 1 is specifically as follows: weighing 50-100 g of chloroplatinic acid solid and placing it in a beaker, adding 200 mL-300 mL of deionized water, stirring sufficiently to completely dissolve the chloroplatinic acid solid, then transferring the beaker to a magnetic stirrer with a heating function, heating at 70-100° C. and slowly adding a potassium nitrite solution under magnetic stirring until the solution completely changes from orange-yellow to rose red, thereby obtaining a potassium tetranitrosoplatinate solution.

3. The method for preparing high-purity tetraammine platinum nitrate according to claim 1, wherein The step 2 specifically comprises: adding a certain amount of oxidant to the potassium tetranitrosoplatinate solution obtained in step 1 and stirring evenly, then transferring the solution to a reactor liner with a polytetrafluoroethylene lining, placing the solution in a stainless steel high-pressure reactor, reacting the reaction in a digital display forced air drying oven at 70-90° C. for 1-2 hours, taking out the reaction after the reaction is completed, cooling the reaction, and pouring out the liquid in the liner to obtain the potassium hexanitroplatinate solution.

4. The method for preparing high-purity tetraammine platinum nitrate according to claim 1, wherein In step 2, the oxidant is NaClO.

5. The method for preparing high-purity tetraammine platinum nitrate according to claim 1, wherein The molar ratio of platinum to the oxidant in the potassium tetranitrosoplatinate solution is 1:

7.

6. The method for preparing high-purity tetraammine platinum nitrate according to claim 1, characterized in that: The step 3 specifically comprises: passing the potassium hexanitroplatinate solution obtained in step 2 through a cation exchange resin, reacting for 30-60 minutes, so that the potassium ions therein are exchanged with the hydrogen ions in the resin to obtain a hexanitroplatinic acid solution; transferring the obtained hexanitroplatinic acid solution to a beaker, and slowly adding ammonia water thereto under magnetic stirring until no precipitate is generated; and filtering, washing and drying the obtained precipitate to obtain tetraammineplatinum nitrate.

7. The method for preparing high-purity tetraammine platinum nitrate according to claim 1, characterized in that: In step 3, the cation exchange resin is 732 type cation exchange resin.