A method for preparing trichlorohexammineruthenium suitable for industrial production

Abstract

The invention provides a preparation method of ruthenium trichloride hexaamine, which is suitable for industrial production, and relates to the technical field of organic chemical synthesis. The method comprises the following steps: ruthenium trichloride is boiled and concentrated with hydrochloric acid, and then transferred into a reactor and deionized water is added; ammonia water and zinc powder are added into the reactor; a filter residue is washed and filtered, and ammonium chloride is added; under the protection of an inert gas, the solid is washed with an ammonium chloride-ammonia solution and anhydrous ethanol respectively, and then the solid is transferred to the reactor; deionized water is added to adjust the concentration of ruthenium ions; silver chloride is added to filter and wash the filter residue; a liquid is extracted and concentrated under reduced pressure until a large number of monocyclic crystals appear; hydrochloric acid is added and the crystals are filtered; the filtrate is continuously concentrated and the operation is repeated until no crystal appears to obtain ruthenium trichloride hexaamine. The preparation method is simplified, and practical operation is convenient, and multiple material transfer is not required. The reaction condition control precision is low, the process is mature, and the operation is simple. The method is suitable for factory-scale production, and the yield of ruthenium trichloride hexaamine is maintained at more than 93% in actual production.

Description

Technical Field

[0001] The invention relates to the technical field of organic chemical synthesis, in particular to a method for preparing trichlorohexammineruthenium suitable for industrial production. Background Art

[0002] Ruthenium is a relatively cheap and abundant precious metal among the platinum group metals. Ruthenium has excellent catalytic and electrochemical properties, making it widely used in the field of electrochemical biosensors and organic preparation. Trichlorohexammineruthenium can be used as an electron transfer mediator in electrochemical biosensors due to its low redox potential and stable storage performance. It is increasingly used in blood sugar detection, enzyme content determination and certain genetic disease detection.

[0003] According to the patent number CN109574097A, the preparation method of trichlorohexaamineruthenium is as follows: 1. dissolving chlororuthenic acid in concentrated ammonia water; 2. adding a catalyst to the solution, heating to 50-100°C under the protection of an inert gas, so that the catalyst is evenly dispersed; 3. slowly dripping an oxidant at 30-50°C until the solution is colorless; 4. filtering and removing the catalyst, cooling and crystallizing at room temperature or low temperature, washing and drying the crystals to obtain white or light yellow solid trichlorohexaamineruthenium. The preparation method of the present invention is simple to operate, low in cost and time, the product is precipitated in the form of crystals, and no other salts are added during the preparation process, so the purity is high. The ruthenium complex prepared by the method of the present invention is widely used in fields requiring high-purity products, including electrochemical biosensors, and as a precursor of high-purity metallocene compounds.

[0004] The above patent introduces the preparation method of trichlorohexammineruthenium. Both the above patent and the existing preparation method of trichlorohexammineruthenium are cumbersome in actual operation, involve multiple material transfers, and require high control of reaction conditions, and are not suitable for industrial production. Summary of the invention

[0005] Technical issues solved

[0006] In view of the deficiencies in the prior art, the present invention provides a method for preparing ruthenium trichloride hexaamine, which is suitable for industrial production. After ruthenium trichloride is activated in hydrochloric acid, ammonia water and zinc powder are added to react for a period of time, ammonium chloride is added to obtain dichlorohexaamineruthenium, and then silver chloride is added to react to obtain trichlorohexaamineruthenium. The method solves the problems of simplification of the preparation method, convenience in practical operation, no need for multiple material transfers, low precision in reaction condition control, mature technology, simple operation, and suitability for factory-scale production. In actual production, the yield of trichlorohexaamineruthenium is maintained at more than 93%.

[0007] Technical Solution

[0008] To achieve the above purpose, the present invention is implemented by the following technical scheme to provide a method for preparing trichlorohexammineruthenium suitable for industrial production, comprising ruthenium trichloride. The preparation method of trichlorohexammineruthenium is as follows:

[0009] Sp1: Mix ruthenium trichloride and hydrochloric acid and boil, transfer to the reactor and adjust the concentration to 25g / L;

[0010] Sp2: Add ammonia water to the reactor to adjust the pH value;

[0011] Sp3: Heat the inside of the reactor until the temperature reaches 80°C and then add zinc powder;

[0012] Sp4: washing the filter residue and filtering it, adding the washing liquid and the filtrate together to the reactor, and adding ammonium chloride;

[0013] Sp5: washed with ammonium chloride-ammonia solution and anhydrous ethanol respectively under inert gas protection;

[0014] Sp6: Transfer the solid to a reactor under the protection of an inert gas and add deionized water to adjust the ruthenium ion concentration;

[0015] Sp7: Add silver chloride to the reactor and stir evenly and wait for the reaction time;

[0016] Sp8: filtering the washed residue and combining the washing liquid and the filtrate;

[0017] Sp9: extract the liquid and concentrate it under reduced pressure until a large number of monocyclic crystals appear, add hydrochloric acid and filter the crystals;

[0018] Sp10: The filtrate is concentrated and the operation is repeated until no crystals appear to obtain trichlorohexammineruthenium.

[0019] Preferably, the ruthenium trichloride is added to the hydrochloric acid and boiled for 1 hour, and is boiled and concentrated to a syrup before being transferred into the reactor, and the solution for adjusting the ruthenium ion concentration is deionized water, and the concentration of hydrochloric acid is 12 molar, the concentration of the ammonia solution is 25%-28%, and the pH is adjusted to 9, the temperature is raised to 80°C and the zinc powder is added for 30 minutes, and the amount of zinc powder added is calculated as 0.8 times the mass of ruthenium trichloride.

[0020] Preferably, the solution for filtering the washing residue is dilute ammonia water, and the dilute ammonia water is obtained by a volume ratio of water: ammonia water = 1:1, the number of times the ammonium chloride-ammonia solution is used to wash the residue under the protection of inert gas is 4-5 times, and the number of times the anhydrous ethanol is washed is 3 times, and the ruthenium ion concentration is adjusted to 10g / L by dissolving deionized water, the amount of silver chloride added is 1.1 times the molar amount of dichlorohexaammineruthenium, and the stirring reaction time is 1h in total, and the solution for filtering and washing the residue is deionized water.

[0021] Preferably, the liquid is extracted into a rotary evaporator, and the temperature of reduced pressure concentration is 80°C until a large amount of light yellow crystals appear, and hydrochloric acid is added to precipitate more crystals. After filtering the crystals, ethanol is used to neutralize the pH, and vacuum drying is performed at 60°C. The filtrate is further concentrated until no crystals appear.

[0022] Beneficial Effects

[0023] The present invention provides a method for preparing trichlorohexammineruthenium suitable for industrial production, which has the following beneficial effects:

[0024] The invention activates ruthenium trichloride in hydrochloric acid, boils and concentrates it into a syrupy state, adds deionized water to adjust the concentration, adds ammonia water and zinc powder to react for a period of time, adds ammonium chloride to obtain dichlorohexaammineruthenium, and then adds silver chloride to react, filters and concentrates to obtain trichlorohexaammineruthenium. The preparation method is simplified, convenient for actual operation, does not need to transfer materials many times, has low control precision of reaction conditions, is mature in process, is easy to operate, is suitable for factory-scale production, and the yield of trichlorohexaammineruthenium is maintained at more than 93% in actual production. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 It is a schematic diagram of the process of the present invention. DETAILED DESCRIPTION

[0026] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. 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.

[0027] Embodiment 1:

[0028] like Figure 1 As shown, the embodiment of the present invention provides a preparation method of trichlorohexaamineruthenium suitable for industrial production, comprising ruthenium trichloride. The preparation method of trichlorohexaamineruthenium is as follows:

[0029] Sp1: Mix ruthenium trichloride and hydrochloric acid and boil, transfer to the reactor and adjust the concentration to 25g / L;

[0030] Sp2: Add ammonia water to the reactor to adjust the pH value;

[0031] Sp3: Heat the inside of the reactor until the temperature reaches 80°C and then add zinc powder;

[0032] Sp4: washing the filter residue and filtering it, adding the washing liquid and the filtrate together to the reactor, and adding ammonium chloride;

[0033] Sp5: washed with ammonium chloride-ammonia solution and anhydrous ethanol respectively under inert gas protection;

[0034] Sp6: Transfer the solid to a reactor under the protection of an inert gas and add deionized water to adjust the ruthenium ion concentration;

[0035] Sp7: Add silver chloride to the reactor and stir evenly and wait for the reaction time;

[0036] Sp8: filtering the washed residue and combining the washing liquid and the filtrate;

[0037] Sp9: extract the liquid and concentrate it under reduced pressure until a large number of monocyclic crystals appear, add hydrochloric acid and filter the crystals;

[0038] Sp10: The filtrate is concentrated and the operation is repeated until no crystals appear to obtain trichlorohexammineruthenium.

[0039] Embodiment 2:

[0040] like Figure 1 As shown, the embodiment of the present invention provides a preparation method of trichlorohexammineruthenium suitable for industrial production, wherein 1000 grams of ruthenium trichloride (ruthenium content is 37.5%) is added to hydrochloric acid and boiled for 1 hour, and the solution is boiled and concentrated to a syrupy state and then transferred to a reactor, and the solution for adjusting the ruthenium ion concentration is deionized water, and the concentration of hydrochloric acid is 12 moles, the concentration of the ammonia solution is 25%-28%, and 25%-28% ammonia water is added to the reactor for adjustment, and the pH is adjusted to 9, the temperature is increased to 80°C, 300 grams of zinc powder is added, and the reaction time is 30 minutes, and the amount of zinc powder added is calculated as 0.8 times the mass of ruthenium trichloride, the solution filtered by the washing filter residue is dilute ammonia water, and the dilute ammonia water is obtained by water: ammonia water volume ratio = 1:1, and ammonium chloride is added to the reactor. The method comprises the following steps: the first step is to wash the filter residue with a 5% ammonium chloride-ammonia solution for 4-5 times under the protection of an inert gas, and the second step is to wash the filter residue with an anhydrous ethanol solution for 3 times, and the concentration of ruthenium ions is adjusted to 10 g / L by dissolving in deionized water, the amount of silver chloride added is 1.1 times the molar amount of dichlorohexaammineruthenium, and the stirring reaction time is 1 h. The solution for filtering and washing the filter residue is deionized water, the liquid is extracted into a rotary evaporator, and the temperature of the reduced pressure concentration is 80°C until a large number of light yellow crystals appear, and the concentration is stopped. Hydrochloric acid is added to precipitate more crystals. After filtering the crystals, the pH is neutralized with ethanol, and vacuum drying is performed at 60°C. The filtrate is further concentrated until no crystals appear. After measurement, 1076.22 g of trichlorohexaammineruthenium is obtained, with a yield of 93.56%.

[0041] Embodiment three:

[0042] The present invention provides a method for preparing trichlorohexammineruthenium suitable for industrial production. Sp1: Take 1000 g of ruthenium trichloride (ruthenium content 37.5%), dissolve it in 20% hydrochloric acid and boil it.

[0043] 1 hour;

[0044] Sp2: Filter the boiled solution, collect the filtrate and concentrate it to a syrup under reduced pressure;

[0045] Sp3: Transfer the concentrated syrupy ruthenium solution into the reactor and adjust the Ru3+ concentration to 20g / L;

[0046] Sp4: Add pure ammonia gas into the ruthenium solution with adjusted concentration to raise the pH value of the solution to 9;

[0047] Sp5: Add 300 g of zinc powder under stirring, react for 30 minutes, filter quickly, and rinse with 20% ammonia solution 5 times;

[0048] Sp6: Collect the filtrate, add ammonium chloride under the protection of inert gas to precipitate yellow crystals, filter the yellow crystals, and rinse the yellow crystals with 5% ammonium chloride aqueous solution for 5 times, and then rinse with ethanol for 3 times;

[0049] Sp7: Transfer the yellow crystals to a reactor under the protection of inert gas and add pure water to dissolve.

[0050] The ruthenium ion concentration was adjusted to 15 g / L;

[0051] Sp8: Add 1.1 times the molar amount of freshly prepared silver chloride solid according to the ruthenium content, start stirring to allow the silver chloride and the solution to fully contact, react for 1 hour, filter the reaction, rinse the insoluble matter with pure water 5 times, collect the filtrate and concentrate under reduced pressure;

[0052] Sp9: Concentrate until a light yellow crystal film forms on the surface of the solution, cool to room temperature, add 35%-37% hydrochloric acid, then a large amount of light yellow crystals will form, filter out the crystals, rinse with ethanol until neutral, and dry in a vacuum at 60°C;

[0053] Sp10: Repeat the above concentration operation until no light yellow crystals are produced;

[0054] 1085.08 g of trichlorohexammineruthenium was obtained, with a yield of 94.33%.

[0055] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the statement "comprising a reference structure" do not exclude the existence of other identical elements in the process, method, article or device including the elements.

[0056] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing hexaammineruthenium trichloride suitable for industrial production, characterized in that: The preparation method of the trichlorohexammineruthenium is as follows: Sp1: Mix ruthenium trichloride and hydrochloric acid and boil for 1 hour. Boil and concentrate to syrupy state and then transfer to the reactor. Adjust the concentration of ruthenium ions to 25g / L. The solution for adjusting the concentration of ruthenium ions is deionized water. Sp2: Add ammonia water into the reactor and adjust the pH value to 9, wherein the mass fraction of the ammonia water solution is 25%-28%; Sp3: Heat the inside of the reactor until the temperature rises to 80°C and then add zinc powder. The reaction time is 30 minutes. The amount of zinc powder added is calculated as 0.8 times the mass of ruthenium trichloride. Sp4: Filter the washed residue, combine the washing liquid and the filtrate into the reactor, and add ammonium chloride; Sp5: washed with ammonium chloride-ammonia solution and anhydrous ethanol respectively under inert gas protection; Sp6: Transfer the solid to a reactor under the protection of an inert gas and add deionized water to adjust the ruthenium ion concentration; Sp7: Add silver chloride to the reactor and stir evenly and wait for the reaction time; Sp8: filtering the washed residue and combining the washing liquid and the filtrate; Sp9: extract the liquid and concentrate it under reduced pressure until a large number of monocyclic crystals appear, add hydrochloric acid and filter the crystals; Sp10: The filtrate is concentrated and the operation is repeated until no crystals appear to obtain trichlorohexammineruthenium.

2. A method for preparing hexaammineruthenium trichloride suitable for industrial production according to claim 1, characterized in that: The solution for washing the filter residue is dilute ammonia water, and the dilute ammonia water is obtained by a volume ratio of water: ammonia water = 1:

1. The number of times the filter residue is washed with ammonium chloride-ammonia solution under the protection of inert gas is 4-5 times, and the number of times it is washed with anhydrous ethanol is 3 times, and the concentration of ruthenium ions is adjusted to 10g / L by dissolving deionized water. The amount of silver chloride added is 1.1 times the molar amount of dichlorohexaammineruthenium, and the stirring reaction time is 1h in total. The solution for filtering and washing the filter residue is deionized water.

3. The method for preparing hexaammineruthenium trichloride suitable for industrial production according to claim 1, characterized in that: The liquid was extracted into a rotary evaporator and concentrated under reduced pressure at 80°C until a large amount of light yellow crystals appeared. Hydrochloric acid was added to precipitate more crystals. After filtering the crystals, the pH was rinsed with ethanol until it was neutral, and vacuum dried at 60°C. The filtrate was further concentrated until no crystals appeared.

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