Method for preparing chlorogermanic acid and synthesizing organic germanium Ge-132 by pressurizing and strengthening germanium dioxide chloride

Abstract

The invention relates to a method for preparing chlorogermanic acid and synthesizing organic germanium Ge-132 by pressurizing and strengthening germanium dioxide chloride, and belongs to the technical field of chemical engineering. The method comprises the following steps: 1, adding GeO2, glucose and concentrated hydrochloric acid into an autoclave, carrying out a chlorination reaction, and filtering to obtain a filtrate I; 2, adding ammonia water into the filtrate I to react, and filtering to obtain a precipitate I; 3, adding concentrated HCl into the precipitate I, and reacting to obtain a solution I; 4, adding acrylic acid into the solution I to react, and filtering to obtain a precipitate II; step 5, adding deionized water into the precipitate II to react, and filtering to obtain a precipitate III; and step 6, washing and drying the precipitate III to obtain the Ge-132. According to the method, the problems of volatilization, leakage, loss and environmental pollution of hydrochloric acid are avoided, the germanium dioxide reaction is complete, the problem that GeCl4 is easy to volatilize and easy to decompose when meeting water when the GeCl4 is used as a raw material in the prior art is effectively avoided, the operation is simpler and more convenient, the control is easier, and the yield and purity of Ge-132 are higher.

Description

Technical Field

[0001] The invention relates to a method for preparing chlorogermanic acid and synthesizing organic germanium Ge-132 by pressurizing and strengthening germanium dioxide chloride, and belongs to the technical field of chemical industry. Background Art

[0002] β-Carboxyethyl germanium sesquioxide (Ge-132) is one of the organic germanium varieties with extremely low toxicity, strong anti-cancer, immune function enhancement, prevention and treatment of various diseases and fitness effects, and has broad market application prospects.

[0003] The synthesis of Ge-132 is usually divided according to the germanium raw materials. The raw materials are generally divided into three types: Ge, GeCl4 and GeO2. But in essence, all of them are to convert germanium into chlorogermanic acid (HGeCl3) first.

[0004] 1. Using metal Ge as raw material, Ge reacts with HCl gas at 450-500℃, and the reaction product is a mixture of HGeCl3 and GeCl4. The reaction equipment in this process has extremely high requirements for corrosion resistance, safety and operation, and is difficult to control. In addition, GeCl4 is very unstable and easily decomposes into GeO2 when it comes into contact with water, resulting in the synthesized Ge-132 containing inorganic germanium, which will cause germanium poisoning to those who consume Ge-132.

[0005] 2. Using GeCl4 as raw material, such as the patent: "An organic germanium sesquioxide Ge-132 and its preparation method and application" (application number: CN201910845553.X). In addition to the serious problem that GeCl4 will easily generate inorganic germanium, leading to germanium poisoning in Ge-132 consumers, this method is also difficult to operate because GeCl4 has a low boiling point (84°C) and is easily volatile during the synthesis of Ge-132, which will cause germanium loss and environmental pollution.

[0006] 3. With GeO2 as raw material, the existing method is to prepare HGeCl3 by reacting GeO2, NaH2PO2 and concentrated HCl under normal pressure. There are disadvantages such as volatilization and leakage of concentrated hydrochloric acid, loss, environmental pollution, incomplete reaction of germanium dioxide, resulting in loss of germanium and low yield of Ge-132, introduction of Na and P impurities, and long reaction time. In the process of preparing HGeCl3, it is inevitable that GeO2 reacts with concentrated HCl to form GeCl4. Even if GeCl4 can be reduced to HGeCl3, it is very difficult to ensure that GeCl4 is 100% reduced. Therefore, the finally prepared Ge-132 also contains inorganic germanium. In addition, if the prepared HGeCl3 is extracted with an organic solvent, acrylic acid is added dropwise to the extract, the organic flux is evaporated after the reaction, and the remaining product is hydrolyzed with water to obtain Ge-132, the organic solvent used for extraction is flammable and volatile, which pollutes the air, and the extraction and evaporation processes are complicated and the synthesis efficiency is low.

[0007] In view of the defects of the above-mentioned preparation methods, it is urgent to invent a synthesis method with simple operation and control, environmentally friendly process, no inorganic germanium and impurities such as Na and P remaining in Ge-132, and high yield and purity of Ge-132. Summary of the invention

[0008] In order to solve or partially solve the problems existing in the related art, the present application provides a method for preparing chlorogermanic acid and synthesizing organic germanium Ge-132 by pressurized intensified germanium dioxide chloride. The method is simple to operate and control, and the process is environmentally friendly. Ge-132 does not contain inorganic germanium and impurities such as Na and P. At the same time, the yield and purity of the obtained Ge-132 are both high.

[0009] To achieve its purpose, the technical solution adopted by the present invention is:

[0010] A method for preparing chlorogermanic acid and synthesizing organic germanium Ge-132 by pressurized intensified chlorinated germanium dioxide, comprising the following steps:

[0011] Step 1, adding GeO2, glucose and concentrated hydrochloric acid into a pressure autoclave for chlorination reaction and then filtering to obtain filtrate I;

[0012] The specific reaction is: 12GeO2+36HCl+C6H 12 O6→12GeHCl3+6CO2+18H2O

[0013] Step 2, adding ammonia water to the filtrate I, reacting and filtering to obtain precipitate I;

[0014] The specific reaction is: 3NH3+2H2O+GeHCl3→Ge(OH)2↓+3NH4Cl

[0015] Step 3, adding concentrated HCl to the precipitate I to obtain a solution I after reaction;

[0016] The specific reaction is: Ge(OH)2+2HCl→GeHCl3+2H2O

[0017] Step 4, adding acrylic acid to solution I, reacting and filtering to obtain precipitate II;

[0018] The specific reaction is: GeHCl3+CH2CHCOOH→Cl3GeCH2CH2COOH

[0019] Step 5, adding deionized water to the precipitate II and filtering to obtain the precipitate III;

[0020] The specific reaction is: 2Cl3GeCH2CH2COOH+3H2O→(GeCH2CH2COOH)2O3↓+6HCl

[0021] Step 6: Wash and dry the precipitate III to obtain Ge-132.

[0022] Furthermore, in step 1, impurities such as Na and P are not introduced, and glucose is used as the reducing agent. The specific process is: temperature 50-75°C, pressure 0.1-0.5MPa, time 1-3h, stirring speed 200-800rpm, and the filtrate I obtained after cooling and filtration has HGeCl3 as the main component.

[0023] Furthermore, in step 2, ammonia water is added to the filtrate I obtained in step 1 to react and generate Ge(OH)2. The specific process is: the amount of ammonia water added is 1.5-3 times the amount of GeO2 in step 1, the temperature is 20-40°C, the time is 2-4h, and the stirring speed is 200-500rpm.

[0024] Furthermore, in step 3, concentrated HCl is added to the precipitate I obtained in step 2 to react and obtain a purified HGeCl3 solution I. The specific process is: the amount of hydrochloric acid added is 1-2 times the amount of GeO2 in step 1, the temperature is 65-74°C, the time is 1-4h, and the stirring speed is 200-500rpm.

[0025] Furthermore, in step 4, acrylic acid is added to solution I obtained in step 3. The specific reaction process is: the amount of acrylic acid added is 0.7-2 times the amount of GeO2 in step 1, the reaction temperature is 0-50°C, the time is 2-6h, the stirring speed is 200-600rpm, and the precipitate II obtained after filtration is Cl3GeCH2CH2COOH.

[0026] Furthermore, in step 5, deionized water is added to the precipitate II obtained in step 4, and the specific reaction process is: liquid-solid ratio 8-20 ml / g, temperature 0-50° C., time 1-2 h, and stirring speed 200-500 rpm.

[0027] Furthermore, in step 6, the precipitate III obtained in step 5 is washed, and the specific process is: ultrasonic dispersion washing, the detergent is one or two of food-grade ethanol aqueous solution and food-grade acetone aqueous solution in a volume ratio of 1:1-1:5, and the washing times are 3-5 times. By using ultrasonic dispersion washing, the washing is thorough and efficient.

[0028] Furthermore, in step 6, the precipitate III obtained in step 5 is dried, and the specific process is: drying with microwave energy at a temperature of 80-110° C. for 4-6 hours. (1) Drying with microwave energy has a short drying time and high production efficiency.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] (1) The present invention uses GeO2, glucose and concentrated hydrochloric acid to perform pressurized enhanced chlorination and glucose reduction in a pressure autoclave to prepare HGeCl3. There is no problem of hydrochloric acid volatilization, leakage, loss, and environmental pollution. The germanium dioxide reaction is complete, which effectively avoids the problem of GeCl4 being easy to volatilize and decompose when it comes into contact with water when GeCl4 is used as a raw material in the prior art. Therefore, the operation is simpler and easier to control.

[0031] (2) The present invention uses glucose as a reducing agent, and does not introduce impurities such as Na and P. It is safe and non-toxic and beneficial to human health.

[0032] (3) The present invention performs ammonia precipitation and hydrochloric acid re-dissolution purification on HGeCl3 prepared by pressurized enhanced chlorination and glucose reduction, and the average yield of Ge-132 obtained is 89.3%, and the average purity is above 99.9%. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] The above and other objects, features and advantages of the present application will become more apparent through a more detailed description of exemplary embodiments of the present application in conjunction with the accompanying drawings, wherein the same reference numerals generally represent the same components in the exemplary embodiments of the present application.

[0034] Figure 1 is the IR spectrum of the finished product Ge-132 obtained in Example 1 of the present application;

[0035] Figure 2 This is the NMR spectrum of the finished product Ge-132 obtained in Example 1 of the present application. DETAILED DESCRIPTION

[0036] The embodiments of the present application will be described in more detail below with reference to examples. Although the embodiments of the present application are shown in the examples, it should be understood that the present application can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided to make the present application more thorough and complete, and the scope of the present application can be fully communicated to those skilled in the art.

[0037] Example 1

[0038] The method for preparing chlorogermanic acid and synthesizing organic germanium by pressurized intensified chlorinated germanium dioxide mainly comprises the following steps:

[0039] Step 1: Take 10g GeO2, 26g glucose and 120ml concentrated hydrochloric acid and add them into an autoclave for chlorination reaction. The reaction temperature is 75℃, the pressure is 0.5MPa, the time is 1h, the stirring speed is 200rpm, and the filtrate I obtained after cooling and filtration has HGeCl3 as the main component.

[0040] Step 2: Add 1.5 times the amount of ammonia water as much as the amount of GeO2 in step 1 to the filtrate I obtained in step 1, with a reaction temperature of 40°C, a time of 2h, a stirring speed of 500rpm, and obtain Ge(OH)2 precipitate after filtration.

[0041] Step 3: Add hydrochloric acid in an amount equal to the amount of GeO2 in step 1 to the precipitate I obtained in step 2, with the reaction temperature at 74°C, the reaction time at 1h, and the stirring speed at 200rpm to obtain a purified HGeCl3 solution I.

[0042] Step 4: Add 0.7 times the amount of acrylic acid as GeO2 in step 1 to solution I obtained in step 3, with a reaction temperature of 50°C, a reaction time of 2h, a stirring speed of 200rpm, and filter to obtain precipitate II of Cl3GeCH2CH2COOH.

[0043] Step 5: Add deionized water to the precipitate II obtained in step 4 at a liquid-solid ratio of 20 ml / g, react at a temperature of 50°C, for 1 h, with a stirring speed of 200 rpm, and filter to obtain precipitate III, i.e., Ge-132.

[0044] Step 6. Wash the precipitate III obtained in step 5 by adding a food-grade ethanol aqueous solution with a volume ratio of 1:1, and wash it by ultrasonic dispersion for 3 times. After filtering, dry it with microwave energy at a temperature of 80° C. for 6 hours.

[0045] According to statistics, the yield of the finished product Ge-132 is >89.5%. The finished product Ge-132 was sent to Shanghai Microspectral Testing Technology Group Co., Ltd. for testing. The C, H, O, Ge and impurity elements arsenic, lead and cadmium were analyzed. Combined with the standard, the results showed that its purity was 99.95%. At the same time, the IR spectrum and NMR spectrum of the finished product obtained in Example 1 are as follows: Figure 1 and Figure 2 As shown. Fourier transform infrared spectrometer was used to measure 2800-3300, 1690, 1410, 1240cm -1 There are characteristic peaks of -COOH group at 900 and 800 cm -1 The above purity determination results and IR spectrum and NMR spectrum can show that the finished product in Example 1 is indeed Ge-132.

[0046] Example 2

[0047] Step 1: Take 10g GeO2, 35g glucose and 100ml concentrated hydrochloric acid and add them into an autoclave for chlorination reaction. The reaction temperature is 50℃, the pressure is 0.1MPa, the time is 3h, the stirring speed is 800rpm, and the filtrate I obtained after cooling and filtration has HGeCl3 as the main component.

[0048] Step 2: Add 3 times the amount of ammonia water as much as the amount of GeO2 in step 1 to the filtrate I obtained in step 1, with the reaction temperature at 20°C, the time at 4h, and the stirring speed at 200rpm. After filtering, obtain Ge(OH)2 precipitate.

[0049] Step 3: Add hydrochloric acid in an amount twice the amount of GeO2 in step 1 to the precipitate I obtained in step 2, with a reaction temperature of 65°C, a time of 4 hours, and a stirring speed of 500 rpm to obtain a purified HGeCl3 solution I.

[0050] Step 4: Add twice the amount of acrylic acid as the amount of GeO2 in step 1 to solution I obtained in step 3, with the reaction temperature at 0°C, the time at 6h, and the stirring speed at 600rpm. After filtering, the precipitate II is Cl3GeCH2CH2COOH.

[0051] Step 5: Add deionized water to the precipitate II obtained in step 4 at a liquid-solid ratio of 8 ml / g, react at 0°C for 2 h, and stir at 500 rpm. After filtering, obtain precipitate III, i.e., Ge-132.

[0052] Step 6: Wash the precipitate III obtained in step 5 by adding a food-grade acetone aqueous solution with a volume ratio of 1:5, and wash it with ultrasonic dispersion for 5 times. After filtering, dry it with microwave energy at a temperature of 110° C. for 4 hours.

[0053] According to statistics and testing, the yield of the finished product Ge-132 is >88.3% and the purity is 99.92%.

[0054] Example 3

[0055] Step 1: Take 10g GeO2, 50g glucose and 80ml concentrated hydrochloric acid and add them into a pressure autoclave for chlorination reaction. The reaction temperature is 65℃, the pressure is 0.3MPa, the time is 2h, the stirring speed is 500rpm, and the filtrate I obtained after cooling and filtration has HGeCl3 as the main component.

[0056] Step 2: Add twice the amount of ammonia water as much as the amount of GeO2 in step 1 to the filtrate I obtained in step 1, with a reaction temperature of 30°C, a time of 3h, a stirring speed of 400rpm, and obtain Ge(OH)2 precipitate after filtration.

[0057] Step 3: Add 1.5 times the amount of hydrochloric acid as the amount of GeO2 in step 1 to the precipitate I obtained in step 2, with the reaction temperature at 70°C, the time at 3h, and the stirring speed at 400rpm to obtain a purified HGeCl3 solution I.

[0058] Step 4: Add 1.5 times the amount of acrylic acid as GeO2 in step 1 to solution I obtained in step 3, with a reaction temperature of 25°C, a time of 4 hours, a stirring speed of 300 rpm, and filter to obtain precipitate II of Cl3GeCH2CH2COOH.

[0059] Step 5: Add deionized water to the precipitate II obtained in step 4 at a liquid-to-solid ratio of 12 ml / g, react at a temperature of 20°C, for 2 hours, with a stirring speed of 400 rpm, and filter to obtain precipitate III, i.e., Ge-132.

[0060] Step 6: Wash the precipitate III obtained in step 5 by adding a food-grade acetone aqueous solution with a volume ratio of 1:3, and wash it by ultrasonic dispersion for 4 times. After filtering, dry it with microwave energy at a temperature of 100° C. for 5 hours.

[0061] According to statistics and testing, the yield of the finished product Ge-132 is 90.1% and the purity is 99.96%.

[0062] The embodiments of the present application have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The selection of terms used herein is intended to best explain the principles of the embodiments, practical applications, or improvements to the technology in the market, or to enable other persons of ordinary skill in the art to understand the embodiments disclosed herein.

Claims

1. A method for preparing chlorogermanic acid and synthesizing organic germanium Ge-132 by pressurized strengthening of germanium dioxide chloride, characterized in that: The following steps are involved: Step 1, adding GeO2, glucose and concentrated hydrochloric acid into a pressure autoclave for chlorination reaction and then filtering to obtain filtrate I; Step 2, adding ammonia water to the filtrate I, reacting and filtering to obtain precipitate I; Step 3, adding concentrated HCl to the precipitate I to obtain a solution I after reaction; Step 4, adding acrylic acid to solution I, reacting and filtering to obtain precipitate II; Step 5, adding deionized water to the precipitate II and filtering to obtain the precipitate III; Step 6: Wash and dry the precipitate III to obtain organic germanium Ge-132.

2. The method for preparing chlorogermanic acid and synthesizing organic germanium Ge-132 by pressurized strengthening of germanium dioxide chloride according to claim 1, characterized in that: The specific process of step 1 is: temperature 50-75°C, pressure 0.1-0.5MPa, time 1-3h, stirring speed 200-800rpm, and the main component of the filtrate I obtained after cooling and filtration is HGeCl3.

3. The method for preparing chlorogermanic acid and synthesizing organic germanium Ge-132 by pressurized strengthening of germanium dioxide chloride according to claim 1, characterized in that: The amount of ammonia water added is 1.5-3 times the amount of GeO2 in step 1, the temperature is 20-40°C, the time is 2-4h, the stirring speed is 200-500rpm, and the precipitate I obtained after filtration is Ge(OH)2.

4. The method for preparing chlorogermanic acid and synthesizing organic germanium Ge-132 by pressurized strengthening of germanium dioxide chloride according to claim 1, characterized in that: The specific process of step 3 is: the amount of concentrated HCl added is 1-2 times the amount of GeO2 in step 1, the temperature is 65-74°C, the time is 1-4h, the stirring speed is 200-500rpm, and the solution I obtained after the reaction is purified HGeCl3.

5. The method for preparing chlorogermanic acid and synthesizing organic germanium Ge-132 by pressurized strengthening of germanium dioxide chloride according to claim 1, characterized in that: The specific process of step 4 is: the amount of acrylic acid added is 0.7-2 times the amount of GeO2 in step 1, the reaction temperature is 0-50°C, the time is 2-6h, the stirring speed is 200-600rpm, and the precipitate II obtained after filtration is Cl3GeCH2CH2COOH.

6. The method for preparing chlorogermanic acid and synthesizing organic germanium Ge-132 by pressurized strengthening of germanium dioxide chloride according to claim 1, characterized in that: The specific process of step 5 is: liquid-to-solid ratio 8-20 ml / g, temperature 0-50° C., time 1-2 h, stirring speed 200-500 rpm.

7. The method for preparing chlorogermanic acid and synthesizing organic germanium Ge-132 by pressurized strengthening of germanium dioxide chloride according to claim 1, characterized in that: The specific washing process of step 6 is: ultrasonic dispersion washing, the detergent is one or two of food-grade ethanol aqueous solution and food-grade acetone aqueous solution in a volume ratio of 1:1-1:5, and the washing times are 3-5 times.

8. The method for preparing chlorogermanic acid and synthesizing organic germanium Ge-132 by pressurized strengthening of germanium dioxide chloride according to claim 1, characterized in that: The specific process of drying in step 6 is: drying by microwave energy at a temperature of 80-110° C. for 4-6 hours.

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