CN109455742B - Method for simply producing pharmaceutic adjuvant anhydrous sodium sulfite - Google Patents
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Abstract
The invention discloses a method for simply producing pharmaceutic adjuvant anhydrous sodium sulfite, relating to the field of chemical industry and comprising the following process steps: preparing a sodium bisulfite solution with a certain concentration by using distilled water, adding a sodium hydroxide solution with a certain concentration at a certain reaction temperature while stirring, controlling the pH value of the reaction end point to be alkaline, and stirring for reacting for about 20 min; after the reaction is finished, continuously stirring to control the pH value of the reaction end point to be within the range of 12.0-12.30; and (3) carrying out reduced pressure vacuum distillation on the reaction liquid, evaporating until a large amount of crystals appear in the reaction liquid, cooling, carrying out centrifugal separation, drying solid crystals, and analyzing and detecting the obtained product to obtain the qualified pharmaceutical adjuvant anhydrous sodium sulfite. The production method for preparing the anhydrous sodium sulfite as the medical auxiliary material by using the food-grade sodium bisulfite and the refined sodium hydroxide as the raw materials through one-step reaction has the characteristics of short process flow and simple and convenient operation, and ensures the product quality through the detection of the raw materials, the production links and the product.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a method for simply producing anhydrous sodium sulfite serving as a pharmaceutic adjuvant.
Background
The anhydrous sodium sulfite as one kind of medicinal supplementary material is one kind of inorganic compound, white granular powder at room temperature, has sulfur dioxide smell, is stable in drying, sensitive to humidity, soluble in water, glycerin and ethanol, and alkaline in water solution to react with acid to produce toxic sulfur dioxide gas, which is decomposed into sodium sulfide and sodium sulfate while heating and oxidized into sodium sulfate while being set in air. Is widely used as bleaching agent, preservative, loosening agent, antioxidant and medicine synthesis, and is mainly used as reducing agent in the production of medicine preparation.
The production process of anhydrous sodium sulfite at present mainly adopts an absorption method, namely SO generated by burning sulfur2Introducing gas into an absorption tower to perform countercurrent absorption with a soda solution with the relative density of 1.21 to generate a sodium bisulfite solution, neutralizing the sodium bisulfite solution in a neutralization tank to be slightly acidic by using the soda solution with the relative density of 1.21, and then heating to the temperature of over 102 ℃; adding caustic soda solution with the relative density of 1.19 for neutralization until the pH value is 11-12, removing iron, and obtaining sodium sulfite solution at the same time; the neutralized liquid is evaporated, concentrated, crystallized and separated in vacuum (26.7kPa), and dried in air flow at 250-300 DEG CDrying and removing crystal water to obtain the product. The main chemical reaction equation in the production process is as follows:
S+O2→SO2
Na2CO3+SO2→Na2SO3+CO2↑
Na2SO3+SO2+H2O→2NaHSO3
NaHSO3+NaOH→Na2SO3+H2O
the production process has the advantages of large equipment investment, multiple production procedures and long process flow, and is suitable for large-scale enterprises with large production capacity. The absorption method has the characteristics that: 1. the main equipment required by the process for producing the pharmaceutic adjuvant anhydrous sodium sulfite by the absorption method comprises the following steps: the device comprises a sulfur incinerator, a sulfur remover, an absorption tower, a neutralization tank, a blending tank, a vacuum distillation system, a cooling tank, a centrifugal machine, an air flow dryer and the like. 2. The main production processes for producing the pharmaceutic adjuvant anhydrous sodium sulfite by the absorption method comprise the steps of sulfur combustion, sulfur dioxide furnace gas purification treatment, sulfur dioxide absorption by a sodium carbonate solution, sodium carbonate solution blending, sodium hydroxide neutralization, impurity removal, vacuum heating concentration, cooling crystallization, centrifugal separation, drying and the like. 3. The process for producing anhydrous sodium sulfite as a pharmaceutic adjuvant by an absorption method has the characteristics of large equipment investment, long process flow and suitability for large-scale and large-scale production, and is not suitable for small pharmaceutical adjuvant production enterprises.
Because the anhydrous sodium sulfite used as the pharmaceutic adjuvant is not large in use amount, most of pharmaceutical adjuvant production enterprises are manufacturers with multiple product types and low yield at present, so the enterprises need a production method with simple and convenient operation and short process flow, and therefore, a production process for simply producing the anhydrous sodium sulfite as the pharmaceutic adjuvant needs to be designed and developed.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a process for producing anhydrous sodium sulfite as a medicinal auxiliary material, which has the advantages of short production process flow, simple and convenient operation, suitability for small-sized pharmaceutical auxiliary material production enterprises, low equipment investment, flexible production and easy control of product quality.
A method for simply producing pharmaceutic adjuvant anhydrous sodium sulfite comprises the following process steps:
(1) preparing a sodium bisulfite solution with a certain concentration by using distilled water, adding a sodium hydroxide solution with a certain concentration at a certain reaction temperature while stirring, controlling the pH value of the reaction end point to be alkaline, and stirring for reacting for about 20 min;
(2) after the reaction is finished, continuously stirring to control the pH value of the reaction end point to be within the range of 12.0-12.30;
(3) and (3) carrying out reduced pressure vacuum distillation on the reaction liquid, evaporating until a large amount of crystals appear in the reaction liquid, cooling, carrying out centrifugal separation, drying solid crystals, and analyzing and detecting the obtained product to obtain the qualified pharmaceutical adjuvant anhydrous sodium sulfite.
Preferably, in step (1), the reaction equation is:
NaHSO3+NaOH＝Na2SO3+H2O
preferably, in the step (1), the reaction temperature is (40 +/-5) DEG C, wherein the sodium bisulfite is food grade, and the quality of the sodium bisulfite conforms to the GB2760-2014 food additive standard.
Preferably, in step (1), the concentration of the sodium bisulfite solution is (260. + -. 10) g/L and the concentration of the sodium hydroxide solution is (60. + -. 1) g/L.
Preferably, in step (2), after the reaction is completed, the stirring is continued for 10min or more.
Preferably, in step (3), the reaction solution is fed into an evaporator, reduced in pressure to a vacuum state to prevent oxidation of sodium sulfite during evaporative concentration, and then heated for evaporative concentration until a large amount of crystals appear in the solution and only a small amount of solution exists, the heating is stopped, and then cooled to below 20 ℃, and then centrifugal separation is performed.
Preferably, in the step (3), the evaporation condensate in the vacuum evaporation and concentration process is distilled water, which can be used as a prepared reaction solution for recycling; and (3) detecting impurities in the filtrate, wherein the content of various impurities meets the requirement (according to the quality standard of anhydrous sodium sulfite as a pharmaceutical adjuvant) and does not exceed the standard, and returning to the concentration process for recycling.
Wherein, the product detection is according to the detection and analysis method of YY0205-95 pharmaceutic adjuvant anhydrous sodium sulfite standard, and the pharmaceutic adjuvant anhydrous sodium sulfite quality standard is as follows: the content (calculated by Na2SO 3) is more than or equal to 97.0 percent; chloride is less than or equal to 0.002 percent; heavy metal (calculated as Pb) is less than or equal to 0.001 percent; iron (Fe) is less than or equal to 0.0005 percent; arsenic (As) is less than or equal to 0.0001 percent; water insoluble matter is less than or equal to 0.005 percent; thiosulfate, the solution acidified without turbidity.
Preferably, in the reaction process, the reaction solution is recycled, so that impurities are gradually accumulated to increase the content of the impurities, and when certain impurities are generated during detection of the filtrate and exceed the standard requirement, the filtrate is separately collected for preparing industrial-grade sodium sulfite.
The scheme also provides the application of the method for simply producing the pharmaceutic adjuvant anhydrous sodium sulfite,
preferably, the method is applied to production of small pharmaceutical excipient manufacturers with simple and convenient operation and short process flow.
The key points of the invention are as follows:
(1) food-grade sodium bisulfite and refined sodium hydroxide which meet the quality requirement are selected as raw materials, and distilled water is used for preparing reaction solution, so that impurities are prevented from being brought in.
(2) Controlling the concentration, temperature and end point pH value of the reaction of the sodium bisulfite and the sodium hydroxide.
(3) The raw materials, production links and products are detected according to requirements, and the product quality is ensured.
(4) The evaporation condensate and the filtrate are recycled, and three wastes are not discharged in the production process.
The comprehensive effects brought by the invention comprise:
(1) the production process flow is short, and the operation is simple and convenient;
(2) the equipment investment is small, the production period is short, and the production capacity is convenient to control according to market quotations;
(3) raw materials, production links and product detection are carried out, so that the product quality is ensured;
(4) the production process is suitable for small pharmaceutical adjuvant production enterprises.
In particular, the production method for preparing the anhydrous sodium sulfite as the medical auxiliary material by using food-grade sodium bisulfite and sodium hydroxide as raw materials through one-step reaction has the characteristics of short process flow and simple and convenient operation, and ensures the product quality through the detection of the raw materials, production links and products.
Drawings
FIG. 1 is a block diagram of the production process of anhydrous sodium sulfite as a pharmaceutical adjuvant in example 1 of the present invention.
Detailed Description
The following examples of the present invention are merely illustrative of specific embodiments for carrying out the present invention and are not to be construed as limiting the invention. Other changes, modifications, substitutions, combinations, and simplifications which may be made without departing from the spirit and principles of the invention are intended to be equivalent substitutions and are within the scope of the invention.
The invention relates to a production process of anhydrous sodium sulfite as a pharmaceutic adjuvant, which comprises the following steps:
1. and (3) analyzing and detecting the food-grade sodium bisulfite, wherein the quality of the food-grade sodium bisulfite meets the GB2760-2014 food additive standard.
2. Preparing a sodium bisulfite solution with a proper concentration by using distilled water, wherein if the concentration of the sodium bisulfite solution is too low, the energy consumption in the evaporation concentration process is high and the time is long; the concentration of the sodium bisulfite solution is too high, which affects the quality of anhydrous sodium sulfite as a pharmaceutic adjuvant. The experimental result shows that the concentration of the sodium bisulfite solution is controlled to be about 260 g/L.
3. The concentration of the refined sodium hydroxide solution is not too high, otherwise the pH value at the end point of the reaction is not easy to control. Distilled water is selected to prepare refined sodium hydroxide solution with the concentration of about 60 g/L.
4. And heating the sodium bisulfite solution to 40 ℃, adding the prepared sodium hydroxide solution while stirring, detecting the pH value of the reaction solution in due time, and controlling the pH value at the end point of the reaction to be 12.0-12.30.
The reaction equation is:
NaHSO3+NaOH＝Na2SO3+H2O
5. and (3) after the reaction is finished, continuously stirring for 10min until the pH value of the reaction end point is within the range of 12.0-12.30 and is constant.
6. Adding the reaction solution into an evaporator, reducing the pressure to a vacuum state to prevent sodium sulfite from being oxidized during evaporation concentration, then heating, evaporating and concentrating until a large amount of crystals appear in the solution, stopping heating, cooling to below 20 ℃, filtering, separating, drying and detecting (detecting and analyzing products according to the method for detecting and analyzing anhydrous sodium sulfite of the YY0205-95 pharmaceutic adjuvant). The qualified product is the anhydrous sodium sulfite as the pharmaceutic adjuvant.
7. The evaporation condensate in the process of vacuum evaporation and concentration under reduced pressure is distilled water which is used as a prepared reaction solution; and (3) detecting impurities in the filtrate, wherein the content of various impurities meets the requirement (according to the quality standard of anhydrous sodium sulfite as a pharmaceutical adjuvant) and does not exceed the standard, and returning to the concentration process for recycling. In the reaction process, the reaction solution is recycled, so that impurities are gradually accumulated to increase the content of the impurities, and if certain impurities are generated during detection of the filtrate and exceed the standard requirement, the filtrate is separately collected for preparing industrial-grade sodium sulfite.
Example 1
Pilot test of pharmaceutic adjuvant anhydrous sodium sulfite
Preparing a sodium bisulfite solution by using distilled water, adding a sodium hydroxide solution under stirring at a certain reaction temperature, controlling the pH value of a reaction end point, exploring the influence of the concentration of the sodium bisulfite solution, the reaction temperature and the end point pH value on the yield and quality of the anhydrous sodium sulfite of the pharmaceutic adjuvant, carrying out reduced pressure vacuum distillation on a reaction solution after the reaction is finished, evaporating until a large amount of crystals appear in the reaction solution and only a small amount of solution exists, cooling to below 20 ℃, carrying out centrifugal separation, drying solid crystals, and detecting to be qualified to obtain the anhydrous sodium sulfite of the pharmaceutic adjuvant. The experimental result shows that the concentration of the sodium bisulfite solution is about 260g/L, the reaction temperature is about 40 ℃, the pH value of the reaction end point is controlled to be 12.0-12.3, and the anhydrous sodium sulfite of the pharmaceutic adjuvant with qualified quality and high yield can be obtained. The results of the experiments are shown in tables 1, 2, 3 and 4.
TABLE 1 influence of the reaction end-point pH on the product quality and yield
TABLE 2 influence of reaction temperature on product quality and yield
TABLE 3 Effect of reactant concentrations on product quality and yield
TABLE 4 test results of product
Note: product detection and analysis method according to YY0205-95 pharmaceutic adjuvant anhydrous sodium sulfite standard
Pilot test of anhydrous sodium sulfite as medicinal adjuvant
By using the method described in the examples, pilot test of anhydrous sodium sulfite as a pharmaceutical adjuvant was carried out by a pharmaceutical company of Shandong, and the test data are shown in Table 5. The produced pharmaceutic adjuvant anhydrous sodium sulfite product reaches the quality standard required by the national pharmacopoeia through analysis and detection
TABLE 5 pilot plant test results for anhydrous sodium sulfite as medicinal adjuvant
| Name of material | Index (I) |
| Concentration of sodium bisulfite solution, kg/m3 | 260 |
| Concentration of sodium hydroxide solution, kg/m3 | 60 |
| Amount of sodium bisulfite solution added, m3 | 0.6 |
| Reaction temperature of | 43 |
| Reaction end point pH value | 12.10 |
| Vacuum degree of vacuum evaporation and concentration | 35kPa |
| Amount of mother liquor after separation of crystals, m3 | 0.2 |
| Drying temperature of | 230 |
| Theoretical yield of anhydrous sodium sulfite, kg | 188.95 |
| Actual yield of anhydrous sodium sulfite kg | 156.0 |
| Yield of anhydrous sodium sulfite% | 82.56 |
| Anhydrous sodium sulfite product detection | Qualified |
Although the present invention has been described in detail, modifications within the spirit and scope of the invention will be apparent to those skilled in the art. Further, it should be understood that the various aspects recited herein, portions of different embodiments, and various features recited may be combined or interchanged either in whole or in part. In the various embodiments described above, those embodiments that refer to another embodiment may be combined with other embodiments as appropriate, as will be appreciated by those skilled in the art. Furthermore, those skilled in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention.
Claims (5)
1. A method for simply producing pharmaceutic adjuvant anhydrous sodium sulfite is characterized by comprising the following process steps:
(1) preparing a sodium bisulfite solution with a certain concentration by using distilled water, adding a sodium hydroxide solution with a certain concentration at a certain reaction temperature while stirring, controlling the pH value of the reaction end point to be alkaline, and stirring for reaction for 20 min;
(2) after the reaction is finished, continuously stirring to control the pH value of the reaction end point to be within the range of 12.0-12.30;
(3) vacuum distilling the reaction liquid under reduced pressure, evaporating until a large amount of crystals appear in the reaction liquid, cooling, filtering and separating, drying solid crystals, and analyzing and detecting the obtained product to obtain qualified anhydrous sodium sulfite serving as a pharmaceutical adjuvant;
in the step (1), the reaction temperature is (40 +/-5) DEG C, wherein the sodium bisulfite is food grade, and the quality of the sodium bisulfite meets the standard of GB2760-2014 food additives;
in the step (1), the concentration of the sodium bisulfite solution is (260 +/-10) g/L, and the concentration of the sodium hydroxide solution is (60 +/-1) g/L;
in the step (2), after the reaction is finished, continuously stirring for more than 10 min;
in the step (3), adding the reaction solution into an evaporator, reducing the pressure to a vacuum state to prevent sodium sulfite from being oxidized during evaporation and concentration, heating, evaporating and concentrating until a large amount of crystals appear in the solution and only a small amount of solution exists, stopping heating, cooling to below 20 ℃, and filtering and separating;
in the step (3), the evaporation condensate in the vacuum evaporation and concentration process is distilled water which can be used as a prepared reaction solution for recycling; and (3) carrying out impurity detection on the filtrate, wherein the content of various impurities meets the requirements according to the quality standard of the pharmaceutic adjuvant anhydrous sodium sulfite, and the filtrate can be returned to the vacuum evaporation concentration process for recycling.
2. The method for simply producing anhydrous sodium sulfite as a pharmaceutical excipient according to claim 1, wherein in the step (1), the reaction equation is as follows:
3. the method for simply producing the anhydrous sodium sulfite as the pharmaceutic adjuvant is characterized in that the product detection is performed according to the detection and analysis method of the YY0205-95 anhydrous sodium sulfite standard, and the quality standard of the anhydrous sodium sulfite as the pharmaceutic adjuvant is as follows: content (in Na)2SO3Calculated) is more than or equal to 97.0 percent; chloride is less than or equal to 0.002 percent; heavy metal (calculated as Pb) is less than or equal to 0.001 percent; iron (Fe) is less than or equal to 0.0005 percent; arsenic (As) is less than or equal to 0.0001 percent; water insoluble matter is less than or equal to 0.005 percent; thiosulfate, the solution acidified without turbidity.
4. The method for simply producing anhydrous sodium sulfite as a pharmaceutical adjuvant according to claim 3, wherein the impurities are gradually accumulated to increase the content thereof due to the recycling of the reaction solution during the reaction, and when a certain impurity is detected to exceed the standard requirement, the filtrate is separately collected for preparing industrial-grade sodium sulfite.
5. The application of the method for simply producing anhydrous sodium sulfite as a pharmaceutic adjuvant according to any one of claims 1 to 4 is applied to the production of small pharmaceutic adjuvant manufacturers with simple operation and short process flow.
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