CN103172510B - Preparation method of bismuth citrate - Google Patents
Preparation method of bismuth citrate Download PDFInfo
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- CN103172510B CN103172510B CN201110431838.2A CN201110431838A CN103172510B CN 103172510 B CN103172510 B CN 103172510B CN 201110431838 A CN201110431838 A CN 201110431838A CN 103172510 B CN103172510 B CN 103172510B
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- citric acid
- acid solution
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Abstract
The invention provides a preparation method of bismuth citrate, which comprises the following steps: crushing bismuth oxide to a specified average particle size; step two, preparing a citric acid aqueous solution with a preset concentration and heating the citric acid aqueous solution to a preset temperature lower than the boiling point of water; step three, according to the chemical reaction equation Bi2O3+2C6H8O7＝2C6H5BiO7+3H2O maintaining an initial excess coefficient of citric acid in the aqueous citric acid solution below 1, gradually adding the pulverized bismuth oxide to the heated aqueous citric acid solution to react the citric acid with the bismuth oxide; gradually adding citric acid aqueous solution with another concentration along with the reaction to keep the initial liquid-solid ratio; and step five, after the reaction is finished, filtering and drying. In the second step, the preset concentration of the citric acid aqueous solution is 200-500 g/L; in the fourth step, the concentration of the supplemented citric acid aqueous solution with the other concentration is 50-200 g/L; in the fourth step, gradually adding the citric acid aqueous solution with another concentration is performed by measuring the viscosity of the citric acid aqueous solution before adding in real time.
Description
Technical field
The present invention relates to a kind of preparation method of bismuth compound, particularly relate to a kind of preparation method of bismuth citrate.
Background technology
Bismuth citrate (also known as bismuth citrate) is treatment stomach trouble, the intermediate of anti-ulcerative drug.Be used for the treatment of stomach ulcer, duodenal ulcer, complex ulcer, multiple ulcers and stoma ulcer.And for chronic superficial gastritis and the treatment with Helicobacter pylori infection.The method of traditional mode of production bismuth citrate mainly adds citric acid reactions generation product or generates product with citric acid reactions after regulating the pH value of Bismuth trinitrate to make it generate bismuth hydroxide in bismuth nitrate solution.NO in the bismuth citrate of produced in conventional processes
3-higher.
Chinese invention application publication number CN1793101A discloses a kind of method of Hydrothermal Synthesis bismuth citrate disclosed in the 28 days June in 2006, it adopts bismuth oxide and citric acid to be ground and puts into autoclave, then autoclave is placed in baking oven 100 ~ 150 DEG C of constant temperature 1 ~ 12 hour, washing and drying obtains bismuth citrate.This method needs to carry out in hyperbaric environment, higher to equipment requirements, and autoclave need put into baking oven, is unfavorable for scale operation.
Chinese invention patent application publication number CN101041617A discloses a kind of method that electrolyzing active metal bismuth produces bismuth citrate disclosed in 26 days September in 2007.This method first by electrolysis production particle diameter at the ultra-fine bismuth of 20 ~ 350nm scope, then make its directly and citric acid reactions generate bismuth citrate.The condition of this method electrolysis production superfine metal bismuth is harsh, and ultra-fine bismuth is very easily oxidized, is not suitable for industrial production.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of preparation method of bismuth citrate, it can reduce the requirement to equipment, is easy to realize suitability for industrialized production.
Another object of the present invention is to a kind of preparation method of bismuth citrate, it can reduce preparation condition, and convenient operation controls.
In order to realize above-mentioned purpose of the present invention, the invention provides a kind of preparation method of bismuth citrate, comprising step: step one, bismuth oxide is crushed to regulation median size; Step 2, the preparation aqueous citric acid solution of predetermined concentration the preset temperature be heated to lower than water boiling point; Step 3, according to chemical equation Bi
2o
3+ 2C
6h
8o
7=2C
6h
5biO
7+ 3H
2o makes the initial excess coefficient of the citric acid in aqueous citric acid solution remain on less than 1, is progressively added to by the bismuth oxide of pulverizing in the aqueous citric acid solution of described heating, reacts to make citric acid and bismuth oxide; Step 4, along with the carrying out of reaction, progressively adds the aqueous citric acid solution of another concentration, to keep initial liquid-solid ratio; Step 5, after reaction terminates, filters and dries, and namely obtains bismuth citrate goods.In step 2, the predetermined concentration of aqueous citric acid solution is 200 ~ 500g/L; In step 4, described in the concentration of the aqueous citric acid solution of another concentration added be 50 ~ 200g/L; In step 4, the aqueous citric acid solution progressively adding another concentration is undertaken by the viscosity measuring the aqueous citric acid solution before adding in real time.
Beneficial effect of the present invention is as follows.
The preparation method of bismuth citrate of the present invention is easy to realize suitability for industrialized production without particular requirement to equipment.
Simple and the convenient operation of preparation method's preparation flow of bismuth citrate of the present invention controls.
The preparation method of bismuth citrate of the present invention very easily realizes suitability for industrialized production.
The productive rate of the bismuth citrate of preparation method's acquisition of bismuth citrate of the present invention is high, impurity is few.
Embodiment
The following detailed description of the preparation method of bismuth citrate according to the present invention.
According to the preparation method of bismuth citrate of the present invention, comprise step: step one, bismuth oxide is crushed to regulation median size; Step 2, the preparation aqueous citric acid solution of predetermined concentration the preset temperature be heated to lower than water boiling point; Step 3, according to chemical equation Bi
2o
3+ 2C
6h
8o
7=2C
6h
5biO
7+ 3H
2o makes the initial excess coefficient of the citric acid in aqueous citric acid solution remain on less than 1, is progressively added to by the bismuth oxide of pulverizing in the aqueous citric acid solution of described heating, reacts to make citric acid and bismuth oxide; Step 4, along with the carrying out of reaction, progressively adds the aqueous citric acid solution of another concentration, to keep initial liquid-solid ratio; Step 5, after reaction terminates, filters and dries, and namely obtains bismuth citrate goods.
Wherein, the initial excess coefficient of citric acid refer to add on the basis of the amount of the citric acid needed for the chemical equation theory of computation into the mole number of citric acid; Initial liquid-solid ratio refers to the mass ratio of the liquid before bismuth oxide and citric acid solution reaction and solid.
According in the preparation method of bismuth citrate of the present invention, preferably, in step one, the median size of described bismuth oxide is 0.1 ~ 0.5 μm.
According in the preparation method of bismuth citrate of the present invention, preferably, in step 2, the predetermined concentration of aqueous citric acid solution is 200 ~ 500g/L.
According in the preparation method of bismuth citrate of the present invention, preferably, in step 2, preset temperature is 60 ~ 90 DEG C.
According in the preparation method of bismuth citrate of the present invention, preferably, in step 3, initial excess coefficient is 0.3 ~ 1.
According in the preparation method of bismuth citrate of the present invention, preferably, in step 3, time in the aqueous citric acid solution bismuth oxide of pulverizing progressively being added to described heating, be added with stirring.Preferably, stirring velocity is 250 ~ 300rpm.Preferably, churning time is 28 ~ 48h.
According in the preparation method of bismuth citrate of the present invention, preferably, in step 4, described in the concentration of the aqueous citric acid solution of another concentration added be 50 ~ 200g/L.
According in the preparation method of bismuth citrate of the present invention, preferably, in step 4, the aqueous citric acid solution progressively adding another concentration is undertaken by the viscosity measuring the aqueous citric acid solution before adding in real time.
According in the preparation method of bismuth citrate of the present invention, preferably, in step 5, bake out temperature is 60 DEG C.
Next provides the embodiment of the preparation method of bismuth citrate of the present invention.
Embodiment 1
Step one, bismuth oxide being crushed to median size is 0.1 μm.The broken test-type micronizer mill adopting Shanghai Sai Shan powder machinery Manufacturing Co., Ltd to produce.
Step 2, configuration 200mL concentration is the aqueous citric acid solution of 200g/L, and is heated to 60 DEG C.
Step 3, the initial excess coefficient controlling citric acid is 0.3, takes the Bismuth oxide particles of 43.7g pulverizing and will progressively join in the aqueous citric acid solution of step 2, stirring reaction 28h.
Step 4, in reaction process, according to the toughness of reaction soln, the aqueous citric acid solution progressively adding 200g/L maintains the initial liquid-solid ratio of reaction.
Step 5, reaction end to filter cake pH=5 ~ 7 with ultrapure water filtration washing product bismuth citrate, is dried filter cake for 60 DEG C in vacuum drying oven, is obtained white powder bismuth citrate product.
Adopt EDTA complexometric titration to detect the product analyzed and obtain, bi content is 53.07%.The quality of qualified product is 66.44g, ratio defective product be 89% (ratio defective product is calculated with the gauge of the bismuth oxide added, the ratio for product actual output and theoretical yield).
Embodiment 2
Step one, bismuth oxide being crushed to median size is 0.2 μm.The broken test-type micronizer mill adopting Shanghai Sai Shan powder machinery Manufacturing Co., Ltd to produce.
Step 2, configuration 200mL concentration is the aqueous citric acid solution of 300g/L, and is heated to 70 DEG C.
Step 3, the initial excess coefficient controlling citric acid is 0.5, takes the Bismuth oxide particles of 56.83g pulverizing and will progressively join in the aqueous citric acid solution of step 2, stirring reaction 36h.
Step 4, in reaction process, according to the toughness of reaction soln, the aqueous citric acid solution progressively adding 150g/L maintains the initial liquid-solid ratio of reaction.
Step 5, reaction end to filter cake pH=5 ~ 7 with ultrapure water filtration washing product bismuth citrate, is dried filter cake for 60 DEG C in vacuum drying oven, is obtained white powder bismuth citrate product.
Adopt EDTA complexometric titration to detect the product analyzed and obtain, bi content is 52.8%.The quality of qualified product is 88.34g, and calculate with the gauge of the bismuth oxide added, ratio defective product is 91%.
Embodiment 3
Step one, bismuth oxide being crushed to median size is 0.3 μm.The broken test-type micronizer mill adopting Shanghai Sai Shan powder machinery Manufacturing Co., Ltd to produce.
Step 2, configuration 200mL concentration is the aqueous citric acid solution of 400g/L, and is heated to 80 DEG C.
Step 3, the initial excess coefficient controlling citric acid is 0.8, takes the Bismuth oxide particles of 63.15g pulverizing and will progressively join in the aqueous citric acid solution of step 2, stirring reaction 36h.
Step 4, in reaction process, according to the toughness of reaction soln, the aqueous citric acid solution progressively adding 100g/L maintains the initial liquid-solid ratio of reaction.
Step 5, reaction end to filter cake pH=5 ~ 7 with ultrapure water filtration washing product bismuth citrate, is dried filter cake for 60 DEG C in vacuum drying oven, is obtained white powder bismuth citrate product.
Adopt EDTA complexometric titration to detect the product analyzed and obtain, bi content is 52.63%.The quality of qualified product is 93.85g, and calculate with the gauge of the bismuth oxide added, ratio defective product is 87%.
Embodiment 4
Step one, bismuth oxide being crushed to median size is 0.5 μm.The broken test-type micronizer mill adopting Shanghai Sai Shan powder machinery Manufacturing Co., Ltd to produce.
Step 2, configuration 200mL concentration is the aqueous citric acid solution of 500g/L, and is heated to 90 DEG C.
Step 3, the initial excess coefficient controlling citric acid is 1, takes the Bismuth oxide particles of 71g pulverizing and will progressively join in the aqueous citric acid solution of step 2, stirring reaction 48h.
Step 4, in reaction process, according to the toughness of reaction soln, the aqueous citric acid solution progressively adding 50g/L maintains the initial liquid-solid ratio of reaction.
Step 5, reaction end to filter cake pH=5 ~ 7 with ultrapure water filtration washing product bismuth citrate, is dried filter cake for 60 DEG C in vacuum drying oven, is obtained white powder bismuth citrate product.
Adopt EDTA complexometric titration to detect the product analyzed and obtain, bi content is 52.36%.The quality of qualified product is 112.79g, and calculate with the gauge of the bismuth oxide added, ratio defective product is 93%.
Claims (6)
1. a preparation method for bismuth citrate, is characterized in that, comprises step:
Step one, is crushed to regulation median size by bismuth oxide;
Step 2, the preparation aqueous citric acid solution of predetermined concentration the preset temperature be heated to lower than water boiling point;
Step 3, according to chemical equation Bi
2o
3+ 2C
6h
8o
7=2C
6h
5biO
7+ 3H
2o makes the initial excess coefficient of the citric acid in aqueous citric acid solution be 0.3 ~ 1, is progressively added to by the bismuth oxide of pulverizing in the aqueous citric acid solution of described heating, reacts to make citric acid and bismuth oxide;
Step 4, along with the carrying out of reaction, progressively adds the aqueous citric acid solution of another concentration, to keep initial liquid-solid ratio;
Step 5, after reaction terminates, filters and dries, and namely obtains bismuth citrate goods;
In step 2, the predetermined concentration of aqueous citric acid solution is 200 ~ 500g/L;
In step 4, described in the concentration of the aqueous citric acid solution of another concentration added be 50 ~ 200g/L;
In step 4, the aqueous citric acid solution progressively adding another concentration is undertaken by the viscosity measuring the aqueous citric acid solution before adding in real time;
Wherein, the initial excess coefficient of citric acid refer to add on the basis of the amount of the citric acid needed for the chemical equation theory of computation into the mole number of citric acid; Initial liquid-solid ratio refers to the mass ratio of the liquid before bismuth oxide and citric acid solution reaction and solid.
2. the preparation method of bismuth citrate according to claim 1, it is characterized in that, in step one, the median size of described bismuth oxide is 0.1 ~ 0.5 μm.
3. the preparation method of bismuth citrate according to claim 1, it is characterized in that, in step 2, preset temperature is 60 ~ 90 DEG C.
4. the preparation method of bismuth citrate according to claim 1, is characterized in that, in step 3, time in the aqueous citric acid solution bismuth oxide of pulverizing progressively being added to described heating, be added with stirring.
5. the preparation method of bismuth citrate according to claim 4, it is characterized in that, in step 3, stirring velocity is 250 ~ 300rpm, and churning time is 28 ~ 48h.
6. the preparation method of bismuth citrate according to claim 1, it is characterized in that, in step 5, bake out temperature is 60 DEG C.
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| CN103864605B (en) * | 2014-03-24 | 2015-11-25 | 清远先导材料有限公司 | A kind of preparation method of bismuth citrate |
| CN110357778B (en) * | 2019-08-02 | 2022-02-11 | 湖南柿竹园有色金属有限责任公司 | Preparation method of bismuth citrate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1793101A (en) * | 2005-12-23 | 2006-06-28 | 华东师范大学 | Process for hydrothermal synthesizing bismuth citrate |
| CN101628735A (en) * | 2009-08-24 | 2010-01-20 | 中南大学 | Method for preparing bismuth-series chemical product |
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2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1793101A (en) * | 2005-12-23 | 2006-06-28 | 华东师范大学 | Process for hydrothermal synthesizing bismuth citrate |
| CN101628735A (en) * | 2009-08-24 | 2010-01-20 | 中南大学 | Method for preparing bismuth-series chemical product |
Non-Patent Citations (1)
| Title |
|---|
| 柠檬酸铋的制备、结构表征及其在固体推进剂中的催化作用;宋秀铎等;《兵工学报》;20060731;第27卷(第4期);第643-647页 * |
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Effective date of registration: 20220519 Address after: No. 1116-1, building 1, Dianzhong Business Plaza, Dianzhong new area, Kunming, Yunnan 650212 Patentee after: Kunming forerunner New Material Technology Co.,Ltd. Address before: 511500 Industrial Zone, wo Yun town, Qingxin County, Qingyuan, Guangdong (beside the fish dam road) Patentee before: FIRST RARE MATERIALS Co.,Ltd. |
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