CN115849429B - Preparation method of small-particle-size lanthanum carbonate tetrahydrate - Google Patents
Preparation method of small-particle-size lanthanum carbonate tetrahydrate Download PDFInfo
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- CN115849429B CN115849429B CN202310021176.4A CN202310021176A CN115849429B CN 115849429 B CN115849429 B CN 115849429B CN 202310021176 A CN202310021176 A CN 202310021176A CN 115849429 B CN115849429 B CN 115849429B
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- lanthanum carbonate
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- PKOQIYFBOVTYOH-UHFFFAOYSA-H lanthanum(3+);tricarbonate;tetrahydrate Chemical compound O.O.O.O.[La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PKOQIYFBOVTYOH-UHFFFAOYSA-H 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 74
- 239000000243 solution Substances 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 48
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims abstract description 37
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 37
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 37
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 31
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 20
- GAYSPCNXZCAPHX-UHFFFAOYSA-H lanthanum(3+);tricarbonate;octahydrate Chemical compound O.O.O.O.O.O.O.O.[La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GAYSPCNXZCAPHX-UHFFFAOYSA-H 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 2
- 229910017569 La2(CO3)3 Inorganic materials 0.000 abstract description 40
- 229960001633 lanthanum carbonate Drugs 0.000 abstract description 40
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 20
- 238000004090 dissolution Methods 0.000 abstract description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 6
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 239000002245 particle Substances 0.000 description 38
- 239000008213 purified water Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001514 detection method Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- -1 lanthanum cations Chemical class 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- GZHCNRONBGZNAH-UHFFFAOYSA-N phosphanylidynelanthanum Chemical compound [La]#P GZHCNRONBGZNAH-UHFFFAOYSA-N 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000002603 lanthanum Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 208000020832 chronic kidney disease Diseases 0.000 description 1
- 208000022831 chronic renal failure syndrome Diseases 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229940099065 fosrenol Drugs 0.000 description 1
- 238000001631 haemodialysis Methods 0.000 description 1
- 230000000322 hemodialysis Effects 0.000 description 1
- 201000005991 hyperphosphatemia Diseases 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a preparation method of small-particle-size lanthanum carbonate tetrahydrate, which is characterized in that excessive hydrochloric acid reacts with lanthanum oxide to prepare a mixed solution of hydrochloric acid and lanthanum chloride; then transferring the mixed solution of hydrochloric acid and lanthanum chloride into a sealed reaction kettle, slowly adding sodium bicarbonate solution into the sealed reaction kettle, wherein the molar ratio of sodium bicarbonate to lanthanum oxide is 6.5-7:1, the reaction temperature is 0-10 ℃, controlling the discharge of carbon dioxide generated by the neutralization reaction, keeping the pressure in the sealed reaction kettle at a positive pressure of 100-1000 Pa, performing the reaction in a positive pressure environment rich in carbon dioxide, filtering after the reaction is completed, and washing to obtain a lanthanum carbonate octahydrate wet product; and drying the wet lanthanum carbonate octahydrate to obtain small-particle-size lanthanum carbonate tetrahydrate. The invention adopts the positive pressure environment rich in carbon dioxide to inhibit the crystallization process, so that the crystal nucleus grows slowly, the obtained crystal grain diameter D90 is smaller than 25 mu m, the grain diameter is uniform, and meanwhile, the preparation has better fluidity, can meet the preparation requirement, and improves the dissolution effect and the phosphoric acid removal speed of the lanthanum carbonate preparation.
Description
Technical Field
The invention relates to the technical field of inorganic drug preparation, in particular to a preparation method of small-particle-size lanthanum carbonate tetrahydrate.
Background
Lanthanum carbonate Fosrenol is a salt formed by lanthanum cations and carbonate anions, is a novel phosphorus binding agent and is used for treating hyperphosphatemia of patients suffering from chronic renal failure in hemodialysis or continuous ambulatory peritoneal dialysis. The known synthesis method is that lanthanum oxide reacts with acid solution to obtain lanthanum salt solution firstly, the lanthanum salt solution reacts with alkali metal carbonate to obtain lanthanum carbonate octahydrate wet product, and sodium bicarbonate has mild physicochemical property and convenient use, and is an ideal raw material for preparing lanthanum carbonate. By controlling the drying temperature and time, a certain amount of lanthanum carbonate with crystal water is obtained.
The particle size of lanthanum carbonate has a great influence on the function of the preparation, but the prior literature reports how to better control the particle size of lanthanum carbonate. Zocine et al report the removal rate of lanthanum carbonate phosphoric acid with different particle sizes in application TW103141071A, and prove that the removal rate of the phosphoric acid is obviously improved when the D90 is smaller than 29.8 mu m, but the traditional grinding and crushing are adopted in the preparation method of the lanthanum carbonate with different particle sizes in the patent.
Patent CN111533159a discloses a method for preparing large-particle lanthanum carbonate with D90 of 120-150 μm by gradient cooling, sectional charging and gradual induced crystallization, but the large-particle lanthanum carbonate particles are difficult to dissolve out after preparation, and the phosphoric acid removal rate is obviously reduced.
At present, the conventional direct reaction production method has the advantages that the particle diameter D90 of the prepared lanthanum carbonate is 50-100 mu m, the smaller particle diameter lanthanum carbonate can enable the preparation to have a faster dissolution effect and a phosphoric acid removal speed, the main way of obtaining the smaller particle diameter lanthanum carbonate at present is ball milling and crushing, but the lanthanum carbonate tetrahydrate can cause certain damage to lanthanum carbonate crystallization in the crushing process, so that the phosphoric acid removal effect of the lanthanum carbonate can be influenced, a large amount of dust can be generated, the environment is not friendly, and meanwhile, the material loss can be caused.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of small-particle-size lanthanum carbonate tetrahydrate, which is characterized in that the synthesis process of lanthanum carbonate is controlled under the micro-positive pressure carbon dioxide environment, the nucleation speed of lanthanum carbonate is controlled, and the crystallization process is inhibited, so that the small-particle-size lanthanum carbonate tetrahydrate with the particle size D90 of less than 25 mu m is prepared, and the dissolution effect and the phosphoric acid removal speed of a lanthanum carbonate preparation are improved.
In order to achieve the above purpose, the present invention firstly provides a preparation method of small-particle size lanthanum carbonate tetrahydrate, comprising the following steps:
s1, preparing a mixed solution of hydrochloric acid and lanthanum chloride: mixing concentrated hydrochloric acid and lanthanum oxide according to a molar ratio of 6.2-6.5:1 for reaction, and filtering the reaction solution to obtain a hydrochloric acid and lanthanum chloride mixed solution;
s2, preparing lanthanum carbonate octahydrate: transferring the mixed solution of hydrochloric acid and lanthanum chloride prepared in the step S1 into a sealed reaction kettle, slowly adding sodium bicarbonate solution into the sealed reaction kettle, controlling the discharge of carbon dioxide generated by the neutralization reaction, keeping the pressure in the sealed reaction kettle at a positive pressure of 100-1000 Pa, performing the reaction in a positive pressure environment rich in carbon dioxide, filtering after the reaction is finished, and washing with water to obtain a lanthanum carbonate octahydrate wet product;
s3, preparing small-particle-size lanthanum carbonate tetrahydrate: and (3) drying the lanthanum carbonate octahydrate wet product prepared in the step (S2) to obtain the small-particle-size lanthanum carbonate tetrahydrate.
When lanthanum chloride is prepared, hydrochloric acid is properly excessive, so that the generated lanthanum chloride solution contains a proper amount of hydrochloric acid; the added sodium bicarbonate solution is mainly used for neutralizing free hydrochloric acid to generate carbon dioxide, so that the added sodium bicarbonate can be prevented from directly and rapidly reacting with lanthanum chloride to generate lanthanum carbonate, the lanthanum chloride generation speed is high, the nucleation of lanthanum carbonate particles is low, and the particle size is increased; meanwhile, the generated carbon dioxide can raise the pressure in the sealed reaction kettle, when the pressure in the sealed reaction kettle is more than 100Pa, the PH of a reaction liquid system in the kettle reaches about 4, lanthanum carbonate starts to slowly nucleate and separate out solids, and the quantity of nucleation is more at the moment and the rapid growth of the lanthanum carbonate cannot be increased; with the increase of the adding amount of the sodium bicarbonate solution, the pressure in the reaction kettle is gradually increased as the carbon dioxide is generated, the pressure in the reaction kettle is properly released through a pressure regulating valve of the sealed reaction kettle, the pressure in the reaction kettle is maintained at 100-1000 Pa, the carbon dioxide is rich in a positive pressure environment, the carbon dioxide can be partially dissolved in the reaction liquid under the positive pressure environment, the rise of the pH value of a reaction system can be slowed down, the growth speed of crystal nucleus is inhibited, and the generation of lanthanum carbonate products with smaller particle sizes can be ensured.
Meanwhile, the growth speed of crystal grains can be reduced by a lower reaction temperature (lower than 10 ℃), but the energy consumption can be increased by too low temperature, water can be frozen when the temperature is lower than 0 ℃, the industrial production is not facilitated, and the reaction temperature is 0-10 ℃.
Preferably, in the step S1, the mass concentration of lanthanum chloride in the mixed solution of hydrochloric acid and lanthanum chloride is 7% -8%.
Preferably, the mass concentration of sodium bicarbonate in the step S2 is 7% to 8%.
Preferably, the reaction is completed by continuing stirring for 20-30 min after the sodium bicarbonate is added in the step S2.
Preferably, the pH of the solution after the completion of the reaction in the step S2 is 5.5 to 6.
Preferably, the grain diameter D90 of the tetrahydrate lanthanum carbonate is less than or equal to 25 mu m.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the preparation method of the small-particle-size lanthanum carbonate tetrahydrate, a proper amount of hydrochloric acid is mixed in the generated lanthanum chloride, so that carbon dioxide can be generated by preferentially reacting with most of sodium bicarbonate during the addition of sodium bicarbonate, on one hand, the generation of large-particle lanthanum carbonate through the rapid reaction of the lanthanum chloride and the sodium bicarbonate during the addition of the sodium bicarbonate is prevented, on the other hand, the generated carbon dioxide forms proper micro-positive pressure in a sealed reaction kettle, and the carbon dioxide is dissolved in a reaction system under the positive pressure, so that the rise of the pH value of the reaction system can be slowed down, the crystallization process is inhibited, the growth of crystal nuclei is slow, and the obtained lanthanum carbonate tetrahydrate has the particle size D10: 1-2 mu m, D50: 6-10 mu m, D90: 16-25 mu m;
2. according to the preparation method, mechanical grinding such as ball milling is not needed, the particle size D90 of the directly generated lanthanum carbonate tetrahydrate product is smaller than 25 mu m, the generated lanthanum carbonate tetrahydrate structure is not damaged, the particle size is uniform, meanwhile, the preparation method has good fluidity, the preparation requirement can be met, and the dissolution effect and the phosphoric acid removal speed of the lanthanum carbonate preparation are obviously improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a chart showing the analysis report of the particle size detection of lanthanum carbonate tetrahydrate in example 1 of the present invention;
FIG. 2 is a chart showing the analysis report of the particle size detection of lanthanum carbonate tetrahydrate in example 2 of the present invention;
FIG. 3 is a chart showing the analysis report of the particle size detection of lanthanum carbonate tetrahydrate in comparative example 1 of the present invention;
FIG. 4 is a chart showing the analysis of the particle size detection of lanthanum carbonate tetrahydrate in comparative example 2 of the present invention;
FIG. 5 is a graph showing the dissolution effect of lanthanum carbonate tetrahydrate tablets in Experimental example 1 of the present invention;
FIG. 6 is a graph showing the results of lanthanum phosphorus binding kinetics test of lanthanum carbonate tetrahydrate tablet in experimental example 1 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
The following examples are illustrative of the invention and are not intended to limit the scope of the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit and nature of the invention are intended to be within the scope of the present invention.
The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated; the reagents used in the examples were all commercially available unless otherwise specified.
Example 1
Preparation of small-particle-size lanthanum carbonate tetrahydrate
(1) Preparation of lanthanum chloride solution
1000g of purified water is added into a 2L three-mouth bottle, 99.0g of lanthanum oxide is added under stirring, 192.0g of 36% concentrated hydrochloric acid is slowly added dropwise, and the solution is dissolved and filtered to obtain a lanthanum chloride solution.
(2) Preparation of sodium bicarbonate solution
197g of sodium bicarbonate was weighed out, and 2343g of purified water was added to dissolve the sodium bicarbonate, thereby obtaining 1mol/L sodium bicarbonate solution.
(2) Preparation of lanthanum carbonate octahydrate
Cooling lanthanum chloride solution to 10 ℃, adding the lanthanum chloride solution into a sealed reaction kettle for sealing, arranging a differential pressure meter and an exhaust valve on the sealed reaction kettle, slowly dripping sodium bicarbonate solution into the lanthanum chloride solution, when the PH of a reaction system in the reaction kettle reaches 4, keeping the positive pressure in the sealed reaction kettle at 100Pa, starting to precipitate solid, continuously dripping sodium bicarbonate solution, adjusting the exhaust valve, keeping the pressure at 100Pa until the sodium bicarbonate solution is completely added, stirring the reaction solution for 30min again, decompressing, filtering, and soaking the solid wet product with purified water for 4 times to obtain the lanthanum carbonate octahydrate wet product.
(3) Preparation of lanthanum carbonate tetrahydrate
And drying the wet lanthanum carbonate octahydrate to obtain small-particle-size lanthanum carbonate tetrahydrate.
The particle size detection result of the prepared small-particle-size lanthanum carbonate tetrahydrate is shown in figure 1. As can be seen from FIG. 1, the small particle size lanthanum carbonate tetrahydrate product D10 prepared in this example was 1.668 μm, D50 was 8.412 μm, and D90 was 16.8. Mu.m.
Example 2
Preparation of small-particle-size lanthanum carbonate tetrahydrate
(1) Preparation of lanthanum chloride solution
1000g of purified water is added into a 2L three-mouth bottle, 99.0g of lanthanum oxide is added under stirring, 192.0g of 36% concentrated hydrochloric acid is slowly added dropwise, and the solution is dissolved and filtered to obtain a lanthanum chloride solution.
(2) Preparation of sodium bicarbonate solution
197g of sodium bicarbonate was weighed out, and 2343g of purified water was added to dissolve the sodium bicarbonate, thereby obtaining 1mol/L sodium bicarbonate solution.
(2) Preparation of lanthanum carbonate octahydrate
Cooling lanthanum chloride solution to 5 ℃, adding the lanthanum chloride solution into a sealed reaction kettle for sealing, arranging a differential pressure meter and an exhaust valve on the sealed reaction kettle, slowly dripping sodium bicarbonate solution into the lanthanum chloride solution, when the PH of a reaction system in the reaction kettle reaches 4.5, keeping the positive pressure in the sealed reaction kettle at 1000Pa, starting to precipitate solids, continuously dripping sodium bicarbonate solution, adjusting the exhaust valve, keeping the pressure at 1000Pa until the sodium bicarbonate solution is completely added, stirring the reaction solution at 5.5 PH for 30min, decompressing, filtering, and soaking the solid wet product with purified water for 4 times to obtain the lanthanum carbonate octahydrate wet product.
(3) Preparation of lanthanum carbonate tetrahydrate
And drying the wet lanthanum carbonate octahydrate to obtain small-particle-size lanthanum carbonate tetrahydrate.
The particle size detection result of the prepared small-particle-size lanthanum carbonate tetrahydrate is shown in figure 2. As can be seen from FIG. 2, the small particle size lanthanum carbonate tetrahydrate product D10 prepared in this example was 1.299 μm, D50 was 6.272 μm, and D90 was 16.34. Mu.m.
Comparative example 1
Preparation of lanthanum carbonate tetrahydrate by traditional method
(1) Preparation of lanthanum chloride solution
1000g of purified water is added into a 2L three-mouth bottle, 99.0g of lanthanum oxide is added under stirring, 192.0g of 36% concentrated hydrochloric acid is slowly added dropwise, and the solution is dissolved and filtered to obtain a lanthanum chloride solution.
(2) Preparation of sodium bicarbonate solution
197g of sodium bicarbonate was weighed out, and 2343g of purified water was added to dissolve the sodium bicarbonate, thereby obtaining 1mol/L sodium bicarbonate solution.
(3) Preparation of lanthanum carbonate octahydrate
Slowly dripping sodium bicarbonate solution into lanthanum chloride solution at room temperature and normal pressure, stirring for 30min until the pH of the reaction solution is 6.4, filtering, and soaking and washing the solid wet product with purified water for 4 times to obtain 8-water lanthanum carbonate wet product.
(4) Preparation of lanthanum carbonate tetrahydrate
And drying the lanthanum carbonate octahydrate wet product to obtain lanthanum carbonate tetrahydrate.
As a result of the measurement of the particle size of lanthanum carbonate, as shown in FIG. 3, the particle size distribution of the product obtained in this comparative example was 6.951. Mu.m, 29.96. Mu.m, and 73.11. Mu.m, as D50.
Comparative example 2
Pressurized preparation of lanthanum carbonate tetrahydrate
(1) Preparation of lanthanum chloride solution
1000g of purified water is added into a 2L three-mouth bottle, 99.0g of lanthanum oxide is added under stirring, 187.0g of 36% concentrated hydrochloric acid is slowly added dropwise, the solution is dissolved and filtered, and the lanthanum chloride solution is obtained after the basic reaction of the hydrochloric acid, and the pH value of the lanthanum chloride solution is nearly neutral.
(2) Preparation of sodium bicarbonate solution
197g of sodium bicarbonate was weighed out, and 2343g of purified water was added to dissolve the sodium bicarbonate, thereby obtaining 1mol/L sodium bicarbonate solution.
(2) Preparation of lanthanum carbonate octahydrate
Cooling lanthanum chloride solution to 10 ℃, adding the lanthanum chloride solution into a sealed reaction kettle for sealing, installing a differential pressure meter and an exhaust valve on the sealed reaction kettle, introducing nitrogen to control the pressure in the reaction kettle to be 100Pa, slowly dripping sodium bicarbonate solution into the lanthanum chloride solution until the sodium bicarbonate solution is completely added, stirring the reaction solution for 30min, decompressing, filtering, and soaking the solid wet product with purified water for 4 times to obtain the lanthanum carbonate octahydrate wet product.
(3) Preparation of lanthanum carbonate tetrahydrate
And drying the lanthanum carbonate octahydrate wet product to obtain lanthanum carbonate tetrahydrate.
The lanthanum carbonate particle size measurement results are shown in FIG. 4, and the lanthanum carbonate product prepared in this comparative example has a particle size distribution D10 of 6.289 μm, D50 of 22.46 μm and D90 of 42.80. Mu.m.
Experimental example 1
The dissolution effect and the phosphoric acid removal rate of the prepared lanthanum carbonate preparation are examined
Lanthanum carbonate tetrahydrate prepared in example 1 and comparative example 1 were added with auxiliary materials, respectively, and tablet samples were prepared according to formulation prescriptions, lanthanum carbonate prepared in comparative example 1 was used as sample 1, and lanthanum carbonate prepared in example 1 was used as sample 2.
1. Lanthanum carbonate dissolution experiment
The dissolution effect of the lanthanum carbonate tablets prepared above was examined by the paddle method (50 r/min) in 0.1mol/L hydrochloric acid medium, and the results are shown in FIG. 5 and Table 1.
TABLE 1 elution results of lanthanum carbonate tablets
| Time (h) | 0.08 | 0.17 | 0.25 | 0.33 | 0.5 | 0.67 | 1 | 1.5 | 2 | 2.5 | 3 | 4 | 5 | 6 |
| Sample 1 (%) | 9.2 | 19.5 | 19.1 | 20.4 | 23.7 | 26.6 | 31.3 | 40.4 | 48.5 | 55.8 | 62.2 | 73.1 | 84.5 | 93.9 |
| Sample 2 (%) | 28.5 | 53.7 | 65.7 | 78.4 | 91.4 | 98.1 | 100.1 | 102.1 | 102.6 | / | / | / | / | / |
From the results shown in fig. 5 and table 1, it is clear that the tablet (sample 2) prepared from lanthanum carbonate tetrahydrate with small particle size can achieve 100% dissolution in about 1h, the dissolution speed is fast and the dissolution rate reaches 100%, the effect of lanthanum carbonate can be exerted more rapidly, and the lanthanum carbonate can be basically and effectively utilized; the tablet prepared by the lanthanum carbonate particles with larger particle size prepared by the conventional method in comparative example 1 (sample 1) dissolves 31.3% in 1 hour, and the dissolution rate reaches 93.9% in time after 6 hours, so that the dissolution rate and the dissolution rate are obviously different from those of the small-particle-size lanthanum carbonate tetrahydrate prepared by the method.
2. Lanthanum phosphorus binding rate experiment:
the phosphorus content detection method comprises the following steps: and adding a monopotassium phosphate solution into a 0.1mol/L hydrochloric acid solution medium to prepare a solution with 10-60mmol/L total phosphorus, adding a sample 1 and a sample 2, detecting the residual phosphate amount in a reaction system according to an ammonium molybdate spectrophotometry of GB11893-89, and thus calculating the binding rate of the sample 1 and the sample 2 to phosphoric acid, wherein the results are shown in Table 2 and FIG. 6.
TABLE 2 lanthanum phosphorus binding kinetics test results of binding Rate test
As can be seen from table 2 and fig. 6, the binding efficiency of the small-particle lanthanum carbonate tablet prepared by the method of the present invention and phosphorus is significantly higher than that of the larger-particle lanthanum carbonate prepared by the conventional method, which benefits not only from the efficient dissolution of the small-particle lanthanum carbonate active ingredient, but also from the increased specific surface area of the small-particle lanthanum carbonate tetrahydrate, and the binding with phosphoric acid is more rapid and effective.
The above embodiments are only preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to apply equivalents and modifications according to the technical solution and the concept of the present invention within the scope of the present invention.
Claims (5)
1. The preparation method of the small-particle-size lanthanum carbonate tetrahydrate is characterized by comprising the following steps of:
s1, preparing a mixed solution of hydrochloric acid and lanthanum chloride: mixing concentrated hydrochloric acid and lanthanum oxide according to a molar ratio of 6.2-6.5:1 for reaction, and filtering the reaction solution to obtain a mixed solution of hydrochloric acid and lanthanum chloride;
s2, preparing lanthanum carbonate octahydrate: transferring the mixed solution of hydrochloric acid and lanthanum chloride prepared in the step S1 into a sealed reaction kettle, slowly adding sodium bicarbonate solution into the sealed reaction kettle, wherein the molar ratio of sodium bicarbonate to lanthanum oxide is 6.5-7:1, the reaction temperature is 0-10 ℃, controlling the discharge of carbon dioxide generated by the neutralization reaction, keeping the pressure in the sealed reaction kettle at a positive pressure of 100-1000 Pa, performing the reaction in a positive pressure environment rich in carbon dioxide, filtering after the reaction is completed, and washing with water to obtain a lanthanum carbonate octahydrate wet product;
s3, preparing small-particle-size lanthanum carbonate tetrahydrate: drying the lanthanum carbonate octahydrate wet product prepared in the step S2 to obtain small-particle-size lanthanum carbonate tetrahydrate;
the grain diameter D90 of the tetrahydrate lanthanum carbonate is less than or equal to 25 mu m.
2. The method for preparing small-particle-size lanthanum carbonate tetrahydrate according to claim 1, wherein the mass concentration of lanthanum chloride in the mixed solution of hydrochloric acid and lanthanum chloride in the step S1 is 7% -8%.
3. The method for preparing small-particle-size lanthanum carbonate tetrahydrate according to claim 1, wherein the mass concentration of sodium bicarbonate in the step S2 is 7% -8%.
4. The method for preparing small-particle-size lanthanum carbonate tetrahydrate according to claim 1, wherein the reaction is completed by continuing stirring for 20-30 min after the sodium bicarbonate is added in the step S2.
5. The method for preparing small-particle-size lanthanum carbonate tetrahydrate according to claim 1, wherein the pH value of the solution after the completion of the reaction in the step S2 is 5.5-6.
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