CN114380315B - Purification method and production equipment of medicinal calcium carbonate - Google Patents
Purification method and production equipment of medicinal calcium carbonate Download PDFInfo
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- CN114380315B CN114380315B CN202210157071.7A CN202210157071A CN114380315B CN 114380315 B CN114380315 B CN 114380315B CN 202210157071 A CN202210157071 A CN 202210157071A CN 114380315 B CN114380315 B CN 114380315B
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 289
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 144
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 238000000746 purification Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 77
- 238000001035 drying Methods 0.000 claims abstract description 48
- 238000005406 washing Methods 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 239000000047 product Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000012065 filter cake Substances 0.000 claims abstract description 31
- 238000000926 separation method Methods 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 17
- 239000000706 filtrate Substances 0.000 claims abstract description 14
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 14
- -1 alkali metal salt Chemical class 0.000 claims abstract description 13
- 238000003825 pressing Methods 0.000 claims abstract description 13
- 239000000428 dust Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910001425 magnesium ion Inorganic materials 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 3
- 239000001095 magnesium carbonate Substances 0.000 description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101000777134 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 43 Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 102100031311 Ubiquitin carboxyl-terminal hydrolase 43 Human genes 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 229940124531 pharmaceutical excipient Drugs 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
A method for purifying pharmaceutical calcium carbonate comprising the steps of: 1) Washing with hot water: adding the calcium carbonate raw material into hot water with the mass of 0.8-1.5 times of that of the calcium carbonate and the temperature of 55-65 ℃ to be stirred and mixed for 1-2 hours at constant temperature, and removing filtrate by solid-liquid separation to obtain a calcium carbonate filter cake; repeatedly washing the filter cake with hot water with the mass of 0.8-1.5 times of that of the calcium carbonate and the temperature of 55-65 ℃ for more than 1 time to obtain a calcium carbonate primary product; 2) Drying and crushing: and (3) carrying out filter pressing, drying and crushing on the calcium carbonate primary product obtained in the step (1). The invention also discloses production equipment for purifying the medicinal calcium carbonate. The purification method of the medicinal calcium carbonate can effectively remove impurities such as magnesium salt, alkali metal salt and the like in the calcium carbonate, and improves the product quality. The production equipment is provided with CO below the reaction kettle 2 The charging pipe can enable the calcium carbonate to be charged with CO while being washed by hot water 2 The efficiency of removing impurities by hot water washing is obviously improved.
Description
Technical Field
The invention relates to a production technology of pharmaceutical excipients, in particular to a purification method and production equipment of pharmaceutical calcium carbonate.
Background
Calcium carbonate (CaCO) 3 ) The calcium source is the most widely used medical and edible calcium source at present because of rich resources, high calcium content (40%) and low cost. With the continuous improvement of the quality standard of medicinal and edible calcium carbonate, the requirements of the international market on the impurity limit in medicines and foods are higher and higher, wherein the standard of the quality of the medicinal and edible calcium carbonate is CP2020 Chinese pharmacopoeia, USP43 United states pharmacopoeia, EP10 European pharmacopoeia, GB 1886.214-2016 and food safety national standard food additive calcium carbonate (comprising light and heavy calcium carbonate). In the Products (PCC) produced by the traditional calcium carbonate production process, the content of impurities such as lead, arsenic, iron, mercury and the like is difficult to reach a new standard, and the granularity is inconvenient to adjust. In general ground calcium carbonate (natural calcium carbonate)The magnesium salt and the alkali metal salt, iron, silicon and other impurities have high content and are difficult to remove.
CN204298075U discloses a device for removing iron and magnesium from calcium carbonate, which comprises a base, wherein a shell is installed on the upper part of the base, a fixed pipe is installed at the bottom of the inner side of the shell, a plurality of third through holes are installed on the side periphery of the fixed pipe, a support is installed on one side of the base, a fixed plate is installed on one side of the support, a second through hole is vertically formed in the fixed plate, the second through hole is positioned above the shell, a first motor is installed on the upper part of the fixed plate, and a gearbox is installed on the lower part of the fixed plate. The device for removing iron and magnesium from the calcium carbonate provides the purity of the calcium carbonate to a certain extent, but has low purification efficiency.
Disclosure of Invention
The invention aims to solve the technical problems that: overcomes the defects of the prior art, and provides a purification method of medicinal calcium carbonate, which is simple to operate and can efficiently remove impurities such as magnesium salt, alkali metal salt and the like.
The technical scheme adopted for solving the technical problems is as follows:
a method for purifying pharmaceutical calcium carbonate comprising the steps of:
1) Washing with hot water: adding the calcium carbonate raw material into hot water with the mass of 0.8-1.5 times of that of the calcium carbonate and the temperature of 55-65 ℃ to be stirred and mixed for 1-2 hours at constant temperature, and removing filtrate by solid-liquid separation to obtain a calcium carbonate filter cake; repeatedly washing the filter cake with hot water with the mass of 0.8-1.5 times of that of the calcium carbonate and the temperature of 55-65 ℃ for more than 1 time to obtain a calcium carbonate primary product;
2) Drying and crushing: and (3) carrying out filter pressing, drying and crushing on the calcium carbonate primary product obtained in the step (1).
In the step 1), CO is continuously introduced from the bottom of the reaction kettle in the hot water washing process 2 ，CO 2 The flow rate of the mixture is 20-30 Kg/h, CO 2 The calcium carbonate material is introduced into the reaction kettle to facilitate the dispersion of the calcium carbonate material in the washing process, so that the dissolution of magnesium ions and alkali metals in hot water is promoted, and the magnesium ions and the alkali metals are removed in the solid-liquid separation process; next, CO is introduced 2 The stability of the calcium carbonate can be improved, and the magnesium ions can be removed by forming a magnesium carbonate micro-solution.
Preferably, the number of times of the hot water washing is 3 to 5.
The utility model provides a production facility is used in purification of medicinal calcium carbonate, includes reation kettle, solid-liquid separation device, drying device and reducing mechanism, be equipped with agitating unit and heating constant temperature jacket in the reation kettle, its bottom is connected with and lets in CO to reation kettle in 2 CO of (c) 2 An air charging pipe, said CO 2 The air charging pipe is provided with a one-way valve and is communicated with an air source device; the discharging pipe of the reaction kettle is communicated with the solid-liquid separation device; and returning the filter cake after the solid-liquid separation device to the reaction kettle for washing or sending the filter cake to a drying device for drying, and sending the dried material to a crushing device for crushing.
The air inlet of the drying device is provided with a filter screen, and preferably, the aperture of the filter screen is 100 meshes.
The air outlet of the crushing device is connected with a dust fall pipe, the free end of the dust fall pipe is placed below the liquid level of dust collection liquid of the dust collection tank, so that the dust emission phenomenon in the calcium carbonate crushing process is avoided or reduced, and the production environment of calcium carbonate is improved.
The dust-absorbing liquid is water.
The purification method of the medicinal calcium carbonate has the beneficial effects that:
the invention repeatedly washes the calcium carbonate by adopting hot water with the temperature of 55-65 ℃, promotes the dissolution of magnesium salt and alkali metal salt mixed in the calcium carbonate raw material in water, and is convenient for efficiently removing impurities in the calcium carbonate during the subsequent solid-liquid separation; especially, in the stirring and mixing process, CO is introduced from the bottom of the reaction kettle 2 Along with CO 2 The gas moves upwards in the reaction kettle, so that the dispersion of the calcium carbonate raw material in hot water is quickened, magnesium ions are promoted to form a slightly soluble substance to be removed, and the impurity removal rate of hot water washing is further improved.
The production equipment for purifying the medicinal calcium carbonate has the beneficial effects that:
the production equipment is provided with CO below the reaction kettle 2 The charging pipe can enable the calcium carbonate to be charged with CO while being washed by hot water 2 The efficiency of removing impurities by hot water washing is obviously improved; a filter screen is arranged at an air inlet of the drying equipment, so that the pollution of calcium carbonate in the drying process is avoided; provided in the crushing plantThe dust fall pipe is arranged at the outlet of the air outlet, so that dust mixed in the air flow discharged from the air outlet is settled by dust absorption liquid such as water in the dust removal tank, and the dust emission phenomenon in the calcium carbonate crushing process is avoided.
Drawings
FIG. 1 is a schematic diagram showing the construction of a production facility for purifying a pharmaceutical calcium carbonate according to the present invention;
FIG. 2-is a schematic structural diagram of a reaction kettle of a production facility for purifying pharmaceutical calcium carbonate according to the present invention;
FIG. 3-is a schematic view of the structure of the drying oven in FIG. 1;
FIG. 4-is an enlarged schematic view at A in FIG. 3;
FIG. 5-is a front view of the comminution apparatus of FIG. 1;
fig. 6-is a rear view of the comminution apparatus of fig. 1.
In the figure: 1. a reaction kettle, 11 heating constant temperature jackets, 12 stirring devices, 13 and CO 2 The device comprises an air charging pipe, 131, a one-way valve, 14, a discharging pipe, 2, a solid-liquid separation device, 3, a drying device, 31, an air inlet, 32, a filter screen, 4, a crushing device, 41, an air outlet, 5, an air source device, 6, a dust fall tank, 7, a dust fall pipe, 8 and dust collection liquid, wherein the flow direction of materials is shown in the figure.
Detailed Description
The invention is further described below with reference to the drawings and examples.
Example 1
Referring to fig. 1-4, a production device for purifying medicinal calcium carbonate comprises a reaction kettle 1, a solid-liquid separation device 2, a drying device 3 and a crushing device 4, wherein a stirring device 12 and a heating constant-temperature jacket 11 are arranged in the reaction kettle 1, and the bottom of the reaction kettle is connected with a CO inlet into the reaction kettle 1 2 CO of (c) 2 A gas charging tube 13, said CO 2 The air charging tube 13 is provided with a one-way valve 131 and is communicated with the air source device 5; the discharging pipe 14 of the reaction kettle 1 is communicated with the solid-liquid separation device 2; the filter cake after the solid-liquid separation device 2 is returned to the reaction kettle 1 for washing or is sent to the drying device 3 for drying, and the material dried by the drying device 3 is sent to the crushing device 4 for crushing。
The air inlet 31 of the drying device 3 is provided with a filter screen 32 with the aperture of 100 meshes.
The air outlet 41 of the smashing device 4 is connected with a dust fall pipe 7, the free end of the dust fall pipe 7 is placed below the liquid level of the dust collection liquid 8 of the dust collection tank, and therefore the dust emission phenomenon in the calcium carbonate smashing process is avoided or reduced, and meanwhile the production environment of calcium carbonate is improved.
The dust-absorbing liquid 8 is water.
The invention relates to a working principle of production equipment for purifying medicinal calcium carbonate and a use method thereof, wherein the working principle comprises the following steps:
the heating constant temperature jacket 11 in the reaction kettle 1 can ensure that the calcium carbonate in the reaction kettle 1 is maintained under constant temperature in the hot water washing process, and the stirring device 12 can ensure that the calcium carbonate is fully mixed to form suspension liquid and CO in the hot water washing process 2 The gas charging pipe 13 can continuously charge CO into the reaction kettle 1 at constant speed 2 ，CO 2 The one-way valve 131 on the gas tube 13 prevents calcium carbonate from entering the CO 2 And an inflation tube 13. The calcium carbonate suspension washed by hot water in the reaction kettle 1 is pumped into the solid-liquid separation device 2 through the discharge pipe 14 for solid-liquid separation, the filter cake after solid-liquid separation is returned into the reaction kettle 1 again for washing by hot water, the filter cake is repeatedly separated by the solid-liquid separation device 2, after repeated washing for several times, the filter cake obtained by the separation of the solid-liquid separation device 2 is sent into the drying device 3 for blast drying at 85+/-2 ℃, the dried calcium carbonate is sent into the crushing device 4 for crushing, dust mixed with air flow discharged by the air outlet 41 of the crushing device 4 is settled by the dust fall tank 6, dust in the crushing process can be reduced, and the dust in the dust fall tank 6 can be sent into the reaction kettle 1 for recycling again.
Example 2
The method for purifying the medicinal calcium carbonate comprises the following steps of:
1) Washing with hot water: taking 100KG of an edible grade calcium carbonate raw material, adding the edible grade calcium carbonate raw material into hot water with the temperature of 100KG and 60+/-1 ℃ and stirring and mixing for 1h at constant temperature, and removing filtrate through solid-liquid separation to obtain a calcium carbonate filter cake; repeatedly washing the filter cake with hot water of 100KG and 60+/-1 ℃ for 2 times to obtain a calcium carbonate primary product;
2) Drying and crushing: and (3) carrying out filter pressing, drying and crushing on the calcium carbonate primary product obtained in the step (1).
Example 3
The method for purifying the medicinal calcium carbonate comprises the following steps of:
1) Washing with hot water: taking 100KG of edible calcium carbonate raw material, putting into hot water with the temperature of 100KG and 60+/-1 ℃, and continuously introducing CO from the bottom of the reaction kettle 2 ，CO 2 Introducing flow of 30KG/h, stirring and mixing for 1h at constant temperature, and removing filtrate by solid-liquid separation to obtain a calcium carbonate filter cake; repeatedly washing the filter cake with hot water of 100KG and 60+/-1 ℃ for 2 times to obtain a calcium carbonate primary product;
2) Drying and crushing: and (3) carrying out filter pressing, drying and crushing on the calcium carbonate primary product obtained in the step (1).
Example 4
The method for purifying the medicinal calcium carbonate comprises the following steps of:
1) Washing with hot water: taking 100KG of edible calcium carbonate raw material, putting into hot water with the temperature of 100KG and 60+/-1 ℃, and continuously introducing CO from the bottom of the reaction kettle 2 ，CO 2 Introducing flow of 30KG/h, stirring and mixing for 1h at constant temperature, and removing filtrate by solid-liquid separation to obtain a calcium carbonate filter cake; repeatedly washing the filter cake with hot water of 100KG and 60+/-1 ℃ for 3 times to obtain a calcium carbonate primary product;
2) Drying and crushing: and (3) carrying out filter pressing, drying and crushing on the calcium carbonate primary product obtained in the step (1).
Example 5
The method for purifying the medicinal calcium carbonate comprises the following steps of:
1) Washing with hot water: taking 100KG of edible calcium carbonate raw material, putting into hot water with the temperature of 100KG and 55+/-1 ℃, and continuously introducing CO from the bottom of the reaction kettle 2 ，CO 2 Introducing flow of 30KG/h, stirring and mixing for 2h at constant temperature, and removing filtrate by solid-liquid separation to obtain a calcium carbonate filter cake; repeatedly washing the filter cake with hot water of 100KG and 60+/-1 ℃ for 1 time to obtain a calcium carbonate primary product;
2) Drying and crushing: and (3) carrying out filter pressing, drying and crushing on the calcium carbonate primary product obtained in the step (1).
Example 6
The method for purifying the medicinal calcium carbonate comprises the following steps of:
1) Washing with hot water: taking 100KG of edible calcium carbonate raw material, adding the edible calcium carbonate raw material into hot water with the temperature of 150KG and 65+/-1 ℃, and continuously introducing CO from the bottom of a reaction kettle 2 ，CO 2 Introducing flow of 30KG/h, stirring and mixing for 1.5h at constant temperature, and removing filtrate by solid-liquid separation to obtain a calcium carbonate filter cake; repeatedly washing the filter cake with hot water of 150KG and 60+/-1 ℃ for 1 time to obtain a calcium carbonate primary product;
2) Drying and crushing: and (3) carrying out filter pressing, drying and crushing on the calcium carbonate primary product obtained in the step (1).
Example 7
The method for purifying the medicinal calcium carbonate comprises the following steps of:
1) Washing with hot water: taking 100KG of edible calcium carbonate raw material, adding into hot water with the temperature of 150KG and 80+/-1 ℃, and continuously introducing CO from the bottom of the reaction kettle 2 ，CO 2 Introducing flow of 30KG/h, stirring and mixing for 1.5h at constant temperature, and removing filtrate by solid-liquid separation to obtain a calcium carbonate filter cake; repeatedly washing the filter cake with hot water of 150KG and 60+/-1 ℃ for 1 time to obtain a calcium carbonate primary product;
2) Drying and crushing: and (3) carrying out filter pressing, drying and crushing on the calcium carbonate primary product obtained in the step (1).
Comparative example 1
A method for purifying pharmaceutical calcium carbonate comprising the steps of:
1) Washing with hot water: taking 100KG of an edible grade calcium carbonate raw material, adding the edible grade calcium carbonate raw material into hot water with the temperature of 100KG and 40+/-1 ℃ and stirring and mixing for 1h at constant temperature, and removing filtrate through solid-liquid separation to obtain a calcium carbonate filter cake; repeatedly washing the filter cake with hot water of 100KG and 60+/-1 ℃ for 2 times to obtain a calcium carbonate primary product;
2) Drying and crushing: and (3) carrying out filter pressing, drying and crushing on the calcium carbonate primary product obtained in the step (1).
Comparative example 2
A method for purifying pharmaceutical calcium carbonate comprising the steps of:
1) Washing with hot water: taking 100KG of an edible grade calcium carbonate raw material, adding the edible grade calcium carbonate raw material into hot water with the temperature of 100KG and 80+/-1 ℃ and stirring and mixing for 1h at constant temperature, and removing filtrate through solid-liquid separation to obtain a calcium carbonate filter cake; repeatedly washing the filter cake with hot water of 100KG and 60+/-1 ℃ for 2 times to obtain a calcium carbonate primary product;
2) Drying and crushing: and (3) carrying out filter pressing, drying and crushing on the calcium carbonate primary product obtained in the step (1).
Comparative example 3
A method for purifying pharmaceutical calcium carbonate comprising the steps of:
1) Washing with hot water: taking 100KG of an edible grade calcium carbonate raw material, adding the edible grade calcium carbonate raw material into hot water with the temperature of 100KG and 60+/-1 ℃ and stirring and mixing for 1h at constant temperature, and removing filtrate by solid-liquid separation to obtain a calcium carbonate primary product;
2) Drying and crushing: and (3) carrying out filter pressing, drying and crushing on the calcium carbonate primary product obtained in the step (1).
Comparative example 4
The method for purifying the medicinal calcium carbonate comprises the following steps of:
1) Washing with hot water: taking 100KG of an edible grade calcium carbonate raw material, adding the edible grade calcium carbonate raw material into hot water with the temperature of 100KG and 60+/-1 ℃ and stirring and mixing for 0.5h at constant temperature, and removing filtrate by solid-liquid separation to obtain a calcium carbonate filter cake; repeatedly washing the filter cake with hot water of 100KG and 60+/-1 ℃ for 2 times to obtain a calcium carbonate primary product;
2) Drying and crushing: and (3) carrying out filter pressing, drying and crushing on the calcium carbonate primary product obtained in the step (1).
The calcium carbonate finished products obtained in examples 2 to 5 and comparative examples 1 to 4 were subjected to impurity detection, and specific detection indexes and methods are as follows:
(1) Chloride: 0.10g of the product was taken, 10ml of diluted nitric acid was added thereto, the mixture was boiled for 2 minutes, cooled and filtered if necessary, and the mixture was checked according to law (general rule 0801), and the mixture was not more concentrated (0.03%) than the control solution prepared from 3.0ml of a standard sodium chloride solution.
(2) Sulfate: 0.10g of the product was taken, diluted hydrochloric acid 2ml was added thereto, and the mixture was boiled for 2 minutes, cooled, filtered if necessary, and checked according to law (general rule 0802), and the mixture was not more concentrated (0.2%) than the control solution prepared from 2.0ml of the standard potassium sulfate solution.
(3) Barium salt: mixing 2.0g of the product with 10ml of water, adding diluted hydrochloric acid dropwise to dissolve, diluting with water to 100ml, dipping the solution with platinum wire, and burning in colorless flame to obtain green product
(4) Iron salt: 0.12g of the product was taken and diluted hydrochloric acid 2ml and water were added in an appropriate amount to dissolve it into 25ml, and the test was carried out (general rule 0807), and if color development was carried out, it was not deeper (0.04%) than that of a control solution prepared from 5.0ml of a standard iron solution.
(5) Taking l.og of the magnesium salt and alkali metal salt, adding 20ml of water and 10ml of dilute hydrochloric acid for dissolution, adding 1 drop of methyl red indicator solution, boiling, dripping ammonia test solution for neutralization, adding excessive ammonium oxalate test solution to enable calcium to be completely precipitated, heating on a water bath for 1 hour, cooling, adding water for dilution into 100ml, stirring uniformly, filtering, separating 50ml of filtrate, adding 0.5ml of sulfuric acid, drying by distillation, burning till constant weight, and keeping residue less than 1.0%.
The analysis results of the respective detection indexes of the calcium carbonate finished products obtained in examples 2 to 5 and comparative examples 1 to 4 are shown in Table 1.
As is clear from table 1 above, example 2 shows that the hot water washing temperature is different from comparative examples 1 and 2, and the effect of washing calcium carbonate with hot water at 55 to 65 ℃ is remarkable, the effect of removing magnesium salt and alkali metal salt in calcium carbonate is too high, the effect of removing magnesium salt and alkali metal salt in hot water washing is equivalent, but the energy consumption of production increases with the increase of washing temperature, the water temperature is too low, and the content of magnesium salt and alkali metal salt is not satisfactory.
Examples 3 to 6 compared to example 2 and comparative examples 1 to 4, CO 2 The calcium carbonate is introduced into the reaction kettle, so that the dispersion of the calcium carbonate in hot water is promoted, magnesium salt and alkali metal salt mixed in the calcium carbonate are fully dissolved in the hot water, and the efficiency of washing and removing impurities in the hot water is remarkably improved.
As is clear from a comparison of examples 6 and 7, the CO introduced into the reaction vessel may be caused as the washing temperature of the hot water increases 2 The molecular movement speed is accelerated, the retention time of the calcium carbonate in the mixed solution is shortened, the dispersing effect of the calcium carbonate is weakened, the contact time with magnesium ions mixed in the calcium carbonate is shortened, and the magnesium carbonate and alkali metal are not favorable for forming micro-solubles such as magnesium carbonate and the like, thereby leading the magnesium salt and the alkali metal to beThe removal rate of the belonged salt is reduced. Next, in example 7, the water temperature in the hot water washing was the same as in comparative example 2, but CO was introduced into the reaction vessel in example 7 2 Promoting effect on magnesium salt and alkali metal salt still exists.
As is clear from the comparison between the examples 2 and 4, the stirring and mixing time is too short, which is not beneficial to the full mixing and dispersion of calcium carbonate, and further results in higher impurity content of magnesium salt and alkali metal salt, which is not in accordance with the requirement of medicinal calcium carbonate.
As is clear from the comparison between the example 2 and the comparative example 3, the hot water washing times are smaller, which is unfavorable for the removal of impurities of magnesium salt and alkali metal salt in calcium carbonate, and the impurity content in the finished product is higher and does not meet the requirement of medical calcium carbonate.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present invention. Furthermore, features defining "first", "second" may include one or more such features, either explicitly or implicitly. In the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
Claims (7)
1. A method for purifying pharmaceutical calcium carbonate comprising the steps of:
1) Washing with hot water: adding the calcium carbonate raw material into hot water with the mass being 0.8-1.5 times of that of the calcium carbonate and the temperature being 55-65 ℃ for constant-temperature stirring and mixing for 1-2 hours, and removing filtrate through solid-liquid separation to obtain a calcium carbonate filter cake; repeatedly washing the filter cake with hot water of 0.8-1.5 times of calcium carbonate and at 55-65 ℃ for more than 1 time, and continuously introducing CO from the bottom of the reaction kettle (1) in the hot water washing process 2 ，CO 2 The flow rate of the mixture is 20-30 kg/h, so that magnesium salt and alkali metal salt mixed in the calcium carbonate raw material are dissolved in hot water and removed, and a calcium carbonate primary product is obtained;
2) Drying and crushing: and (3) carrying out filter pressing, drying and crushing on the calcium carbonate primary product obtained in the step (1).
2. The method for purifying pharmaceutical calcium carbonate according to claim 1, wherein the drying temperature is 85±2 ℃.
3. The method for purifying pharmaceutical calcium carbonate according to claim 1 or 2, wherein the number of hot water washes is 3 to 5.
4. The utility model provides a production facility is used in purification of medicinal calcium carbonate, includes reation kettle (1), solid-liquid separation device (2), drying device (3) and reducing mechanism (4), its characterized in that, be equipped with agitating unit (12) and heating constant temperature jacket (11) in reation kettle (1), its bottom is connected with and lets in CO in reation kettle (1) 2 CO of (c) 2 An inflation tube (13), said CO 2 The air charging pipe (13) is provided with a one-way valve (131) and is communicated with the air source device (5); a discharge pipe (14) of the reaction kettle (1) is communicated with the solid-liquid separation device (2); the filter cake after the solid-liquid separation device (2) is returned to the reaction kettle (1) for washing or is sent to the drying device (3) for drying, and the drying device (3) is used for dryingThe materials are sent into a crushing device (4) for crushing.
5. The production facility for purification of pharmaceutical calcium carbonate according to claim 4, characterized in that the air inlet (31) of the drying device (3) is provided with a filter screen (32).
6. The production equipment for purifying medical calcium carbonate according to claim 4 or 5, wherein the air outlet (41) of the crushing device (4) is connected with a dust fall pipe (7), and the free end of the dust fall pipe (7) is placed under the liquid surface of dust collection liquid (8) of the dust collection tank, so that the dust emission phenomenon in the crushing process of calcium carbonate is avoided or reduced, and the production environment of calcium carbonate is improved.
7. The production facility for purifying pharmaceutical calcium carbonate according to claim 6, wherein the dust collection liquid (8) is water.
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