CN112479238A - Method for preparing aluminum magnesium carbonate - Google Patents
Method for preparing aluminum magnesium carbonate Download PDFInfo
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- CN112479238A CN112479238A CN202011422870.XA CN202011422870A CN112479238A CN 112479238 A CN112479238 A CN 112479238A CN 202011422870 A CN202011422870 A CN 202011422870A CN 112479238 A CN112479238 A CN 112479238A
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- alkali solution
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- mixed alkali
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- 238000000034 method Methods 0.000 title claims abstract description 53
- UJOHNXQDVUADCG-UHFFFAOYSA-L aluminum;magnesium;carbonate Chemical compound [Mg+2].[Al+3].[O-]C([O-])=O UJOHNXQDVUADCG-UHFFFAOYSA-L 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 239000003513 alkali Substances 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 30
- 239000012266 salt solution Substances 0.000 claims description 25
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 24
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 15
- 235000017550 sodium carbonate Nutrition 0.000 claims description 15
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 12
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 9
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 6
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 235000011181 potassium carbonates Nutrition 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 abstract description 33
- 229960001545 hydrotalcite Drugs 0.000 abstract description 33
- 229910001701 hydrotalcite Inorganic materials 0.000 abstract description 33
- 238000002360 preparation method Methods 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- 238000013341 scale-up Methods 0.000 abstract description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 2
- 229940069428 antacid Drugs 0.000 abstract description 2
- 239000003159 antacid agent Substances 0.000 abstract description 2
- 230000001458 anti-acid effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 206010020601 Hyperchlorhydria Diseases 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 19
- 235000011121 sodium hydroxide Nutrition 0.000 description 14
- 238000004090 dissolution Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910001051 Magnalium Inorganic materials 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 229940024545 aluminum hydroxide Drugs 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 235000011118 potassium hydroxide Nutrition 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 150000004645 aluminates Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 3
- 239000002370 magnesium bicarbonate Substances 0.000 description 3
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 3
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 208000007882 Gastritis Diseases 0.000 description 1
- 206010030216 Oesophagitis Diseases 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 206010000059 abdominal discomfort Diseases 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229940024546 aluminum hydroxide gel Drugs 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 208000006766 bile reflux Diseases 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 208000000718 duodenal ulcer Diseases 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 208000006881 esophagitis Diseases 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000027119 gastric acid secretion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
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
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
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
The invention discloses a method for preparing aluminum magnesium carbonate, which comprises the step of mixing a reaction material with an alkali solution (containing OH)‑、CO3 2‑) Adding the materials into a reaction system in a dispersing and dropwise adding mode for reaction to prepare the hydrotalcite raw material with excellent acidity, wherein the pH value can be maintained between 3 and 5 for a long time. The prepared preparation product shows excellent performance of producing durable antacid clinical curative effect when treating hyperacidity. The preparation method is simple to operate, high in yield and suitable for industrial scale-up production.
Description
Technical Field
The invention belongs to the field of organic chemistry, inorganic chemistry and pharmaceutical chemistry, and particularly relates to a method for preparing aluminum magnesium carbonate.
Background
The molecular formula of the hydrotalcite is Al2Mg6(OH)16 CO3·4H2O, molecular weight 604, is a white or off-white granular powder, is almost insoluble in water, and is dissolved in dilute hydrochloric acid with generation of bubbles. Is clinically used for treating duodenal ulcer and acute and chronic stomachInflammation, bile reflux esophagitis, stomach discomfort associated with excess gastric acid secretion.
The aluminum magnesium carbonate belongs to one kind of aluminum magnesium hydrotalcite, and the aluminum magnesium hydrotalcite has the structural general formula of AlaMgb(OH)c XCO3·YH2O, prepared on the basis of Al3+Aluminum salt and Mg-containing2+The magnesium salt is obtained by coprecipitation under alkaline environment (such as sodium hydroxide, potassium hydroxide, ammonium bicarbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, etc.). Among the documents disclosed in the prior art, there are two main types of methods for producing aluminum magnesium hydrotalcite.
The method comprises the following steps: CN1507944 discloses a method for synthesizing magnesium aluminum hydrotalcite, which comprises mixing active MgO with aqueous solution of Al (OH)3, NaOH and Na2CO3, controlling pH value at 10-12, and reacting for 4-15 hours under stirring at 60-100 deg.C to obtain magnesium aluminum hydrotalcite with single phase.
The second method comprises the following steps: with water-soluble Mg2+(e.g., magnesium sulfate, magnesium chloride, etc.) with Al3+(such as aluminum sulfate, aluminum nitrate, aluminum chloride and the like) in an alkaline environment to prepare the aluminum-magnesium hydrotalcite. Structural general formula Al of aluminum magnesium hydrotalciteaMgb(OH)c XCO3·YH2O is not difficult to find, and OH must be simultaneously present in the reaction process-、CO3 2-To ensure the alkaline environment of the system. Wherein CO is3 2-Derived from metal carbonates (e.g. ammonium bicarbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, etc.), and OH-Can be derived from metal hydroxide (such as sodium hydroxide, potassium hydroxide, etc.), or from hydrolysis of excess metal carbonate in water to produce OH-. Therefore, the preparation method can be further divided into the following 2 subclasses according to the different substances providing alkaline environment.
The method comprises the following steps: such as disclosed in CN101381094, will contain Al3+(e.g., aluminum sulfate, aluminum nitrate, aluminum chloride, etc.) with a compound containing Mg2+(e.g., magnesium sulfate, magnesium chloride, etc.) with a large excess of a metal carbonate (e.g., ammonium bicarbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, etc.) in waterAnd reacting to obtain the aluminum magnesium hydrotalcite.
The method 2 comprises the following steps: such as CN103395808, CN101386424, CN101381094, etc., the Al-containing compound is obtained by3+(e.g., aluminum sulfate, aluminum nitrate, aluminum chloride, etc.) with a compound containing Mg2+(such as magnesium sulfate, magnesium chloride, etc.) are dissolved in water together to form a mixed salt solution, and then reacted with a mixed alkali solution in which a metal carbonate (such as ammonium bicarbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, etc.) and a metal hydroxide (such as sodium hydroxide, potassium hydroxide, etc.) are dissolved in water to obtain the aluminum magnesium hydrotalcite.
CN107986306A discloses a method for preparing hydrotalcite, which comprises the following steps: s1, preparing a magnesium hydroxide and aluminum hydroxide suspension, adding an ammonium bicarbonate solution into the magnesium hydroxide and aluminum hydroxide suspension, and stirring and mixing uniformly; s2, slowly heating the mixed solution in the step S1 from room temperature to 85-90 ℃, wherein the heating rate is not more than 0.5 ℃/min, and reacting for 2-3 h at the temperature of 85-90 ℃; and S3, cooling the substance reacted in the step S2 to room temperature, and washing, separating and drying to obtain the hydrotalcite.
CN101343078 discloses a process for preparing aluminium magnesium carbonate, which comprises adding aluminium hydroxide into sodium hydroxide solution to dissolve, obtaining sodium aluminate, diluting with water, introducing carbon dioxide to slowly and uniformly react to obtain alkaline-aluminium carbonate-gel (gel) and sodium carbonate, adding magnesium chloride and sodium hydroxide to generate magnesium bicarbonate, maintaining the temperature at 85 deg.c, and reacting to obtain aluminium magnesium carbonate.
CN101386424 discloses a preparation method of modified and molded magnesium-aluminum hydrotalcite, which is characterized by comprising the following steps: separately preparing a mixture containing Mg2+、Al3+The mixed salt aqueous solution and the mixed alkaline aqueous solution are mixed, aging and crystallization are carried out after complete reaction, and the magnalium hydrotalcite is obtained after filtration, washing and drying.
CN101381094 discloses a method for preparing nano magnesium-aluminum hydrotalcite, which comprises preparing a magnesium-aluminum mixed salt solution; preparing an ammonium bicarbonate solution; simultaneously adding the two mixed solutions into a static mixer to perform chemical reaction to generate the magnalium hydrotalcite microcrystal; and then growing the magnalium hydrotalcite microcrystal in a curing reactor to obtain the nano magnalium hydrotalcite product.
CN106379924 discloses a preparation method of nano magnesium-aluminum hydrotalcite, which takes magnesium chloride, aluminum chloride, sodium carbonate and sodium hydroxide as main raw materials, adds a foaming auxiliary agent sodium oleate, firstly prepares a precursor filter cake through a bubble liquid film reaction, and then prepares the nano magnesium-aluminum hydrotalcite through a hydrothermal reaction, filtration, washing and drying.
CN 102139901A method for preparing magnesium-aluminum hydrotalcite comprises reacting soluble magnesium salt solution with ammonia water solution to generate magnesium hydroxide precipitate, introducing carbon dioxide, dissolving the precipitate gradually to generate magnesium bicarbonate solution, mixing magnesium hydroxide, aluminum hydroxide gel and magnesium bicarbonate according to a molar ratio of 5: 2: 1, adding the mixture into a reaction kettle, controlling the temperature to react to obtain the magnesium-aluminum hydrotalcite, and drying the magnesium-aluminum hydrotalcite by a spray dryer.
However, the above-described known production methods all have their disadvantages, such as the use of magnesium oxide as Mg, which is a water-insoluble substance, in the first method2+Because the magnesium oxide is insoluble in water, the magnesium oxide which is not completely reacted exists in the form of impurities in the target product, and the influence on the acid-making power is generated to a certain extent. Whereas in method 1 hydrolysis with carbonate provides OH-But from the formula Al of hydrotalcite2Mg6(OH)16CO3·4H2O has a hydroxyl number of 16 and is only dependent on OH provided by hydrolysis of carbonate-The reaction requirement is difficult to meet, the number of hydroxyl in the structure of the aluminum-magnesium hydrotalcite prepared by the method 1 is less than 16, 14 or even less, and the final result is that the acid resistance time of the aluminum-magnesium hydrotalcite product prepared by the method 1 is too short (the pH is maintained between 3 and 5 for only 60min or less). However, in the prior published documents, the mixed salt solution and the mixed alkali solution are directly mixed and reacted, and as a result, the obtained hydrotalcite is in a colloidal state due to local over-strong alkalinity (the pH value is more than 14) in the reaction system, and subsequent washing cannot be realized (due to the post-treatment process of the medicinal hydrotalciteThe excessive OH in the system must be removed by a large amount of water washing-、CO3 2-) And solid-liquid separation, even by prolonging the aging time (making the solid particles as large as possible) as mentioned in the literature, the practical experimental results are still very limited. Therefore, although the method 2 can obtain a hydrotalcite sample with a long acid-making capacity to some extent, it cannot realize industrial scale-up production.
In view of the problems of the prior art, the present inventors have conducted extensive studies, for example, the present inventors have also tried to solve the colloidal morphology in the method 2 by using other conventional methods, such as reacting a part of the mixed salt solution with a part of the carbonate, and adding the rest of the mixed salt solution and the mixed alkali solution; for example, the stirring speed of the reaction kettle is increased; further prolonging the aging time (24h or even longer) is also exemplified, but none of them is solved. The problems cannot be finally solved until the novel preparation method of feeding the mixed alkali solution by adopting the dispersed dropwise feeding mode, controlling the feeding speed of the mixed alkali solution to be 0.9-2.5 kg/min and simultaneously controlling the pH value of the system to be stable between 10-12 is adopted.
Disclosure of Invention
The invention aims to provide a method for preparing aluminum magnesium carbonate. The method comprises the steps of feeding the mixed alkali solution in a dispersing and dropwise adding feeding mode, controlling the feeding speed of the mixed alkali solution to be 0.9-2.5 kg/min, controlling the pH value of a reaction system to be 10-12, not needing to age after the feeding of the materials is finished, completing the reaction for about 1h, enabling the system not to present a colloidal state any more, enabling subsequent washing and solid-liquid separation to be smooth, enabling the obtained magnesium aluminate carbonate to have excellent acid making performance, and enabling the time for the pH value to be 3-5 to be more than 90min in an in-vitro acid making force test.
To achieve the object of the present invention, the following embodiments are provided.
The invention relates to a method for preparing aluminum magnesium carbonate, which comprises the following steps:
1) preparing Al-containing material according to molar ratio3+、Mg2+And a mixed salt solution of (2), and containing OH-、CO3 2-The mixed alkali solution of (1);
2) adding the prepared mixed salt solution and the prepared mixed alkali solution into a reaction kettle for reaction, wherein the mixed alkali solution is added into the reaction kettle in a dispersed dropwise adding feeding mode, and the pH value range of a reaction system is controlled to be 10-12;
3) after the reaction is finished, the target product can be obtained by washing, filtering and drying.
The method of the present invention described above, step 1) said Al3+Is derived from one or more of aluminum sulfate, aluminum nitrate, aluminum chloride and the like, and the Mg2+Derived from magnesium sulfate, magnesium chloride, etc. or mixtures thereof, the OH-Derived from sodium hydroxide, potassium hydroxide, the like or mixtures thereof, said CO3 2-Is one or more of ammonium bicarbonate, sodium carbonate, potassium carbonate and sodium bicarbonate; step 1) the molar ratio is nAl3+：mMg2+：xOH-：yCO3 2-1: 3: (9-14): (1 to 1.5), preferably, the molar ratio is nAl3+：mMg2+：xOH-：yCO3 2-1: 3: (9-12): (1-1.2); the feeding mode of the dispersing and dripping in the step 2) is
Feeding the mixed alkali solution into a reaction kettle for reaction in a mode of multiple dropping positions at a proper speed (the dropping schematic diagram of the mixed alkali solution is shown in the attached figure 1 in detail), wherein the proper feeding speed is as follows: the dispersion and dropwise addition speed of the mixed alkali solution is 0.9 kg/min-2.5 kg/min, preferably 0.9 kg/min-1.6 kg/min. Preferably, the pH value range in the step 2) is 10-11.
In one embodiment, the method for preparing aluminum magnesium carbonate comprises the following steps:
1) according to nAl3+：mMg2+：xOH-：y CO3 2-1: 3: 9: 1.0 material molar ratio to prepare a mixed salt solution containing aluminum chloride and magnesium chloride and a mixed alkali solution of sodium hydroxide and sodium carbonate;
2) dropwise adding the mixed alkali solution into a reaction kettle in a dispersing and dropwise adding feeding mode of 0.9-1.6 kg/min, dropwise adding the mixed salt solution into the reaction kettle for reaction in a conventional (single-point dropwise adding) dropwise adding mode, controlling the pH value of a reaction system to be 10-11, and heating to about 80 ℃ for reaction for 1h after the feeding is finished;
3) after the reaction is finished, the target product can be obtained by adding water for washing for 2-5 times, filtering and drying.
Effects of the invention
According to the method, a mixed alkali solution (material) is fed in a dispersing and dropwise adding feeding mode, the feeding speed of the mixed alkali solution is controlled to be 0.9 kg/min-2.5 kg/min, and the pH value of a feeding process system is stabilized to be 10-12. The material is not required to be aged after the feeding is finished, the reaction can be finished after about 1h, the system does not show a colloidal form any more, the subsequent washing and the solid-liquid separation are very smooth, the operation is simple and convenient, and the method is suitable for industrial scale-up production. Meanwhile, the obtained hydrotalcite-like acid-making capacity is excellent in performance, and the time for testing the pH value to be between 3 and 5 in an in-vitro acid-making capacity is more than 90 min.
Drawings
FIG. 1 is a schematic view of a reaction apparatus.
In the figure: 1-mixed alkali liquor dripping tank; 2-mixed salt solution dropping tank; 3-a multi-position point dropping hole or spraying device for dispersedly dropping the mixed alkali liquor; 4-a reaction kettle.
Detailed Description
The following examples serve to further understand the nature of the invention, but do not limit the scope of the invention in any way.
Example 1 preparation of hydrotalcite by Dispersion dropwise addition of a Mixed alkali solution
The molar ratio of the materials is as follows: nAl3+：mMg2+：xOH-：yCO3 2-1: 3: 9: and 1.0, controlling the pH value of the reaction system to be 10-11 in the dropping process. The reaction equipment is schematically shown in figure 1.
The preparation process comprises the following steps:
preparing a mixed salt solution: dissolving 150.4kg of magnesium chloride and 70.4kg of aluminum chloride into 200kg of water together, stirring and dissolving to form a mixed salt solution;
preparing a mixed alkali solution: dissolving 56.2kg of sodium carbonate and 190.8kg of sodium hydroxide into 200kg of water together, and stirring for dissolving to form a mixed alkali solution;
and dispersing and dropwise adding the prepared mixed alkali solution into a reaction kettle at the speed of 0.9kg/min, dropwise adding the prepared mixed salt solution into the reaction kettle in a conventional (single-point dropwise adding) dropwise adding manner for reaction, and controlling the pH value of the whole feeding process to be 10-11. After the addition is finished, the temperature is raised to about 80 ℃ for reaction for 1 h.
After the reaction is finished, water is added for washing for 5 times, and solid-liquid separation is smoothly realized each time. After washing, the mixture was filtered and dried at 100 ℃ for 3 hours to obtain a 54.2kg sample of hydrotalcite.
The acid making capacity of the sample is measured:
the method for measuring the acid-making capacity of the sample comprises the following steps: about 1.0g of each of the above samples was precisely weighed. Adding 30ml of water and 70ml of 0.1mol/L hydrochloric acid solution into the dissolution cup, uniformly stirring, placing in a dissolution instrument, heating to 37 ℃, stirring at the speed of 200 revolutions per minute, monitoring the change of the pH value of the solution in the dissolution cup by using a pH meter, and recording the initial pH value of the solution. Putting a sample into the dissolution cup, starting a peristaltic pump, pumping 0.1mol/L hydrochloric acid solution at 37 ℃ into the dissolution cup at the flow rate of 2.0 +/-0.1 ml/min, and recording the time when the pH value of the solution reaches 3.0 as TpH3(ii) a The time for which the pH value of the solution is kept between 3.0 and 5.0 is recorded as TpH3～5. The final sample is kept at pH 3.0-5.0 for 98 min.
Example 2 preparation of hydrotalcite by Dispersion dropwise addition of a Mixed alkali solution
The molar ratio of the materials is as follows: nAl3+：mMg2+：xOH-：yCO3 2-1: 3: 14: and 1.5, controlling the pH value of the reaction system to be 11-12 in the dropwise adding process. The reaction equipment is schematically shown in figure 1.
The preparation process comprises the following steps:
preparing a mixed salt solution: dissolving 117.3kg of magnesium chloride and 70.4kg of aluminum sulfate together into 200kg of water to form a mixed salt solution;
preparing a mixed alkali solution: dissolving 44.5kg of sodium carbonate and 151.2kg of sodium hydroxide together in 200kg of water to form a mixed alkali solution;
and then dispersing and dropwise adding the mixed alkali solution into a reaction kettle at the speed of 2.5kg/min, dropwise adding the prepared mixed salt solution into the reaction kettle for reaction in a conventional (single-point dropwise adding) dropwise adding manner, and controlling the pH value of the whole feeding process to be 11-12. After the spraying and feeding are finished, the temperature is raised to about 80 ℃ for reaction for 1 h.
After the reaction is finished, water is added for washing for 3-5 times, and solid-liquid separation is smoothly realized each time. After washing, the mixture was filtered and dried at 100 ℃ for 3 hours to obtain 52.4kg of sample.
The acidity of the sample was measured in the same manner as in example 1: the pH is maintained at 3.0-5.0 for a period of 93 min.
Example 3 preparation of hydrotalcite by Dispersion dropwise addition of a Mixed alkali solution
The molar ratio of the materials is as follows: nAl3+：mMg2+：xOH-：yCO3 2-1: 3: 12: and 1.2, controlling the pH value of the reaction system to be 10-11 in the dropwise adding process.
The preparation process comprises the following steps:
preparing a mixed salt solution: 191.4kg magnesium sulfate and 70.4kg aluminium chloride are dissolved together in 200kg water to form a mixed salt solution;
preparing a mixed alkali solution: dissolving 67.4kg of sodium carbonate and 254.4kg of sodium hydroxide together in 200kg of water to form a mixed alkali solution;
and then dispersing and dropwise adding the mixed alkali solution into a reaction kettle at the speed of 1.6kg/min, dropwise adding the prepared mixed salt solution into the reaction kettle for reaction in a conventional (single-point dropwise adding) dropwise adding manner, and controlling the pH value of the whole feeding process to be 10-11. After the spraying and feeding are finished, the temperature is raised to about 80 ℃ for reaction for 1 h.
After the reaction is finished, water is added for washing for 5 times, and solid-liquid separation is smoothly realized each time. After washing, the mixture was filtered and dried at 100 ℃ for 3 hours to obtain 54.8kg of a sample.
The acidity of the sample was measured in the same manner as in example 1: the pH is kept at 3.0-5.0 for 96 min.
Comparative example 1 preparation of magnesium Aluminocarbonate by conventional dropping method (repeat Prior Art published method 2)
Material(s)The molar ratio is as follows: nAl3+：nMg2+：nOH-：nCO3 2-＝1：3：9：1.0；
The preparation process comprises the following steps:
preparing a mixed salt solution: dissolving 150.4g of magnesium chloride and 70.4g of aluminum chloride together into 200g of water to form a mixed salt solution;
preparing a mixed alkali solution: dissolving 56.2g of sodium carbonate and 190.8g of sodium hydroxide together in 200g of water to form a mixed alkali solution;
then, the prepared mixed salt solution and the mixed alkali are respectively added into a 1L reaction bottle by a conventional glass constant pressure dropping funnel in a conventional dropping mode (single-point dropping), and the reaction is carried out for 5 hours at the temperature of about 80 ℃. After the reaction is finished, the system is found to be in a glue state, emulsification occurs when water is added for washing, solid-liquid separation cannot be realized, a small amount of materials are finally taken for filtration, the filtration is found to be difficult, and only 4g of magnesium aluminum carbonate samples are finally obtained.
The acid making force of the sample is determined by the same method, and the time for keeping the pH value at 3.0-5.0 is 80 min.
Comparative example 2 the prior published method 1 was repeated
Dissolving 20.8g of aluminum hydroxide, 24.0g of sodium hydroxide and 8.68g of sodium carbonate into 250ml of hot water, adding 11.4g of newly purchased light magnesium oxide, stirring and mixing, carrying out reflux reaction at 100 ℃ for 10h, and finally washing, filtering and drying to obtain a magnesium aluminate carbonate sample.
The method for measuring the acid-making capacity of the sample comprises the following steps: about 1.0g of each of the above samples was precisely weighed. Adding 30ml of water and 70ml of 0.1mol/L hydrochloric acid solution into the dissolution cup, uniformly stirring, placing in a dissolution instrument, heating to 37 ℃, stirring at the speed of 200 revolutions per minute, monitoring the change of the pH value of the solution in the dissolution cup by using a pH meter, and recording the initial pH value of the solution. Putting a sample into the dissolution cup, starting a peristaltic pump, pumping 0.1mol/L hydrochloric acid solution at 37 ℃ into the dissolution cup at the flow rate of 2.0 +/-0.1 ml/min, and recording the time when the pH value of the solution reaches 3.0 as TpH3(ii) a The time for which the pH value of the solution is kept between 3.0 and 5.0 is recorded as TpH3～5. The final sample is kept at pH 3.0-5.0 for a period of 62 min.
Comparative example 3 repeat the prior published procedure 1
Firstly, 90.5g of ammonium bicarbonate is dissolved in 500ml of hot water, 70.4g of aluminum sulfate and 58.0g of magnesium chloride are added, stirred and mixed, reacted for 5 hours at about 80 ℃, and finally, a magnesium aluminate carbonate sample is obtained through washing, filtering and drying.
The acid making force of the sample is measured by the same method, and the time length for keeping the pH value at 3.0-5.0 is 52 min.
Based on the results of the above examples and comparative examples, the method of the present invention produces hydrotalcite with significantly better antacid capacity than hydrotalcite produced by the prior methods of publication one, publication 1 and publication 2.
It is also within the scope of the present invention to make simple changes and substitutions to the examples and embodiments of the present invention described above without departing from the spirit and scope of the present invention.
Claims (9)
1. A method for preparing aluminum magnesium carbonate, comprising the steps of:
1) preparing Al-containing material according to molar ratio3+、Mg2+And a mixed salt solution of (2), and containing OH-、CO3 2-The mixed alkali solution of (1);
2) adding the prepared mixed salt solution and the prepared mixed alkali solution into a reaction kettle for reaction, wherein the mixed alkali solution is added into the reaction kettle in a dispersed dropwise adding feeding mode, and the pH value range of a reaction system is controlled to be 10-12;
3) after the reaction is finished, the target product can be obtained by washing, filtering and drying.
2. The method of claim 1, step 1) the Al3+One or more selected from aluminum sulfate, aluminum nitrate and aluminum chloride, wherein Mg is2+Selected from magnesium sulfate, magnesium chloride and mixtures thereof, said OH-Selected from sodium hydroxide, potassium hydroxide and mixtures thereof, said CO3 2-Is selected from one or more of ammonium bicarbonate, sodium carbonate, potassium carbonate and sodium bicarbonate.
3. The method of claim 1, wherein the first and second light sources are selected from the group consisting of a red light source, a green light source, and a blue light source,step 1) the molar ratio is as follows: nAl3+：mMg2+：xOH-：yCO3 2-＝1：3：(9～14)：(1～1.5)。
4. The method of claim 3, wherein the molar ratio is nAl3+：mMg2+：xOH-：yCO3 2-＝1：3：(9～12)：(1～1.2)。
5. The method of claim 1, wherein the dispersing and dropping in step 2) is carried out by: and (3) feeding the mixed alkali solution into a reaction kettle for reaction in a multi-position dropwise adding mode at a proper speed.
6. The method according to claim 1, wherein the addition rate of the dispersed dropwise addition of the mixed alkali solution is 0.9kg/min to 2.5 kg/min.
7. The method according to claim 6, wherein the addition rate of the dispersed dropwise addition of the mixed alkali solution is 0.9kg/min to 1.6 kg/min.
8. The process of claim 1, 6 or 7, wherein the dispersed dropwise addition is spray dropwise addition or multi-site dropwise addition.
9. The method of claim 1, wherein the pH value in step 2) is in the range of 10 to 11.
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| WO2023056675A1 (en) * | 2021-10-09 | 2023-04-13 | 安徽大学绿色产业创新研究院 | Method for preparing magnesium-aluminum hydrotalcite by means of mother liquor circulation |
| CN116102046A (en) * | 2023-01-17 | 2023-05-12 | 山东省分析测试中心 | Crystallization method of micron-sized aluminum magnesium carbonate with narrow particle size distribution |
| CN116239137A (en) * | 2021-12-03 | 2023-06-09 | 湖南九典宏阳制药有限公司 | Preparation method of low-sodium aluminum magnesium alloy |
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