CN111453750B - Clean synthesis process of magnesium aluminum hydrotalcite - Google Patents
Clean synthesis process of magnesium aluminum hydrotalcite Download PDFInfo
- Publication number
- CN111453750B CN111453750B CN202010475473.2A CN202010475473A CN111453750B CN 111453750 B CN111453750 B CN 111453750B CN 202010475473 A CN202010475473 A CN 202010475473A CN 111453750 B CN111453750 B CN 111453750B
- Authority
- CN
- China
- Prior art keywords
- magnesium
- aluminum hydrotalcite
- aluminum
- hydrotalcite
- hydroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 105
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 105
- 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 title claims abstract description 104
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 23
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 20
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 19
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 12
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 abstract description 9
- 239000000047 product Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000008188 pellet Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 229910001051 Magnalium Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229910003023 Mg-Al Inorganic materials 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910020038 Mg6Al2 Inorganic materials 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 2
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- UJOHNXQDVUADCG-UHFFFAOYSA-L aluminum;magnesium;carbonate Chemical compound [Mg+2].[Al+3].[O-]C([O-])=O UJOHNXQDVUADCG-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 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 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- -1 hydrotalcite compound Chemical class 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002351 wastewater Substances 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 and two or more other elements, with the exception of oxygen and hydrogen
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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 relates to a clean synthesis process of magnesium aluminum hydrotalcite, which comprises the following steps: (1) uniformly mixing magnesium hydroxide, aluminum hydroxide and water, ultrasonically dispersing, and stirring for reacting for 2-4 h to obtain a magnesium-aluminum hydrotalcite precursor; (2) and transferring the magnesium-aluminum hydrotalcite precursor into a gas-liquid reactor, controlling the temperature to be 90-100 ℃, reducing the pressure to normal pressure, introducing carbon dioxide gas to react for 1-3 hours, and after the reaction is finished, filtering, washing, drying and crushing to obtain the magnesium-aluminum hydrotalcite. The magnesium-aluminum hydrotalcite prepared by the invention has high purity and good thermal stability, carbonate is stabilized between layers to the maximum extent, the performance of adsorbing acid gas is excellent, and the magnesium-aluminum hydrotalcite can completely replace imported high-valence hydrotalcite products. Meanwhile, the production process is simple to operate, the preparation speed is high, no by-product is generated at last, the filtrate can be recycled, the economic benefit is high, the industrial production is facilitated, and the national environmental protection requirement is met.
Description
Technical Field
The invention relates to a clean synthesis process of magnesium aluminum hydrotalcite, belonging to the technical field of preparation of magnesium aluminum hydrotalcite.
Background
The chemical composition of magnesium aluminum hydrotalcite is usually Mg1-xAlx(OH)2(CO3)0.5x·mH2O, x satisfy 0.2 ≦ x ≦ 0.4. It has a layered structure, the framework of the laminate has positive charges, and the interlayer anions have opposite charges balanced with the positive charges, so that the whole structure is electrically neutral. The interlayer anion has stronger acid gas adsorption capacity, can be used as an acid-absorbing agent in a PVC/PP/PE material, the refractive index of the magnesium-aluminum hydrotalcite is 1.49-1.52, and is similar to that of PVC/PE, so that the transparency is good, in addition, the infrared absorption rate of the magnesium-aluminum hydrotalcite is high, the magnesium-aluminum hydrotalcite can be used for heat-insulating agricultural films, and the magnesium-aluminum hydrotalcite is widely applied in the market at present.
At present, the synthesis method reported in domestic and foreign documents is generally a coprecipitation method, for example, hydrotalcite is prepared by coprecipitation reaction of magnesium and aluminum salt aqueous solution under alkaline condition:
MgCl2+AlCl3+NaOH+Na2CO3→Mg6Al2(OH)16CO3·4H2O+NaCl
MgSO4+Al2(SO4)3+NaOH+Na2CO3→Mg6Al2(OH)16CO3·4H2O+Na2SO4
the reaction is acid-base reaction, which is easy to proceed, but the reaction product is colloidal, which is difficult to wash and filter, and a large amount of NaOH is consumed in the reaction. In addition, NaOH is easy to react with Cl in the raw material-、SO4 2-Reacting to produce low-value NaCl and Na2SO4And the discharge is not beneficial to environmental protection on one hand, and the reaction cost is relatively high on the other hand.
Chinese patent document CN103108907A discloses hydrotalcite with sodium content controlled in trace amount, a method for preparing the same, and a synthetic resin composition containing the same, wherein the hydrotalcite prepared by carbon dioxide needs to be prepared at high temperature and high pressure of 150-250 ℃, which is not conducive to industrial production and has high energy consumption.
Chinese patent document CN107902681A discloses a preparation method of calcium-aluminum hydrotalcite, which comprises the steps of adding calcium hydroxide, aluminum hydroxide and sodium carbonate into a ball mill, wherein the mass ratio of ball materials is controlled to be 8-12: 1, the ball milling rotating speed is 200-500 r/min, the dry milling is carried out for 2-4 h, and the proportion of small, medium and large milling balls (the diameters are respectively 5mm, 8mm and 10mm) is 1-2: 2-3: 5-7; mixing the solid mixture with water, and carrying out microwave hydrothermal crystallization for 5-20 min at the temperature of 70-90 ℃ and under the power of 600-800W; washing, filtering and drying to obtain the calcium-aluminum hydrotalcite. The invention can generate more sodium hydroxide by-products to be treated, is difficult to recover and treat, and still generates a large amount of waste water.
Disclosure of Invention
Aiming at the problems of difficulty in treatment of the byproducts in the synthesis of the magnesium-aluminum hydrotalcite, high treatment cost of industrial wastewater, harsh synthesis conditions and the like, the invention provides a clean synthesis process of the magnesium-aluminum hydrotalcite, which solves the problem of difficulty in dispersion of slurry in industrial production through ultrasonic dispersion. The invention adopts microwave to directly act on hydroxyl, so that the raw materials can rapidly obtain energy, the reaction activity is higher, the raw materials are induced to rapidly react to generate the hydrotalcite precursor, and the hydrotalcite precursor can rapidly react with carbon dioxide in a gas-liquid reactor to obtain the final product.
The technical scheme of the invention is as follows:
a clean synthesis process of magnesium aluminum hydrotalcite comprises the following steps:
(1) uniformly mixing magnesium hydroxide, aluminum hydroxide and water, placing the mixture into a microwave reactor after ultrasonic dispersion, and stirring the mixture for reaction to obtain a magnesium-aluminum hydrotalcite precursor;
(2) and (2) transferring the magnesium-aluminum hydrotalcite precursor obtained in the step (1) into a gas-liquid reactor, controlling the temperature to be 90-100 ℃, reducing the pressure to normal pressure, introducing carbon dioxide gas to react for 1-3 hours, and after the reaction is finished, filtering, washing, drying and crushing to obtain the magnesium-aluminum hydrotalcite.
According to the invention, the molar ratio of the magnesium hydroxide to the aluminum hydroxide in the step (1) is (1.5-3): 1; further preferably 2: 1.
According to the invention, the mass ratio of the mixture of magnesium hydroxide and aluminum hydroxide to water in the step (1) is (1-2): 5; further preferably 1: 4.
Preferably, according to the invention, the purity of the magnesium hydroxide and the aluminum hydroxide in step (1) is more than 97%,
according to the invention, the time of ultrasonic dispersion in the step (1) is preferably 2-6 h; further preferably 2 to 3 hours.
According to the invention, the power of the microwave reactor in the step (1) is preferably 100-1000W, and the reaction time is preferably 2-6 h.
According to the invention, the power of the microwave reactor in the step (1) is preferably 600-1000W, and the reaction time is preferably 3-4 h.
According to the invention, the ratio of the power of the microwave reactor to the volume of water in the step (1) is preferably 200-300: 1, unit is: W/L. If the volume is increased, the reaction time is prolonged or the microwave power is increased.
According to the invention, the solid content of the magnesium-aluminum hydrotalcite precursor in the step (1) is preferably 10-40%.
According to the invention, the preferable introducing speed of the carbon dioxide in the step (2) is 15-25L/h, and the pH value is controlled to be more than 10.
The invention has the technical characteristics that:
the invention selects magnesium hydroxide and aluminum hydroxide as raw materials to react in a microwave reactor, the hydroxyl groups of the two raw materials can quickly absorb microwaves to become active, so that chemical bonds are recombined to form an alkaline magnesium-aluminum hydrotalcite precursor, and the reaction expression is as follows: 4Mg (OH)2+2Al(OH)3＝Mg4Al2(OH)14(ii) a Then, in a gas-liquid reactor, the magnesium-aluminum hydrotalcite precursor reacts with carbon dioxide, and the reaction is carried out through two stepsCarbon oxide replaces conventional sodium carbonate, does not produce by-products, and the pH value in the reaction process is easy to control, and crystal nucleus can regularly grow under the environment of gas phase low alkalinity to form magnalium hydrotalcite, and the expression of the reaction is as follows: mg (magnesium)4Al2(OH)14+CO2+3H2O＝Mg4Al2(OH)12CO3·4H2And O, carrying out solid-liquid separation on the magnesium-aluminum hydrotalcite, drying and crushing to obtain a product, wherein the residual filtrate can be recycled.
The invention has the beneficial effects that:
(1) the magnesium hydroxide and the aluminum hydroxide adopted by the invention are used as raw materials, have wide sources and low price, can greatly reduce the production cost, and are suitable for large-scale industrial production.
(2) The magnesium-aluminum hydrotalcite prepared by the invention has high purity and good thermal stability, carbonate is stabilized between layers to the maximum extent, the performance of adsorbing acid gas is excellent, and the magnesium-aluminum hydrotalcite can completely replace imported high-valence hydrotalcite products.
(3) The production process disclosed by the invention is simple to operate and high in preparation speed, the hydrotalcite precursor is quickly prepared by utilizing the active performance of hydroxyl in the raw materials under the action of microwaves, so that later-stage interlayer anions can be quickly intercalated and can be realized under normal pressure, no by-product is generated, the main component of the filtrate is water, the pH value is 8-8.5, the solid content is less than 1%, the filtrate can be recycled, the economic benefit is high, the industrial production is facilitated, and the national environment-friendly requirement is met.
Drawings
FIG. 1 is an XRD pattern of magnesium aluminum hydrotalcite obtained in example 1 of the present invention.
FIG. 2 is an SEM image of the magnesium aluminum hydrotalcite obtained in example 1 of the present invention.
FIG. 3 is a visual chart of the results of the thermal stability performance test.
In the figure: example 1 the hydrotalcite prepared coupon was sample 1, the commercially available magnesium aluminum hydrotalcite from a domestic source was sample 2, and the commercially available magnesium aluminum hydrotalcite from a Japanese source was sample 3.
Detailed Description
For a better understanding of the present invention, the following preferred examples are provided, the scope of the present invention encompasses but is not limited to these.
Commercially available domestic magnesium aluminum hydrotalcite, and comprises the following components: magnesium aluminum carbonate type hydrotalcite with purity of more than 96 percent.
Commercially available japanese magnesium aluminum hydrotalcite, ingredient: magnesium aluminum carbonate type hydrotalcite with purity of more than 96 percent.
Example 1
A clean synthesis process of magnesium aluminum hydrotalcite comprises the following steps:
(1) weighing 232g of magnesium hydroxide, 156g of aluminum hydroxide and 2000g of water, uniformly mixing, ultrasonically dispersing for 1h, putting into a microwave reactor, adjusting the microwave power to 600W, and stirring for reacting for 3h to obtain a magnesium-aluminum hydrotalcite precursor;
(2) and (2) transferring the magnesium-aluminum hydrotalcite precursor obtained in the step (1) into a flask, controlling the temperature to be 95 ℃, reducing the pressure to be normal pressure, introducing carbon dioxide gas at the rate of 20L/h for 2h, and filtering, washing, drying and crushing to obtain the magnesium-aluminum hydrotalcite.
Wherein, the purity of the magnesium hydroxide and the aluminum hydroxide in the step (1) is 99 percent.
The XRD pattern of the magnalium hydrotalcite prepared in the example is 452g, and is shown in figure 1. As can be seen from fig. 1, the diffraction peaks at positions of 11.59, 23.32, 34.87, etc. of 2 θ are diffraction peaks of the hydrotalcite compound, and the product is single. As shown in fig. 2, the SEM image shows that the synthesized magnesium-aluminum hydrotalcite has a typical lamellar structure, uniform particles, and an average particle size of 4 μm, as shown in fig. 2.
The filtrate produced in this example contains water as the main component, has a pH of 8 and a solid content of < 1%, and can be recycled.
Example 2
A clean synthesis process of magnesium aluminum hydrotalcite comprises the following steps:
(1) weighing 232g of magnesium hydroxide, 156g of aluminum hydroxide and 2000g of water, uniformly mixing, ultrasonically dispersing for 2h, putting into a microwave reactor, adjusting the microwave power to 800W, and stirring for reacting for 4h to obtain a magnesium-aluminum hydrotalcite precursor;
(2) and (2) transferring the magnesium-aluminum hydrotalcite precursor obtained in the step (1) into a flask, controlling the temperature to be 100 ℃, reducing the pressure to be normal pressure, introducing carbon dioxide gas at the rate of 20L/h for 2h, and filtering, washing, drying and crushing to obtain the magnesium-aluminum hydrotalcite.
The Mg-Al hydrotalcite prepared in this example was 452g, with uniform particles and an average particle size of 4 μm.
Wherein, the purity of the magnesium hydroxide and the aluminum hydroxide in the step (1) is 99 percent.
The filtrate produced in this example contains water as the main component, has a pH of 8.5 and a solid content of < 1%, and can be recycled.
Example 3
A clean synthesis process of magnesium aluminum hydrotalcite comprises the following steps:
(1) weighing 232g of magnesium hydroxide, 156g of aluminum hydroxide, 1000g of water and 1000g of filtrate in example 1, uniformly mixing, ultrasonically dispersing for 1h, putting into a microwave reactor, adjusting the microwave power to 600W, and stirring for reacting for 3h to obtain a magnesium-aluminum hydrotalcite precursor;
(2) and (2) transferring the magnesium-aluminum hydrotalcite precursor obtained in the step (1) into a flask, controlling the temperature to be 95 ℃, reducing the pressure to be normal pressure, introducing carbon dioxide gas at the rate of 15L/h for 2h, and filtering, washing, drying and crushing to obtain the magnesium-aluminum hydrotalcite.
Wherein, the purity of the magnesium hydroxide and the aluminum hydroxide in the step (1) is 99 percent.
The Mg-Al hydrotalcite prepared in this example was 450g, and had uniform fine particles and an average particle size of 3.5. mu.m.
The main component of the filtrate produced in the embodiment is water, the pH value is 8-8.5, the solid content is less than 1%, and the filtrate can be recycled.
Comparative example 1
The synthesis process of the magnesium-aluminum hydrotalcite is as described in example 1, except that in the step (1), the microwave power is 80W, and the stirring reaction is carried out for 1 hour.
The amount of the magnesium-aluminum hydrotalcite prepared in this example was 300g, and the particles were not uniform.
As can be seen from the comparison between example 1 and comparative example 1, the low microwave power results in the decrease of the yield of the Mg-Al hydrotalcite and the non-uniformity of the particles.
The magnesium aluminum hydrotalcite prepared in example 1 and commercially available domestic and commercially available japanese magnesium aluminum hydrotalcites were subjected to performance testing.
Test example 1: test for thermal stability
The specific test method comprises the following steps: the magnalium hydrotalcite prepared in example 1, the magnalium hydrotalcite sold in China and the magnalium hydrotalcite sold in Japan are uniformly mixed by a high-speed mixer according to the formula of 100g of polyvinyl chloride (PVC), 20g of dioctyl terephthalate (DOTP), 2g of calcium-zinc auxiliary stabilizer, 1g of hydrotalcite, processing aid and 8g of calcium powder, then the mixture is pressed into a flaky sample sheet with the thickness of 1mm by a double-roll open mill, the flaky sample sheet is cut into the size of 15cm and 15cm, the flaky sample sheet is put into a rotary oven with the temperature of 180 ℃, a small amount of sample sheets are taken out every 5min, and the test result is shown in figure 3, wherein the sample sheet prepared by the hydrotalcite in example 1 is sample No. 1, the sample sheet prepared by the magnalium hydrotalcite sold in China is sample No. 2, and the sample sheet prepared by the magnalium hydrotalcite sold in Japan is sample No. 3.
As can be seen from FIG. 3, the color of the coupon changed from light to dark and the faster the discoloration, indicating that the thermal stability was worse, the static thermal stability of example 1 was consistent with that of the domestic product and was slightly worse than that of the Japanese product, but the difference was not great.
Test example 2: adsorption Performance test
The specific test method comprises the following steps: the magnesium-aluminum hydrotalcite prepared in example 1, commercially available magnesium-aluminum hydrotalcite produced in China and commercially available magnesium-aluminum hydrotalcite produced in Japan were prepared according to the following formulas: 100g of polyvinyl chloride (PVC), 30g of dioctyl terephthalate (DOTP), 10g of No. 52 chlorinated paraffin, 2g of calcium-zinc auxiliary stabilizer, 1g of hydrotalcite, processing aid and 8g of calcium powder, uniformly mixing by using a high-speed mixer, extruding the mixture into strips by using a single-screw extrusion platform, cutting the strips into granules with the length of 0.8cm, weighing 2g of the granules respectively, putting the granules into a test tube, putting the test tube into a Congo red testing machine at 200 ℃, and recording the discoloration time and the final color of a sample, wherein the test results are shown in the following table: example 1 the pellets made from the hydrotalcite were sample # 1, the pellets made from the commercially available magnesium aluminum hydrotalcite were sample # 2, and the pellets made from the commercially available japanese magnesium aluminum hydrotalcite were sample # 3.
Table 1 adsorption performance test results
| Item | Sample No. 1 | Sample No. 2# | Sample No. 3 |
| Congo red adsorption time | 31min | 25.5min | 28min |
| End point sample color | Deep red color | Dark brown color | Dark brown color |
As can be seen from table 1, the adsorption time of congo red for the sample # 1 pellet prepared from the hydrotalcite of example 1 is 31min, while the adsorption time of the sample # 2 pellet prepared from the commercially available magnesium-aluminum hydrotalcite and the adsorption time of the sample # 3 pellet prepared from the commercially available japanese magnesium-aluminum hydrotalcite are not 30min, the color of the end point sample of the sample # 1 pellet prepared from the hydrotalcite of example 1 is dark red, and the color of the end point sample of the sample # 2 pellet prepared from the commercially available magnesium-aluminum hydrotalcite and the color of the end point sample of the sample # 3 pellet prepared from the commercially available japanese magnesium-aluminum hydrotalcite is dark brown, which indicates that the adsorption capacity of the hydrotalcite prepared from example 1 is significantly higher than that of the commercially available magnesium-aluminum hydrotalcite prepared from both countries and japan.
Claims (11)
1. A clean synthesis process of magnesium aluminum hydrotalcite comprises the following steps:
(1) uniformly mixing magnesium hydroxide, aluminum hydroxide and water, placing the mixture into a microwave reactor after ultrasonic dispersion, and stirring the mixture for reaction to obtain a magnesium-aluminum hydrotalcite precursor;
wherein the mass ratio of the mixture of magnesium hydroxide and aluminum hydroxide to water is (1-2) to 5; the power of the microwave reactor is 100-1000W, and the reaction time is 2-6 h;
(2) and (2) transferring the magnesium-aluminum hydrotalcite precursor obtained in the step (1) into a gas-liquid reactor, controlling the temperature to be 90-100 ℃, reducing the pressure to normal pressure, introducing carbon dioxide gas to react for 1-3 hours, and after the reaction is finished, filtering, washing, drying and crushing to obtain the magnesium-aluminum hydrotalcite.
2. The clean synthesis process of the magnesium-aluminum hydrotalcite of claim 1, wherein the molar ratio of magnesium hydroxide to aluminum hydroxide in step (1) is (1.5-3): 1.
3. The clean synthesis process of the magnesium aluminum hydrotalcite of claim 1, wherein the molar ratio of magnesium hydroxide to aluminum hydroxide is 2: 1.
4. The clean synthesis process of the magnesium aluminum hydrotalcite of claim 1, wherein the mass ratio of the mixture of magnesium hydroxide and aluminum hydroxide to water in step (1) is 1: 4.
5. The clean synthesis process of magnesium aluminum hydrotalcite according to claim 1, wherein the purity of magnesium hydroxide and aluminum hydroxide in step (1) is more than 97%.
6. The clean synthesis process of the magnesium aluminum hydrotalcite of claim 1, wherein the ultrasonic dispersion time in the step (1) is 2-6 h.
7. The clean synthesis process of the magnesium aluminum hydrotalcite of claim 6, wherein the ultrasonic dispersion time in the step (1) is 3-4 h.
8. The clean synthesis process of the magnesium-aluminum hydrotalcite of claim 1, wherein the power of the microwave reactor in the step (1) is 600-1000W, and the reaction time is 3-4 h.
9. The clean synthesis process of the magnesium aluminum hydrotalcite of claim 1, wherein the ratio of the power of the microwave reactor to the volume of water in step (1) is 200-300: 1, unit is: W/L.
10. The clean synthesis process of the magnesium-aluminum hydrotalcite of claim 1, wherein the solid content in the magnesium-aluminum hydrotalcite precursor in the step (1) is 10-40%.
11. The clean synthesis process of the magnesium aluminum hydrotalcite of claim 1, wherein the carbon dioxide is introduced at a rate of 15-25L/h in the step (2), and the pH is controlled to be above 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010475473.2A CN111453750B (en) | 2020-05-29 | 2020-05-29 | Clean synthesis process of magnesium aluminum hydrotalcite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010475473.2A CN111453750B (en) | 2020-05-29 | 2020-05-29 | Clean synthesis process of magnesium aluminum hydrotalcite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111453750A CN111453750A (en) | 2020-07-28 |
| CN111453750B true CN111453750B (en) | 2021-09-03 |
Family
ID=71676165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010475473.2A Active CN111453750B (en) | 2020-05-29 | 2020-05-29 | Clean synthesis process of magnesium aluminum hydrotalcite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111453750B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112811449A (en) * | 2020-12-30 | 2021-05-18 | 江苏艾特克阻燃材料有限公司 | Novel method for preparing magnesium-aluminum hydrotalcite |
| CN114956142B (en) * | 2022-05-06 | 2023-08-22 | 山东长泽新材料科技有限公司 | Crystal-adjustable nano hydrotalcite supercritical synthesis process |
| 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 |
| CN116495761B (en) * | 2023-06-27 | 2023-09-12 | 世京(德州)新型材料科技有限公司 | Synthesis method of high-purity magnesium aluminum hydrotalcite |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SK10882001A3 (en) * | 2001-07-30 | 2003-02-04 | Duslo, A. S. Šaľa | Process for the preparation of hydrotalcite and hydrotalcite-like compounds |
| JP2010006640A (en) * | 2008-06-27 | 2010-01-14 | Kyowa Chem Ind Co Ltd | New synthetic hydrotalcite particles and method for producing the same |
| CN102910653A (en) * | 2012-11-09 | 2013-02-06 | 北京化工大学 | Method for preparing magnesium-based layered composite metal hydroxide through high-pressure continuous feeding technology |
| CN104591238A (en) * | 2014-12-04 | 2015-05-06 | 常州大学 | Preparation method for ammonium-polyphosphate-doped magnesium aluminium hydrotalcite |
| CN106276996A (en) * | 2016-08-16 | 2017-01-04 | 福清出入境检验检疫局综合技术服务中心 | The homogeneous hydrothermal synthesis method of microwave of magnalium type brucite |
| CN106395868A (en) * | 2016-09-18 | 2017-02-15 | 福清出入境检验检疫局综合技术服务中心 | One-step synthesis method of magnesium aluminum type toluene-4-sodium sulfonate column hydrotalcite |
| CN107416872A (en) * | 2017-09-01 | 2017-12-01 | 上海华峰新材料研发科技有限公司 | The preparation method of magnalium carbonate form hydrotalcite |
| CN107902681A (en) * | 2017-11-30 | 2018-04-13 | 中南大学 | A kind of preparation method of calcium aluminum hydrotalcite |
| CN108689418A (en) * | 2018-07-26 | 2018-10-23 | 塔里木大学 | A kind of stratiform houghite raw powder's production technology |
| CN109354049A (en) * | 2018-12-22 | 2019-02-19 | 湖北犇星新材料股份有限公司 | A kind of synthetic method of intercalated houghite stabilizer |
| CN109665549A (en) * | 2018-12-25 | 2019-04-23 | 湖南恒光化工有限公司 | A kind of technique preparing calcium aluminum hydrotalcite using carbon dioxide |
-
2020
- 2020-05-29 CN CN202010475473.2A patent/CN111453750B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SK10882001A3 (en) * | 2001-07-30 | 2003-02-04 | Duslo, A. S. Šaľa | Process for the preparation of hydrotalcite and hydrotalcite-like compounds |
| JP2010006640A (en) * | 2008-06-27 | 2010-01-14 | Kyowa Chem Ind Co Ltd | New synthetic hydrotalcite particles and method for producing the same |
| CN102910653A (en) * | 2012-11-09 | 2013-02-06 | 北京化工大学 | Method for preparing magnesium-based layered composite metal hydroxide through high-pressure continuous feeding technology |
| CN104591238A (en) * | 2014-12-04 | 2015-05-06 | 常州大学 | Preparation method for ammonium-polyphosphate-doped magnesium aluminium hydrotalcite |
| CN106276996A (en) * | 2016-08-16 | 2017-01-04 | 福清出入境检验检疫局综合技术服务中心 | The homogeneous hydrothermal synthesis method of microwave of magnalium type brucite |
| CN106395868A (en) * | 2016-09-18 | 2017-02-15 | 福清出入境检验检疫局综合技术服务中心 | One-step synthesis method of magnesium aluminum type toluene-4-sodium sulfonate column hydrotalcite |
| CN107416872A (en) * | 2017-09-01 | 2017-12-01 | 上海华峰新材料研发科技有限公司 | The preparation method of magnalium carbonate form hydrotalcite |
| CN107902681A (en) * | 2017-11-30 | 2018-04-13 | 中南大学 | A kind of preparation method of calcium aluminum hydrotalcite |
| CN108689418A (en) * | 2018-07-26 | 2018-10-23 | 塔里木大学 | A kind of stratiform houghite raw powder's production technology |
| CN109354049A (en) * | 2018-12-22 | 2019-02-19 | 湖北犇星新材料股份有限公司 | A kind of synthetic method of intercalated houghite stabilizer |
| CN109665549A (en) * | 2018-12-25 | 2019-04-23 | 湖南恒光化工有限公司 | A kind of technique preparing calcium aluminum hydrotalcite using carbon dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111453750A (en) | 2020-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111453750B (en) | Clean synthesis process of magnesium aluminum hydrotalcite | |
| US4656156A (en) | Adsorbent and substrate products and method of producing same | |
| CN102050472B (en) | Method for preparing submicron flaky magnesium hydroxide from magnesium oxide | |
| CN102139901B (en) | New method for preparing magnesium-aluminum hydrotalcite | |
| CN107416872B (en) | Preparation method of magnesium-aluminum carbonate hydrotalcite | |
| CN109354049B (en) | Synthesis method of intercalated hydrotalcite stabilizer | |
| CN106674594A (en) | Intercalated layered double hydroxide smoke inhibitor and preparation method thereof | |
| CN102219667A (en) | Higher fatty acid metal salt and preparation method thereof | |
| WO2023056675A1 (en) | Method for preparing magnesium-aluminum hydrotalcite by means of mother liquor circulation | |
| CN102432054A (en) | Method for producing light calcium carbonate slurry and light calcium carbonate paste | |
| CN114988451A (en) | Preparation method for synthesizing magnesium-aluminum intercalation material by using magnesium carbonate | |
| CN109665549A (en) | A kind of technique preparing calcium aluminum hydrotalcite using carbon dioxide | |
| CN113461037A (en) | Preparation method of magnesium-aluminum hydrotalcite | |
| CN110078103A (en) | A kind of calcium aluminium houghite and preparation method thereof | |
| EP3354621B1 (en) | Hydrotalcite and method for producing same | |
| CN1537807A (en) | Method of preparing bimetal oxide and hydrotalcite | |
| CN106673024A (en) | Method for preparing high-purity hexagonal piece-shaped magnesium hydroxide from magnesium oxide | |
| CN115716933B (en) | Easily-dispersible hydrotalcite-based composite material for polymer and preparation method thereof | |
| CN101318672B (en) | Method for preparing magnesium hydroxide with catalysis hydration of organic acid ammonium salts | |
| CN102417195A (en) | Improvement of production process for producing magnesium oxide by carbonization method | |
| KR100486669B1 (en) | Method of synthesizing hydrotalcites | |
| CN112811449A (en) | Novel method for preparing magnesium-aluminum hydrotalcite | |
| CN103979583A (en) | Method for preparing light magnesium carbonate by using boric sludge carbonization method | |
| CN100368371C (en) | Method for preparing calcium formate | |
| CN114229876A (en) | Process for producing hydrotalcite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A Clean Synthesis Process of Magnesium Aluminum Hydrotalcite Effective date of registration: 20231024 Granted publication date: 20210903 Pledgee: Postal Savings Bank of China Co.,Ltd. Zaozhuang Shanting District Sub branch Pledgor: Shandong CHANGZE New Material Technology Co.,Ltd. Registration number: Y2023980062584 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |