CN101993099A - Nano magnesium carbonate crystal and preparation method thereof - Google Patents
Nano magnesium carbonate crystal and preparation method thereof Download PDFInfo
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- CN101993099A CN101993099A CN 201010581761 CN201010581761A CN101993099A CN 101993099 A CN101993099 A CN 101993099A CN 201010581761 CN201010581761 CN 201010581761 CN 201010581761 A CN201010581761 A CN 201010581761A CN 101993099 A CN101993099 A CN 101993099A
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- 239000013078 crystal Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 title abstract description 11
- 239000001095 magnesium carbonate Substances 0.000 title abstract description 11
- 229910000021 magnesium carbonate Inorganic materials 0.000 title abstract description 11
- 239000011777 magnesium Substances 0.000 claims abstract description 78
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 11
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 71
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 71
- 229910052749 magnesium Inorganic materials 0.000 claims description 71
- 235000011089 carbon dioxide Nutrition 0.000 claims description 12
- 239000013543 active substance Substances 0.000 claims description 11
- -1 poly(oxyethylene glycol) Polymers 0.000 claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 230000003292 diminished effect Effects 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 230000003252 repetitive effect Effects 0.000 claims description 6
- 238000005201 scrubbing Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229960003511 macrogol Drugs 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract 6
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 2
- 239000004094 surface-active agent Substances 0.000 abstract 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 11
- 229960001708 magnesium carbonate Drugs 0.000 description 9
- 235000014380 magnesium carbonate Nutrition 0.000 description 9
- 229920006351 engineering plastic Polymers 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- OGWLTJRQYVEDMR-UHFFFAOYSA-F tetramagnesium;tetracarbonate Chemical compound [Mg+2].[Mg+2].[Mg+2].[Mg+2].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O OGWLTJRQYVEDMR-UHFFFAOYSA-F 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- 239000002159 nanocrystal Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- ZEGDXSGIGIQDPG-UHFFFAOYSA-N carbon dioxide;magnesium Chemical compound [Mg].O=C=O ZEGDXSGIGIQDPG-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention relates to a nano magnesium carbonate crystal and a preparation method thereof. The preparation method comprises the following steps of: matching an MgCl2 solution with concentration of 0.4-2.2mol/l; dripping 0.01-1g of surface active agent into 100ml of MgCl2 solution; preparing an ammonia solution with concentration of 1.6-8.8mol/l; introducing a certain amount of carbon dioxide into the ammonia solution, wherein a mol ratio of NH<4+> to CO2 is 2:1; adding 0.001-0.1g of nanometer oxide as a crystal nucleus into 100ml of ammonia and carbon dioxide solution system to slowly and evenly stir; slowly dripping a certain amount of MgCl2 solution added with the surface active agent into the ammonia and carbon dioxide solution added with the nanometer oxide; finally, maintaining the mol ratio of Mg<2+> to NH<4+> to CO2 as 1:4:2; when finishing the dripping process, standing 20-30 minutes after slowly stirring 2-5 minutes; then, filtering by reducing pressure and repeatedly cleaning 2-4 times by using absolute ethyl alcohol; and finally, drying 2-3 hours at the temperature of 150-300 DEG C to obtain a product.
Description
[technical field]
The invention belongs to technical field of inorganic nanometer material, relate to a kind of nano-calcium carbonate magnesium crystal and preparation method thereof.
[background technology]
Magnesiumcarbonate (comprising magnesium basic carbonate and Carbon Dioxide magnesium) is a kind of important inorganic chemical industry material, have good filling property, dispersiveness and mobile, can improve the tensile strength and the wear resistance of engineering plastics, be the good weighting agent and the strengthening agent of engineering plastic product.Since magnesium basic carbonate have do not burn, quality is light, and it is added in the engineering plastics, can significantly improve the thermal insulation of engineering plastics, high temperature resistant and flame retardant properties.
Because micron-sized magnesiumcarbonate can occur disperseing uneven phenomenon in adding other materials to as filling additive, has a strong impact on the characteristic of other materials.
Nano-calcium carbonate magnesium has other more outstanding advantages than micron order or the magnesiumcarbonate more than the micron order, as good dispersed and with the consistency of organic materials, make it can improve the characteristic of this organic materials significantly, and can not constitute great influence again the characteristic of this organic materials itself as additive.
The method that prepare at present magnesiumcarbonate is a lot, and what still prepare mostly is micron-sized magnesiumcarbonate, and it is less to prepare nano level magnesiumcarbonate.Major cause is, the difficult preparation of nano level magnesiumcarbonate, and nano-calcium carbonate magnesium is the same with metal-oxide powder with many nano level inorganic salt, because huge surface energy, very easy gathering is agglomerating, thereby forms micron-sized magnesiumcarbonate.
" salt industry and chemical industry " impurity the 38th is rolled up the 21st～23 page of the 1st phase and has been introduced with MgCl
26H
2O is a raw material, adopts the method for precipitation from homogeneous solution synthesis of nano magnesium basic carbonate, and the concrete steps of this method are as follows:
With MgCl
26H
2O, CO (NH
2)
2Be reaction raw materials, it be made into the easy of desired concn, earlier with CO (NH
2)
2Add in the four-hole boiling flask, be heated to certain temperature, slowly add MgCl again
2Solution; Heating, stir, after reaction for some time, ageing 1h naturally lowers the temperature; Filtration under diminished pressure, being washed to no chlorion repeatedly detects, carry out solvent exchange 3 times with the 20ml absolute ethanol washing again, the magnesium basic carbonate that obtains be deposited in the loft drier 110 ℃ down dry 2h promptly obtain the magnesium basic carbonate powder, find that with this magnesium basic carbonate of electron microscopic observation its median size is 40nm.
This method is because CO (NH
2)
2Hydrolysis rate is very slow in heat-processed, and employing nature ageing, so crystallization time is longer, be unfavorable for large-scale industrial production, and because the surface energy of the nano-calcium carbonate magnesium crystal that crystallizes out is still very big, be easy to reunite, so, the productive rate of the nano-calcium carbonate magnesium that obtains by this method is not high, also has micron-sized magnesiumcarbonate in product.
[summary of the invention]
In order to solve above-mentioned technical problem, the nano-calcium carbonate magnesium crystal that the present invention proposes a kind of preparation method of new nano-calcium carbonate magnesium crystal and utilize this method preparation.It is fast that the preparation method that the present invention proposes prepares nano-calcium carbonate magnesium crystal speed, the nano-calcium carbonate magnesium crystal purity height of preparing.
Concrete technical scheme of the present invention is as follows:
The invention provides a kind of preparation method of nano-calcium carbonate magnesium crystal, it is characterized in that, this method comprises the steps:
(1) compound concentration is the MgCl of 0.4mol/l～2.2mol/l
2Solution;
(2) to the MgCl of every 100ml
2Drip the tensio-active agent of 0.01g-1g in the solution;
(3) compound concentration is the ammonia soln of 1.6mol/l～8.8mol/l;
(4) in above-mentioned ammonia soln, feed a certain amount of carbon dioxide, make NH
4 +With CO
2Mol ratio be 2: 1;
(5) in the ammoniacal liquor carbonic acid gas solution system of every 100ml, add the nano-oxide of 0.001g-0.1g, and slowly stir as nucleus;
(6) under 5 ℃～60 ℃, in the ammoniacal liquor carbonic acid gas solution that is added with nano-oxide, slowly drip a certain amount of MgCl that is added with tensio-active agent
2Solution is kept Mg at last
2+: NH
4 +: CO
2Mol ratio be 1: 4: 2, after dropwising, slowly stir after 2～5 minutes and left standstill 20～30 minutes, filtration under diminished pressure and with dehydrated alcohol repetitive scrubbing 2～4 times at 150 ℃～300 ℃ down dry 2～3h, obtains product at last then.
Described tensio-active agent is Macrogol 200 (PEG200), poly(oxyethylene glycol) 400 (PEG400) or alkylphenol polyoxyethylene (OP-10).
Described nano-oxide as nucleus is that mass percent is the nano-TiO of 0.5%-15%
2Colloidal sol, described nano-TiO
2The volume of colloidal sol is 0.2ml～120ml.
Described nano-oxide thing as nucleus is nano-MgO crystal grain or nanometer SiO
2Powder.
The described median size that is used as the nano-oxide of nucleus is 1～50nm.
The present invention also provides a kind of nano-calcium carbonate magnesium crystal, it is characterized in that, comprises also in this nano-calcium carbonate magnesium crystal that mass percent is 0.1%～10% nano-oxide nucleus.
Described nano-oxide nucleus is nano-MgO, nanometer SiO
2And nano-TiO
2In a kind of.
The median size of described nano-oxide nucleus is 1～50nm.
The median size of described nano-calcium carbonate magnesium crystal is 50～300nm.
The heat decomposition temperature of described nano-calcium carbonate magnesium crystal is 360～420 ℃.
Beneficial technical effects of the present invention is:
In the process of preparation nano-calcium carbonate magnesium crystal, add tensio-active agent, reduce the surface energy of nanocrystal, can effectively prevent the reunion of nanocrystal, make the nano-calcium carbonate magnesium crystal particle diameter that is worth diminish.
In the process of preparation nano-calcium carbonate magnesium crystal, add the nucleus that promotes crystal growth, can accelerate the formation of nanocrystal, saved the time, improved production efficiency.
The nano-oxide nucleus of nano-calcium carbonate magnesium crystal is a kind of nucleator that brings out crystal growth with low cost, not only can improve crystal formation speed, and nanocrystal is when being nano inorganic oxides such as silicon-dioxide or magnesium oxide or titanium dioxide, wrapped up by the nano-calcium carbonate magnesium crystal, not only the performance to the nano-calcium carbonate magnesium crystal can not exert an influence, play the purpose of engineering plastics being carried out modification but also can act synergistically with nano-calcium carbonate magnesium, improved the machinery of engineering plastics, mechanics and chemistry, physicals, even so inner nano-oxide that is enclosed with of the nano-calcium carbonate magnesium crystal that the present invention prepares, also need not purification step, saved production cost.
[Figure of description]
Fig. 1 is the thermogravimetic analysis (TGA) figure (TG) of embodiment 2 nano-calcium carbonate magnesium crystals;
Fig. 2 is the Electronic Speculum figure (SEM) of embodiment 3 nano-calcium carbonate magnesium crystals.
[embodiment]
The nano-calcium carbonate magnesium crystal that the present invention relates to a kind of preparation method of nano-calcium carbonate magnesium crystal and utilize this method preparation.
Below in conjunction with specific embodiment the present invention is done further detailed elaboration and explanation (preparation process of nano-calcium carbonate magnesium unless otherwise indicated is under the normal temperature and pressure and carries out among all embodiment):
Embodiment 1
A kind of nano-calcium carbonate magnesium crystal, the concrete steps that prepare this nano-calcium carbonate magnesium crystal are as follows:
(1) preparation 100ml, volumetric molar concentration are the MgCl of 0.4mol/l
2Solution;
(2) to the MgCl of 100ml
2Drip the Macrogol 200 (PEG200) of 0.1g in the solution as tensio-active agent;
(3) preparation 100ml, concentration are the ammonia soln of 1.6mol/l;
(4) in above-mentioned ammonia soln, feed an amount of carbon dioxide, make NH
4 +With CO
2Mol ratio be 2: 1;
(5) add the nano magnesia crystal grain of 0.04g as nucleus in above-mentioned ammoniacal liquor carbonic acid gas solution system, the median size of described nano magnesia is 50nm;
(6) under 5 ℃, in the ammoniacal liquor carbonic acid gas solution that is added with nano magnesia, slowly drip the MgCl that is added with Macrogol 200 that above-mentioned steps (2) makes
2Solution is kept Mg at last
2+: NH
4 +: CO
2Mol ratio be 1: 4: 2, after dropwising, stir and left standstill 30 minutes after 2 minutes, filtration under diminished pressure and with dehydrated alcohol repetitive scrubbing 2 times then at 150 ℃ of dry 2h down, obtains product at last.
The product that makes is the nano-calcium carbonate magnesium crystal, and the median size of nano-calcium carbonate magnesium crystal is 300nm.Comprise also in the described nano-calcium carbonate magnesium crystal that mass fraction is 1% nano magnesia nucleus, be wrapped in the inside of described nano-calcium carbonate magnesium crystal, the median size of described nano magnesia nucleus is 50nm.The heat decomposition temperature that records the nano-calcium carbonate magnesium crystal that makes by thermogravimetric analyzer is 420 ℃.
Embodiment 2
A kind of nano-calcium carbonate magnesium crystal, the concrete steps that prepare this nano-calcium carbonate magnesium crystal are as follows:
(1) preparation 100ml, volumetric molar concentration are the MgCl of 1.725mol/l
2Solution;
(2) to the MgCl of 100ml
2Drip the poly(oxyethylene glycol) 400 (PEG400) of 0.5g in the solution as tensio-active agent;
(3) preparation 100ml, concentration are the ammonia soln of 7mol/l;
(4) in above-mentioned ammonia soln, feed an amount of carbon dioxide, make NH
4 +With CO
2Mol ratio be 4: 2;
(5) add the nanometer titanium dioxide silicon crystal grain of 0.01g as nucleus in ammoniacal liquor carbonic acid gas solution system, the median size of described nano silicon is 20nm;
(6) under 25 ℃, in the ammoniacal liquor carbonic acid gas solution that is added with nano silicon, slowly drip the MgCl that is added with poly(oxyethylene glycol) 400 that above-mentioned steps (2) makes
2Solution is kept Mg at last
2+: NH
4 +: CO
2Mol ratio be 1: 4: 2, after dropwising, stir and left standstill 25 minutes after 3 minutes, filtration under diminished pressure and with dehydrated alcohol repetitive scrubbing 3 times then at 200 ℃ of dry 2h down, obtains product at last.
The product that makes is the nano-calcium carbonate magnesium crystal, and the median size of nano-calcium carbonate magnesium crystal is 100nm.Comprise also in the described nano-calcium carbonate magnesium crystal that mass fraction is 0.25% nano silicon nucleus, be wrapped in the inside of described nano-calcium carbonate magnesium crystal, the median size of described nano silicon nucleus is 20nm.The heat decomposition temperature that records the nano-calcium carbonate magnesium crystal that makes by thermogravimetric analyzer is 398 ℃, and the thermogravimetic analysis (TGA) of described nano-calcium carbonate magnesium (TG) is schemed as shown in Figure 1.
Embodiment 3
A kind of nano-calcium carbonate magnesium crystal, the concrete steps that prepare this nano-calcium carbonate magnesium crystal are as follows:
(1) preparation 100ml, volumetric molar concentration are the MgCl of 1.725mol/l
2Solution;
(2) to the MgCl of 100ml
2Drip the alkylphenol polyoxyethylene (OP-10) of 0.02mg in the solution as tensio-active agent;
(3) preparation 200ml, concentration are the ammonia soln of 3.5mol/l;
(4) in above-mentioned ammonia soln, feed an amount of carbon dioxide, make NH
4 +With CO
2Mol ratio be 4: 2;
(5) in ammoniacal liquor carbonic acid gas solution system, add 0.5ml, 8% as the nano-TiO of nucleus
2Colloidal sol slowly stirs, described nano-TiO
2The median size of colloidal sol is 8nm;
(6) under 60 ℃, to the above-mentioned nano-TiO that is added with
2The 100ml that slow dropping above-mentioned steps (2) makes in the ammoniacal liquor carbonic acid gas solution of colloidal sol is added with the MgCl of alkylphenol polyoxyethylene (OP-10)
2Solution is kept Mg at last
2+: NH
4 +: CO
2Mol ratio be 1: 4: 2, after dropwising, stir and left standstill 20 minutes after 5 minutes, filtration under diminished pressure and with dehydrated alcohol repetitive scrubbing 4 times then at 300 ℃ of dry 2h down, obtains product at last.
The product that makes is the nano-calcium carbonate magnesium crystal, and the median size of nano-calcium carbonate magnesium crystal is 200nm, and the Electronic Speculum figure of this nano-calcium carbonate magnesium (SEM) as shown in Figure 2.Comprise also in the described nano-calcium carbonate magnesium crystal that mass fraction is 1% nano TiO 2, be wrapped in the inside of described nano-calcium carbonate magnesium crystal, the median size of described nano TiO 2 nucleus is 8nm.
Embodiment 4
A kind of nano-calcium carbonate magnesium crystal, the concrete steps that prepare this nano-calcium carbonate magnesium crystal are as follows:
(1) preparation 100ml, volumetric molar concentration are the MgCl of 2.2mol/l
2Solution;
(2) to the MgCl of 100ml
2Drip the poly(oxyethylene glycol) 400 (PEG400) of 0.5mg in the solution as tensio-active agent;
(3) preparation 100ml, concentration are the ammonia soln of 8.8mol/l;
(4) in above-mentioned ammonia soln, feed an amount of carbon dioxide, make NH
4 +With CO
2Mol ratio be 4: 2;
(5) add the nano-calcium carbonate magnesium crystal grain of 0.01g as nucleus in ammoniacal liquor carbonic acid gas solution system, the median size of described nano-calcium carbonate magnesium crystal grain is 50nm;
(6) under 35 ℃, in the above-mentioned ammoniacal liquor carbonic acid gas solution that is added with nano-calcium carbonate magnesium crystal grain, slowly drip the MgCl that is added with poly(oxyethylene glycol) 400 that above-mentioned steps (2) makes
2Solution is kept Mg at last
2+: NH
4 +: CO
2Mol ratio be 1: 4: 2, after dropwising, slowly stir after 3 minutes and left standstill 25 minutes, filtration under diminished pressure and with dehydrated alcohol repetitive scrubbing 3 times then at 150 ℃ of dry 2h down, obtains product at last.
The product that makes is the nano-calcium carbonate magnesium crystal, and the median size of nano-calcium carbonate magnesium crystal is 50nm.The heat decomposition temperature that records the nano-calcium carbonate magnesium crystal that makes by thermogravimetric analyzer is 360 ℃.
Need to prove that those skilled in the art can also the very simple embodiment that expects other at the above embodiments, and, just can access some improvement by simply repeatedly experiment.But no matter how to improve,, belong to the protection domain of this patent as long as these technical schemes in design scope of the present invention, should be equal to the technical scheme of this patent.
Claims (10)
1. the preparation method of a nano-calcium carbonate magnesium crystal is characterized in that, this method comprises the steps:
(1) compound concentration is the MgCl of 0.4mol/l～2.2mol/l
2Solution;
(2) to the MgCl of every 100ml
2Drip the tensio-active agent of 0.01g～1g in the solution;
(3) compound concentration is the ammonia soln of 1.6mol/l～8.8mol/l;
(4) in above-mentioned ammonia soln, feed a certain amount of carbon dioxide, make NH
4 +With CO
2Mol ratio be 2: 1;
(5) in the ammoniacal liquor carbonic acid gas solution system of every 100ml, add the nano-oxide of 0.001g～0.1g, and slowly stir as nucleus;
(6) under 5 ℃～60 ℃, in the ammoniacal liquor carbonic acid gas solution that is added with nano-oxide, slowly drip a certain amount of MgCl that is added with tensio-active agent
2Solution is kept Mg at last
2+: NH
4 +: CO
2Mol ratio be 1: 4: 2, after dropwising, slowly stir after 2～5 minutes and left standstill 20～30 minutes, filtration under diminished pressure and with dehydrated alcohol repetitive scrubbing 2～4 times at 150 ℃～300 ℃ down dry 2～3h, obtains product at last then.
2. the preparation method of nano-calcium carbonate magnesium crystal according to claim 1 is characterized in that, described tensio-active agent is Macrogol 200 (PEG200), poly(oxyethylene glycol) 400 (PEG400) or alkylphenol polyoxyethylene (OP-10).
3. the preparation method of nano-calcium carbonate magnesium crystal according to claim 1 is characterized in that, described nano-oxide as nucleus is that mass percent is 0.5%～15% nano-TiO
2Colloidal sol, described nano-TiO
2The volume of colloidal sol is 0.2ml～120ml.
4. the preparation method of nano-calcium carbonate magnesium crystal according to claim 1 is characterized in that, described nano-oxide as nucleus is nano-MgO crystal grain or nanometer SiO
2Powder.
5. according to the preparation method of claim 1 or 3 or 4 described nano-calcium carbonate magnesium crystals, it is characterized in that the described median size that is used as the nano-oxide of nucleus is 1～50nm.
6. a nano-calcium carbonate magnesium crystal is characterized in that, comprises also in this nano-calcium carbonate magnesium crystal that mass percent is 0.1%～10% nano-oxide nucleus.
7. nano-calcium carbonate magnesium crystal according to claim 6 is characterized in that, the nano-oxide nucleus is nano-MgO, nanometer SiO
2And nano-TiO
2In a kind of.
8. according to claim 6 or 7 described nano-calcium carbonate magnesium crystals, it is characterized in that the median size of described nano-oxide nucleus is 1～50nm.
9. according to claim 6 or 7 described nano-calcium carbonate magnesium crystals, it is characterized in that the heat decomposition temperature of described nano-calcium carbonate magnesium crystal is 360 ℃～420 ℃.
10. nano-calcium carbonate magnesium crystal according to claim 9 is characterized in that, the median size of described nano-calcium carbonate magnesium crystal is 50～300nm.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104291366A (en) * | 2014-11-03 | 2015-01-21 | 苏州市泽镁新材料科技有限公司 | Preparation method for nanometer magnesium carbonate crystal |
| CN104355329A (en) * | 2014-11-03 | 2015-02-18 | 苏州市泽镁新材料科技有限公司 | Method for preparing nano magnesium carbonate crystal |
| CN104607142A (en) * | 2015-01-20 | 2015-05-13 | 中国科学院合肥物质科学研究院 | MgO/MgCO3 compound adopting micro-nano hierarchical structure and application of MgO/MgCO3 compound serving as fluorine remover |
| CN105036161A (en) * | 2015-07-23 | 2015-11-11 | 韦海棉 | Preparation method of magnesium carbonate crystal |
| CN105060321A (en) * | 2015-07-23 | 2015-11-18 | 韦海棉 | Preparation process for anhydrous magnesium carbonate |
| CN105271318A (en) * | 2015-11-23 | 2016-01-27 | 中国科学院青海盐湖研究所 | Preparation method of magnesium oxide nanocrystalline |
| CN105646940A (en) * | 2015-12-28 | 2016-06-08 | 江南大学 | Method for coating surface of potassium titanate whisker with nanometer calcium carbonate |
| CN109071251A (en) * | 2016-04-04 | 2018-12-21 | 破坏性材料公司 | Getter material and its production method comprising intrinsic composite nanoparticle |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1508072A (en) * | 2002-12-13 | 2004-06-30 | 北京化工大学 | Method for preparing nano magnesium oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1508072A (en) * | 2002-12-13 | 2004-06-30 | 北京化工大学 | Method for preparing nano magnesium oxide |
Non-Patent Citations (1)
| Title |
|---|
| 《盐业与化工》 20090131 周大鹏 等 均匀沉淀法制备纳米碱式碳酸镁粉体的研究 第21-23,31页 1-10 第38卷, 第1期 2 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104291366A (en) * | 2014-11-03 | 2015-01-21 | 苏州市泽镁新材料科技有限公司 | Preparation method for nanometer magnesium carbonate crystal |
| CN104355329A (en) * | 2014-11-03 | 2015-02-18 | 苏州市泽镁新材料科技有限公司 | Method for preparing nano magnesium carbonate crystal |
| CN104607142A (en) * | 2015-01-20 | 2015-05-13 | 中国科学院合肥物质科学研究院 | MgO/MgCO3 compound adopting micro-nano hierarchical structure and application of MgO/MgCO3 compound serving as fluorine remover |
| CN105036161A (en) * | 2015-07-23 | 2015-11-11 | 韦海棉 | Preparation method of magnesium carbonate crystal |
| CN105060321A (en) * | 2015-07-23 | 2015-11-18 | 韦海棉 | Preparation process for anhydrous magnesium carbonate |
| CN105271318A (en) * | 2015-11-23 | 2016-01-27 | 中国科学院青海盐湖研究所 | Preparation method of magnesium oxide nanocrystalline |
| CN105646940A (en) * | 2015-12-28 | 2016-06-08 | 江南大学 | Method for coating surface of potassium titanate whisker with nanometer calcium carbonate |
| CN109071251A (en) * | 2016-04-04 | 2018-12-21 | 破坏性材料公司 | Getter material and its production method comprising intrinsic composite nanoparticle |
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