CN104512921A - Method for preparing nanometer calcium carbonate by using long chain tertiary amine - Google Patents
Method for preparing nanometer calcium carbonate by using long chain tertiary amine Download PDFInfo
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- CN104512921A CN104512921A CN201310653058.1A CN201310653058A CN104512921A CN 104512921 A CN104512921 A CN 104512921A CN 201310653058 A CN201310653058 A CN 201310653058A CN 104512921 A CN104512921 A CN 104512921A
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- tertiary amine
- long chain
- dimethyl
- chain tertiary
- solution
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 31
- 150000003512 tertiary amines Chemical class 0.000 title claims abstract description 30
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 25
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- -1 tertiary amine bicarbonate Chemical class 0.000 claims abstract description 7
- 239000012265 solid product Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000005119 centrifugation Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 4
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- SFBHPFQSSDCYSL-UHFFFAOYSA-N n,n-dimethyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)C SFBHPFQSSDCYSL-UHFFFAOYSA-N 0.000 claims description 2
- ALNKTVLUDWIWIH-UHFFFAOYSA-N 3a-(5-ethenyl-1-azabicyclo[2.2.2]octan-2-yl)-2,4-dihydro-1h-furo[2,3-b]indol-8b-ol Chemical compound C1C(C(C2)C=C)CCN2C1C12OCCC1(O)C1=CC=CC=C1N2 ALNKTVLUDWIWIH-UHFFFAOYSA-N 0.000 claims 2
- ALNKTVLUDWIWIH-HLQCWHFUSA-N Quinamine Natural products C([C@H]([C@H](C1)C=C)C2)CN1[C@@H]2[C@]12OCC[C@@]1(O)C1=CC=CC=C1N2 ALNKTVLUDWIWIH-HLQCWHFUSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000005352 clarification Methods 0.000 claims 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- QMHNQZGXPNCMCO-UHFFFAOYSA-N n,n-dimethylhexan-1-amine Chemical compound CCCCCCN(C)C QMHNQZGXPNCMCO-UHFFFAOYSA-N 0.000 claims 1
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 claims 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 6
- 239000001110 calcium chloride Substances 0.000 abstract description 6
- 229910001628 calcium chloride Inorganic materials 0.000 abstract description 6
- 239000011259 mixed solution Substances 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 239000007789 gas Substances 0.000 abstract 1
- 239000000693 micelle Substances 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 8
- 239000013543 active substance Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000013517 stratification Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910021532 Calcite Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 241000555268 Dendroides Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005285 chemical preparation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
- C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (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 novel synthetic method of nanometer calcium carbonate. The method comprises the following steps: introducing CO2 to a tertiary amine/water mixed solution to form a micelle solution of long chain tertiary amine bicarbonate, adding ammonia water and calcium chloride, and reacting at a constant temperature in CO2 environment for 1h-6d; introducing air after the reaction, stirring at 30-60DEG C until the obtained reaction solution is turbid and layered, centrifuging the reaction solution, washing the obtained white solid product by using water and acetone to remove long chain tertiary amine in order to obtain nanometer calcium carbonate; and standing the solution to layer the solution, removing acetone and water from the obtained oil layer, and recovering the tertiary amine. The method has the advantages of mild reaction conditions and no generation of harmful gases in the reaction process; a template can be removed through directly washing after the reaction, so the operation is simple; and the long chain tertiary amine can be reused, so the cost is saved, and the pollution is reduced.
Description
Technical field
The present invention relates to a kind of method preparing nano-calcium carbonate, belong to technical field of nano material.
Background technology
Because nano material shows many special propertys different from traditional material, thus illustrate wide application prospect in fields such as chemical, biomedicine, matrix material, information, photoelectric conversions.Nano-calcium carbonate has been widely used in the fields such as plastics, rubber, ink, papermaking, medicine, food.Because it has multiple crystal shape (spherical, cube, chain, sheet etc.) and crystal structure (amorphousness, calcite type, aragonitic, vaterite-type), can according to respective performance applications in different industries, oneself becomes study hotspot and the difficult point in this field to prepare the controlled calcium carbonate nano particle of crystal formation, pattern and size.
At present, the method of synthesis of nano calcium carbonate mainly contains double decomposition, carborization, microemulsion method, sol-gel method etc., wherein tensio-active agent mantle plate prepare nanoparticle have simple to operate, size is controlled, particle dispersion good, narrowly distributing, be easy to realize the features such as continuous prodution operation, compared with traditional chemical preparation method, there is obvious advantage.But the method needs to use exhibiting high surface promoting agent and oil phase in operation, how to remove tensio-active agent, Separation and Recovery they, be a major issue urgently to be resolved hurrily.
Summary of the invention
The object of the invention is to prepare in nano-calcium carbonate method to solve conventional surfactant mantle plate, in last handling process, being difficult to removed template method, and tensio-active agent is difficult to the problem of recycling.
Long chain tertiary amine is not tensio-active agent, in the muddy mixed solution of long chain tertiary amine and water, pass into CO
2after, tertiary amine can be protonated and form long chain tertiary amine supercarbonate, and this supercarbonate energy self-assembly forms micellar solution.The present invention passes into CO with long chain tertiary amine
2it is template that rear original position forms the long chain tertiary amine supercarbonate with tensio-active agent, and under this template, synthesis obtains nano-calcium carbonate.After reaction terminates, easily decompose after long chain tertiary amine supercarbonate ingress of air, formed at 30-60 DEG C without surface-active tertiary amine, tertiary amine and nano-calcium carbonate particles Interaction Force less, directly can replace washing granule with water and acetone and can remove the tertiary amine be adsorbed on mesoporous calcium carbonate granule, avoid the difficult problem that conventional surfactant mantle plate removes; Filtrate is recyclable after removing acetone, water obtains long chain tertiary amine.Therefore utilize long chain tertiary amine then to solve and be difficult to removed template method and the problem reclaiming template.
What adopted is long chain tertiary amine, and molecular structural formula is as follows:
R
1=atomicity is the alkyl of 6 ~ 18, R
2=atomicity is the alkyl of 6,8,12
Utilize the synthesising mesoporous SiO of long chain tertiary amine
2method carry out according to the following steps: the long chain tertiary amine of first getting 1-500mmol joins in 1L water, at the CO of 1atm-5atm
2be stirred under pressure environment and clarify completely, add the ammoniacal liquor of 1-500mM wherein, 1-2500mM calcium chloride, at the CO of 1atm-5atm
2under pressure environment, react 1 hour ~ 6 days at 5-60 DEG C.After reaction terminates, pass into air, at 30-60 DEG C, stir 10-30 minute, to the muddy layering of reaction solution.Centrifugation, white solid product water and acetone wash successively for several times and obtain nano-calcium carbonate; Solution left standstill layering, oil reservoir removing acetone and a small amount of water, reclaim and obtain long chain tertiary amine.
Reaction conditions of the present invention is gentle, produces in reaction process without obnoxious flavour, and reaction terminates rear direct washing and can remove template, easy and simple to handle, and long chain tertiary amine can reuse, cost-saving, decreasing pollution.
Accompanying drawing explanation
Fig. 1 is in embodiment 1, and after end of synthesis, alternative water use and acetone respectively wash the X-ray diffractogram of 5 products therefroms.
Fig. 2 is in embodiment 1, and after end of synthesis, alternative water use and acetone respectively wash the scanning electron microscope (SEM) photograph of 5 products therefroms.
Fig. 3 is in embodiment 2, and after end of synthesis, alternative water use and acetone respectively wash the scanning electron microscope (SEM) photograph of 5 products therefroms, and in figure, calcium carbonate is square pattern.
Embodiment
Embodiment example 1: get 1.15g N, N-dimethyl n amino dodecane, in bottle, adds 36g deionized water, at 1.2atm CO
2be stirred to solution under pressure to clarify completely, then in solution, add 0.5g ammoniacal liquor, enter 2.0g calcium chloride, at 1.2atm CO
2under pressure, react 6 hours at 20 DEG C.After reaction terminates, pass into air, stir at 40 DEG C, reaction solution is muddy layering gradually, and centrifugation obtains white solid, washs white solid 5 final vacuums be successively drying to obtain nano-calcium carbonate with water and acetone; Filtrate stratification, oil reservoir removing acetone and a small amount of water, reclaim and obtain N, N-dimethyl n amino dodecane.
Carry out X-ray diffraction analysis discovery to sample, coincide with PDF standard diffraction collection of illustrative plates (JCPDS05-0586) in the peak position in figure and peak intensity figure, its structure known is calcite type.
Scanning electron microscope analysis is carried out to sample and finds that gained calcium carbonate is dendroid pattern.
Embodiment example 2: get 0.8g N, N-dimethyl n amino dodecane amine, in bottle, adds 36g deionized water, at 1.2atm CO
2be stirred to solution under pressure to clarify completely, then in solution, add 0.6g ammoniacal liquor, enter 1.8g calcium chloride, at 1.2atm CO
2under pressure, react 7 hours at 20 DEG C.After reaction terminates, pass into air, stir at 40 DEG C, reaction solution is muddy layering gradually, and centrifugation obtains white solid, washs white solid 5 final vacuums be successively drying to obtain nano-calcium carbonate with water and acetone; Filtrate stratification, oil reservoir removing acetone and a small amount of water, reclaim and obtain N, N-dimethyl n amino dodecane.Scanning electron microscope analysis is carried out to sample and finds that gained calcium carbonate is square pattern.
Embodiment example 3: get 1.5gN, N-dimethyl n tetradecy lamine, in bottle, adds 40g deionized water, at 1.3atm CO
2be stirred to solution under pressure to clarify completely, then in solution, add 0.6g ammoniacal liquor, enter 2.0g calcium chloride, at 1.3atm CO
2under pressure, react 1 day at 20 DEG C.After reaction terminates, pass into air, stir at 50 DEG C, reaction solution is muddy layering gradually, and centrifugation obtains white solid, washs white solid 5 final vacuums be successively drying to obtain nano-calcium carbonate with water and acetone; Filtrate stratification, oil reservoir removing acetone and a small amount of water, reclaim and obtain N, N-dimethyl n tetradecy lamine.
Embodiment example 4: get 1.7g N, N-dimethyl n cetylamine, in bottle, adds 40g deionized water, at 1.3atm CO
2be stirred to solution under pressure to clarify completely, then in solution, add 0.6g ammoniacal liquor, enter 2.1g calcium chloride, at 1.3atm CO
2under pressure, react 2 days at 20 DEG C.After reaction terminates, pass into air, stir at 60 DEG C, reaction solution is muddy layering gradually, and centrifugation obtains white solid, washs white solid 5 final vacuums be successively drying to obtain nano-calcium carbonate with water and acetone; Filtrate stratification, oil reservoir removing acetone and a small amount of water, reclaim and obtain N, N-dimethyl n cetylamine.
Claims (4)
1. utilize long chain tertiary amine to prepare a method for nano-calcium carbonate, it is characterized in that synthesis step is:
(1) long chain tertiary amine 1-500mmol is joined in 1 premium on currency under room temperature, at 1atm-5atm CO
2aqueous solution clarification is stirred under pressure;
(2) in ertiary amine solution, 1-500mM ammoniacal liquor is added, 1-2500mM CaCl
2, at 1atm-5atm CO
2under pressure, react 1 hour ~ 6 days at 5-60 DEG C;
(3) after reaction terminates, pass into air, at 30-60 DEG C, stir 10-30 minute, reaction solution centrifugation, white solid product water and washing with acetone respectively wash for several times, remove long chain tertiary amine, obtain nano-calcium carbonate; Solution left standstill layering, oil reservoir reclaims long chain tertiary amine.
2. long chain tertiary amine according to claim 1, is characterized in that: described long chain tertiary amine is selected from one or more in following material: N, N-dimethyl n hexylamine, N, N-dimethyl n heptyl amice, N, N-dimethyl n octylame, N, N-dimethyl n nonyl amine, N, N-dimethyl n quinamine, N, the positive undecylamine of N-monomethyl, N, N-dimethyl n amino dodecane, N, N-dimethyl n tetradecy lamine, N, N-dimethyl n cetylamine, N, N-dimethyl n stearylamine, the two hexyl methyl tertiary amine of N-, the two octyl methyl tertiary amine of N-, the two dodecyl methyl tertiary amine of N-.
3. method according to claim 1, after it is characterized in that reaction terminates, passes into air, 10-30 minute is stirred at 30-60 DEG C, to the muddy layering of reaction solution, centrifugation obtains white solid product, washs white solid product 1-10 time with water and acetone successively at 20-55 DEG C.
4. method according to claim 1, is characterized in that centrifugation white solid product, solution left standstill layering, after oil reservoir removes acetone and a small amount of water, reclaims long chain tertiary amine.
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|---|---|---|---|
| CN201310653058.1A CN104512921B (en) | 2013-12-06 | 2013-12-06 | Method for preparing nanometer calcium carbonate by using long chain tertiary amine |
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| CN201310653058.1A CN104512921B (en) | 2013-12-06 | 2013-12-06 | Method for preparing nanometer calcium carbonate by using long chain tertiary amine |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459054A (en) * | 2017-08-18 | 2017-12-12 | 武汉华科天元环保科技有限公司 | A kind of desulfurization wastewater technique of zero discharge using carbon dioxide process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1179401A (en) * | 1996-10-16 | 1998-04-22 | 长春市迪瑞检验制品有限责任公司 | Method for producing crystalline form nm-class calcium carbonate |
| CN1938257A (en) * | 2004-01-29 | 2007-03-28 | 齐凯姆公司 | Recovery of organic acids |
| WO2010093092A1 (en) * | 2009-02-12 | 2010-08-19 | Postech Academy-Industry Foundation | Method of removing carbon dioxide using basic polymer |
| KR101221033B1 (en) * | 2012-05-16 | 2013-01-10 | 한국지질자원연구원 | Method for production of calcium carbonate with fly ash and carbon dioxide micro-bubble |
-
2013
- 2013-12-06 CN CN201310653058.1A patent/CN104512921B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1179401A (en) * | 1996-10-16 | 1998-04-22 | 长春市迪瑞检验制品有限责任公司 | Method for producing crystalline form nm-class calcium carbonate |
| CN1938257A (en) * | 2004-01-29 | 2007-03-28 | 齐凯姆公司 | Recovery of organic acids |
| WO2010093092A1 (en) * | 2009-02-12 | 2010-08-19 | Postech Academy-Industry Foundation | Method of removing carbon dioxide using basic polymer |
| KR101221033B1 (en) * | 2012-05-16 | 2013-01-10 | 한국지질자원연구원 | Method for production of calcium carbonate with fly ash and carbon dioxide micro-bubble |
Non-Patent Citations (1)
| Title |
|---|
| 仲伟科等: "萃取复分解法由氯化钙溶液制沉淀碳酸钙", 《化学世界》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459054A (en) * | 2017-08-18 | 2017-12-12 | 武汉华科天元环保科技有限公司 | A kind of desulfurization wastewater technique of zero discharge using carbon dioxide process |
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