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 PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
tertiary amine
long chain
dimethyl
chain tertiary
solution
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.)
Granted
Application number
CN201310653058.1A
Other languages
Chinese (zh)
Other versions
CN104512921B (en
Inventor
蒋建中
张婷
代利
郑饶君
崔正刚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangnan University
Original Assignee
Jiangnan University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Jiangnan University filed Critical Jiangnan University
Priority to CN201310653058.1A priority Critical patent/CN104512921B/en
Publication of CN104512921A publication Critical patent/CN104512921A/en
Application granted granted Critical
Publication of CN104512921B publication Critical patent/CN104512921B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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

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

A kind of method utilizing long chain tertiary amine to prepare nano-calcium carbonate
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.
CN201310653058.1A 2013-12-06 2013-12-06 Method for preparing nanometer calcium carbonate by using long chain tertiary amine Active CN104512921B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310653058.1A CN104512921B (en) 2013-12-06 2013-12-06 Method for preparing nanometer calcium carbonate by using long chain tertiary amine

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310653058.1A CN104512921B (en) 2013-12-06 2013-12-06 Method for preparing nanometer calcium carbonate by using long chain tertiary amine

Publications (2)

Publication Number Publication Date
CN104512921A true CN104512921A (en) 2015-04-15
CN104512921B CN104512921B (en) 2017-01-25

Family

ID=52788842

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310653058.1A Active CN104512921B (en) 2013-12-06 2013-12-06 Method for preparing nanometer calcium carbonate by using long chain tertiary amine

Country Status (1)

Country Link
CN (1) CN104512921B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Also Published As

Publication number Publication date
CN104512921B (en) 2017-01-25

Similar Documents

Publication Publication Date Title
US10016727B2 (en) Method for extracting magnesium and lithium and producing layered double hydroxide from brine
CN103183372B (en) A kind of template solid phase prepares the method for nano zine oxide
CN104724734A (en) Method for producing flower-like sphere type nanometer magnesium hydroxide with characteristics of light weight and high specific surface area
CN101264922A (en) Method for preparing cerium oxide rhombus nano sheet-shaped material
CN105457662B (en) A kind of 3D bouquets structure BiOCl-ZnFe2O4Composite photocatalyst material and preparation method thereof
CN106475100A (en) The preparation method and application of Graphene/ferroferric oxide magnetic nano composite
CN102936019A (en) Method for preparing magnetic 4A molecular sieve by using kaolin
CN109336161B (en) CeO2 nanotube preparation method, CeO2 nanotube and application
CN106315605B (en) The method that 1.1nm tobermorites are prepared using low-grade attapulgite clay
CN106219568A (en) A kind of method utilizing gangue to prepare high-purity molecular sieve ZSM 5
CN106830024B (en) A kind of red mud prepares hydro-thermal-thermal conversion process of active boehmite and aluminum oxide porous microballoon for raw material
CN102295420B (en) Method for preparing alpha-semihydrated gypsum by using aqueous solution of alcohol as crystallization media
CN104512921A (en) Method for preparing nanometer calcium carbonate by using long chain tertiary amine
CN106672941B (en) A kind of preparation of magnetic Nano fluorescent carbon point and separation method
CN103303950B (en) Solvent thermal synthesis method for preparing boehmite powder
CN103073016B (en) Method for synthetizing P1 type zeolite molecular sieve by utilizing industrial solid wastes
CN104773727B (en) Method for synthesizing graphene employing solid-phase calcination
CN102107904A (en) Method for preparing cadmium sulfide or zinc sulfide hollow nano diamonds by using non-template method
CN103896313A (en) Method for preparing high-activity magnesium oxide by adopting old brine in salt lake as material
CN106517304B (en) The preparation method of three-dimensional complex metal hydroxide
CN103588244A (en) Method for preparing sandwiched hollow TiO2 nano material with template free method
CN104512897A (en) Method for preparing meso-porous SiO2 by using long chain tertiary amine
CN1234609C (en) Process of producing high purify superfine aluminium oxide by industrial aluminium hydroxide
CN104803393B (en) One kind prepares stearic acid（Sodium）The method of/Kaolinite/organic Intercalation Compoundies
CN107754817B (en) Ternary metal sulfide/reduced graphene oxide composite material and preparation method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant