CN1594097A - Process for preparing barium carbonate nano-crystalline - Google Patents
Process for preparing barium carbonate nano-crystalline Download PDFInfo
- Publication number
- CN1594097A CN1594097A CN 200410027858 CN200410027858A CN1594097A CN 1594097 A CN1594097 A CN 1594097A CN 200410027858 CN200410027858 CN 200410027858 CN 200410027858 A CN200410027858 A CN 200410027858A CN 1594097 A CN1594097 A CN 1594097A
- Authority
- CN
- China
- Prior art keywords
- nanocrystalline
- barium carbonate
- water
- soluble polymer
- 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
Links
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides a process for preparing barium carbonate nano-crystalline which consists of, mixing Ba#+[2+] solution and CO#-[3]#+[2-] solution by the mol ration of 1 : (1-1.4), charging shape regulating agent, water-soluble macromolecular solution for reacting 2-12 hours at 5-90 deg. C, thus obtaining the disperse system containing BaCO3 nanocrystalline, then proceeding curing, separating, rinsing and drying to obtain the needed barium carbonate nanocrystalline.
Description
(1) technical field
The present invention relates to a kind of barium carbonate preparation of nano crystal, particularly be suitable for preparing different size and the nanocrystalline method of shape barium carbonate, belong to technical field of chemical synthesis.
(2) background technology
The barium carbonate powder as important starting material, has been widely used in multiple inorganic functional material---in the preparation of special cermacis, as barium titanate series ferroelectric condenser pottery, piezoelectric ceramics, dielectric ceramic, semiconductive ceramic; Baric ferrite series magnetic magneto-plumbite type ferrites, Hard Magnetic barium ferrite; Superconductor series La-Ba-Cu-O series superconducting material, Y-Ba-Cu-O series superconducting material, Tl-Ba-Ca-Cu-O series superconducting material etc.Barium carbonate is as the precursor of synthetic above-mentioned functions material, and its grain size is the formation temperature and the performance of crystal form meeting remarkably influenced above-mentioned functions material particularly.Providing the barium carbonate powder of different shapes crystalline, nano-scale to help different barium is the synthetic optimization with technology of the selection of functional materials.
At present, seldom about ultrafine barium carbonate preparation method's patent.The manufacturing process that Li Ruizeng etc. (92105498.X) have invented a kind of ultra-fine low-sulphur barium carbonate.Ground barium sulfate and hard coal cooperated by a certain percentage be placed on evenly that calcining generates the solubility barium sulphide in the 700-1250 ℃ of retort furnace, carry out carbonation reaction again, the reaction desired concn is the 80-90 grams per liter, temperature 50-60 ℃, and time 60-80 minute.With the barium carbonate that generates through getting particle diameter after desulfurization, dehydration, oven dry, the pulverizing below 1.2 μ m, the ultra-fine low-sulphur barium carbonate finished product of total sulfur between 0.1-0.18%.With this finished product is smooth surfaces such as the enamelware made of raw material, pottery, exquisiteness, bright, and product specification improves greatly.The preparation technology that Meng Xiangjian etc. (96116009.8) have invented barium carbonate used in electronic ceramic.With refining bariumchloride, yellow soda ash is that raw material is made into saturated solution respectively, and at a certain temperature, hybrid reaction makes particle diameter at 0.8～1.0 μ m product to its reactant washing, drying.Chen Jianfeng etc. (01122413.4) have invented process for preparing high-purity superfine barium carbonate by reaction deposition method.Utilize purified bariumchloride and bicarbonate of ammonia saturated solution, under the normal temperature in rotating packed bed hybrid reaction, washing, drying can make particle diameter at 20～100nm product.Regulate grain diameter by the rotor speed of regulating rotating packed bed.We are the synthetic method that comprises the nano crystal of ionic compound of barium carbonate (iron continue 03113579.X such as dragon) in the reactant aqueous solution environment of water glass and water-soluble polymer coexistence, comprises steps such as co-precipitation, slaking, separation cleaning and drying and crushing.Utilize the synthetic and industrial mass manufacture in laboratory of most nano crystal of ionic compound that this method can realize comprising that barium carbonate is nanocrystalline, obtain nano crystal of ionic compound different size and shape, the surface coverage soft silica.Therefore also have second kind of components silica in the nanocrystalline barium carbonate that this method obtains, rather than one-component.
This shows that exist following point in the at present relevant synthetic technology of ultrafine barium carbonate: particle diameter is bigger; Production technique is comparatively complicated, cost higher being unfavorable for produce in batches; Deficiencies such as the non-one-component of barium carbonate that obtains.In addition, (particle diameter 1～100nm) particularly comprises morphology Control synthetic technology bibliographical information as yet about the nanocrystalline nano barium carbonate of one-component.Barium carbonate is nanocrystalline to have multiple shapes such as sphere, fusiform, long strip shape, dendriform, and has not yet to see the techniques of mass production of the relevant nanocrystalline barium carbonate of multiple shape.The present invention is intended to solve the nanocrystalline synthetic technology of selectivity of barium carbonate of producing different size, shape in batches, and it is synthetic as the difference in functionality material to satisfy, the pre-reaction material of preparation or the requirement of additive.
(3) Fa Ming content
The objective of the invention is at the deficiencies in the prior art, provide a kind of chemical coprecipitation that utilizes to prepare different size and the nanocrystalline method of shape barium carbonate, utilize this method can realize the synthetic on a small quantity and industrial mass manufacture in the nanocrystalline laboratory of barium carbonate.
Preparation method of the present invention carries out in the reactant aqueous solution environment of morphology control agent and water-soluble polymer coexistence.Concretely, the inventive method is characterised in that: with mol ratio is Ba
2+: CO
3 2-=1: the Ba of (1～1.4)
2+Solution and CO
3 2-Solution mixes, and adds the water-soluble polymer solution of the morphology control agent, 0.01～5% (Wt%, weight percentage) of 0.001～10% (Wt%, weight percentage), reacts 2～12 hours under 5～90 ℃ of temperature, obtains containing barium carbonate (BaCO
3) nanocrystalline dispersion system, it is nanocrystalline to obtain required barium carbonate through slaking, separation, cleaning and drying and crushing again.
In aforesaid method, morphology control agent water soluble is M
2+Compound, phosphoric acid salt, carboxylate salt in one or more compositions constitute.Wherein, M is one or more among Zn, Mg, Mn, Sn, the Ca; Phosphoric acid salt is by PO
4 3-, P
2O
7 4-, (PO
3)
n N-, P
4O
9 2-In one or more negatively charged ion constitute; Carboxylate salt is made of one or more materials in acetic acid, sodium ethylene diamine tetracetate (EDTA), the NTA nitrile triacetic acid (NTA).
Water-soluble polymer among the present invention can be a non-ionic type, one or more formations in the anionic, the water-soluble polymer that also can be two kinds of different molecular weights in single non-ionic type or the single anion type is formed, and the molecular weight of these water-soluble polymers is between 500～30000.
The curing time of dispersion system is 0.5～12 hour in the aforesaid method; It is as follows to separate the concrete operations of cleaning: the dispersion system after the slaking is adopted ordinary method centrifugation, filtration, obtain containing nanocrystalline filter residue, use washed with de-ionized water, remove residual morphology control agent and water-soluble polymer; The concrete operations of drying and crushing are as follows: the filter residue vacuum-drying after will cleaning 3～6 hours or 20～200 ℃ of dryings/oven dry 1～3 hour, pulverize with pulverizer then, and obtain the nanocrystalline product of required barium carbonate.
In the method, the adding mode of morphology control agent and water-soluble polymer is not innovative point of the present invention place, and multiple mode can be arranged, as add simultaneously, add respectively, with adding etc. again after other reactants mix.
The present invention has solved BaCO well
3Size, shape and a dispersed difficult problem in the nanocrystalline preparation process, promptly realize by following approach:
(1) shape control
Selection different shape control agent can obtain single or mix sphere, fusiform, clavate, dendriform, linear BaCO
3Nanocrystalline.Here morphology Control agent mainly plays the growth orientation of sequestrant do in order to the control nucleus, and then obtains the nanocrystalline of desired shape.
(2) size control
Adjust the concentration of water-soluble polymer in reaction mixture, can realize BaCO
3Nanocrystalline small size is to the large size transition.Here water-soluble polymer mainly rises and disperses nucleus to do in order to the control nucleus quantity and the speed of growth, and then obtains the nanocrystalline of desired size.The descending thereupon alternation of nanocrystalline size when water-soluble polymer concentration changes from low to high.
(3) dispersed control
Adjust the BaCO that morphology Control agent and the water-soluble polymer concentration in the aqueous solution can realize high dispersion simultaneously
3Nanocrystalline preparation.
The present invention and existing BaCO
3Nanocrystalline technology of preparing is compared, and has following advantage and effect:
(1) the synthetic technology of selectivity.The present invention realizes one-component BaCO easily
3The size of nanocrystalline wide region, the control of shape are synthesized.
(2) nanocrystalline powder good product dispersibility.The present invention efficiently solves BaCO owing to having introduced water-soluble polymer as the morphology Control agent that dispersion agent is aided with suitable concn
3The problem of nanocrystalline easy generation hard aggregation.
(3) product is easily realized industrialized mass production.In the reaction system that the present invention relates to precursor concentration reached 5% (weight percentage, wt%) more than, prepare CaCO with industrialized already charring at present
3Nanocrystalline precursor Ca (OH)
2Require---(weight percentage, wt%) scope is suitable to keep concentration 7～8%.
(4) description of drawings
Fig. 1 is the FB(flow block) of the inventive method
(5) concrete embodiment
The brilliant BaCO of embodiment 1 ball shaped nano
3Preparation
Containing 0.5% (weight percentage, down together) ZnCl respectively
2(zinc chloride), Na
4P
2O
7In (trisodium phosphate) and 0.01% (weight percentage, down together) sodium polyacrylate mixing solutions, behind the adding 0.5mol/L sodium carbonate solution, add 0.5mol/LBaCl
2Solution stirs simultaneously.20 ℃ of thermotonuses post curing in 2 hours 0.5 hour, cleaning and filtering promptly gets the brilliant BaCO of ball shaped nano 80 ℃ of oven dry pulverizing
3
The nanocrystalline BaCO of embodiment 2 long strip shapes
3Preparation
Containing 1%ZnCl
2In the mixing solutions of (zinc chloride) and 0.2% polyacrylic acid potassium, behind the adding 0.7mol/L sodium carbonate solution, add 0.5mol/LBaCl
2Solution stirs simultaneously.90 ℃ of thermotonuses post curing in 4 hours 2 hours, cleaning and filtering promptly gets the nanocrystalline BaCO of long strip shape 80 ℃ of oven dry pulverizing
3
The nanocrystalline BaCO of embodiment 3 dendriforms
3Preparation
Containing 10%Na
4P
2O
7In (potassium pyrophosphate) and the 0.6% polyacrylic acid-sodium methacrylate multipolymer mixing solutions, behind the adding 0.7mol/L sodium carbonate solution, add 0.5mol/LBaCl
2Solution stirs simultaneously.Room temperature reaction post curing in 6 hours 5 hours, cleaning and filtering promptly gets length-to-diameter ratio greater than the nanocrystalline BaCO of 5 dendriform 80 ℃ of oven dry pulverizing
3
The nanocrystalline BaCO of embodiment 4 fusiforms
3Preparation
In the mixing solutions that contains 0.5%EDTA and 5% polyoxyethylene glycol, behind the adding 0.7mol/L sodium carbonate solution, add 0.5mol/L nitrate of baryta solution, stir simultaneously.React post curing in 10 hours 12 hours, cleaning and filtering promptly gets fusiform BaCO 80 ℃ of vacuum-dryings pulverizing
3Nanocrystalline.
Embodiment 5 has sphere, excellent type BaCO simultaneously
3Nanocrystalline preparation
Containing 0.001%EDTA, 1%ZnCl
2In the mixing solutions of 0.2% polyacrylamide, add the 0.7mol/L sal volatile after, add 0.5mol/LBaCl
2Solution stirs simultaneously.50 ℃ of thermotonuses post curing in 8 hours 4 hours, cleaning and filtering promptly gets the BaCO that has sphere, excellent type 80 ℃ of oven dry pulverizing
3Nanocrystalline.
The brilliant BaCO of embodiment 6 ball shaped nanos
3Preparation
Containing 1%MgCl
2In 0.1% poly-mixing solutions along divinyl acid sodium, add add the 0.5mol/L ammonium bicarbonate soln again behind 1% the tripoly phosphate sodium STPP after, add 0.5mol/LBaCl
2Solution stirs simultaneously.5 ℃ of thermotonuses post curing in 5 hours 5 hours, cleaning and filtering promptly gets the brilliant BaCO of ball shaped nano 80 ℃ of oven dry pulverizing
3
In a word, in morphology Control agent and water-soluble polymer reaction system, realize that easily the nanocrystalline regulation and control of barium carbonate are synthetic, obtain the nanocrystalline product of various barium carbonates of different shapes, size.
Claims (5)
1, a kind of barium carbonate preparation of nano crystal is characterized in that: with mol ratio is Ba
2+: CO
3 2-=1: the Ba of (1～1.4)
2+Solution and CO
3 2-Solution mixes, and the adding mass percent is 0.001～10% morphology control agent, 0.01～5% water-soluble polymer solution, under 5～90 ℃ of temperature, reacted 2～12 hours, obtain containing the nanocrystalline dispersion system of barium carbonate, it is nanocrystalline to obtain required barium carbonate through slaking, separation, cleaning and drying and crushing again.
2, the method for claim 1 is characterized in that: described morphology control agent is by M
2+Compound, phosphoric acid salt, carboxylate salt in one or more compositions constitute, wherein, M is one or more among Zn, Mg, Mn, Sn, the Ca, phosphoric acid salt is by PO
4 3-, P
2O
7 4-, (PO
3)
n N-, P
1O
9 2-In one or more negatively charged ion constitute, carboxylate salt is made of one or more materials in acetic acid, sodium ethylene diamine tetracetate (EDTA), the NTA nitrile triacetic acid (NTA).
3, method as claimed in claim 1 or 2, it is characterized in that: described water-soluble polymer can be one or more formations in non-ionic type, the anionic, the water-soluble polymer that also can be two kinds of different molecular weights in single non-ionic type or the single anion type is formed, and the molecular weight of these water-soluble polymers is between 500～30000.
4, as the described method of the arbitrary claim of claim 1 to 3, it is characterized in that: the curing time of described dispersion system is 0.5～12 hour.
5, as the described method of the arbitrary claim of claim 1 to 4, it is characterized in that: it is as follows to separate the concrete operations of cleaning: the dispersion system after the slaking is adopted ordinary method centrifugation, filtration, obtain containing nanocrystalline filter residue, use washed with de-ionized water, remove residual morphology control agent and water-soluble polymer; The concrete operations of drying and crushing are as follows: the filter residue vacuum-drying after will cleaning 3～6 hours or 20～200 ℃ of dryings/oven dry 1～3 hour, pulverize with pulverizer then, and obtain the nanocrystalline product of required barium carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410027858 CN1273385C (en) | 2004-07-02 | 2004-07-02 | Process for preparing barium carbonate nano-crystalline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410027858 CN1273385C (en) | 2004-07-02 | 2004-07-02 | Process for preparing barium carbonate nano-crystalline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1594097A true CN1594097A (en) | 2005-03-16 |
| CN1273385C CN1273385C (en) | 2006-09-06 |
Family
ID=34664048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410027858 Expired - Fee Related CN1273385C (en) | 2004-07-02 | 2004-07-02 | Process for preparing barium carbonate nano-crystalline |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1273385C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112194162A (en) * | 2020-09-30 | 2021-01-08 | 华北科技学院 | Preparation method of anhydrous barium carbonate crystal with special morphology |
| CN114516652A (en) * | 2022-02-14 | 2022-05-20 | 山东国瓷功能材料股份有限公司 | Barium carbonate with large specific surface area, and preparation method and application thereof |
-
2004
- 2004-07-02 CN CN 200410027858 patent/CN1273385C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112194162A (en) * | 2020-09-30 | 2021-01-08 | 华北科技学院 | Preparation method of anhydrous barium carbonate crystal with special morphology |
| CN114516652A (en) * | 2022-02-14 | 2022-05-20 | 山东国瓷功能材料股份有限公司 | Barium carbonate with large specific surface area, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1273385C (en) | 2006-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100348496C (en) | Low bulk specific weight and large specific surface rare-earth oxide REO and its preparing method | |
| CN102249281B (en) | Lensing spherical vaterite calcium carbonate crystal with high purity and preparation method thereof | |
| CN103011240A (en) | Bulky-grain rare earth carbonate and preparation method and application of carbonate | |
| CN1193106C (en) | Method for preparing nano active zinc oxide from low grade zinc containing material | |
| CN105540623A (en) | Method for preparing nanometer magnesia | |
| US5503815A (en) | Method for the preparation of a lanthanum manganite powder | |
| CN1273385C (en) | Process for preparing barium carbonate nano-crystalline | |
| CN1974885A (en) | Low temperature process of preparing RE borate crystal with oxide as precursor | |
| CN1699175A (en) | Manufacturing method of granular high-activity magnesia | |
| CN116199270B (en) | Treatment process for reducing wastewater in cobalt oxide production process | |
| CN110776015A (en) | Synthesis method of battery-grade trimanganese tetroxide | |
| CN113526540B (en) | Cu3Zn(OH)6Cl2Crystal and method for producing same | |
| CN1872697A (en) | Method for preparing Nano/micro crystal of rare earth vanadate from oxide as precursor body under low temperature | |
| CN103449511A (en) | Strontium titanate submicron crystal and preparation method thereof | |
| CN1151967C (en) | Preparation of magnesium salt whisker | |
| KR19980081407A (en) | Metal hydroxide solid solution, metal oxide solid solution and preparation thereof | |
| CN101863456A (en) | Method for preparing composite metal oxide | |
| US6203774B1 (en) | Method for producing iron oxide powder using a particle size and shape controller | |
| JPS6335571B2 (en) | ||
| CN109867302B (en) | High-purity superfine tetrabasic lead sulfate product and preparation method thereof | |
| CN1215983C (en) | Chemical coprecipitation method for synthesizing powder material of terrae rare salt of normal niobic acid | |
| CN1193810C (en) | Method for Preparing nano crystal of ionic compound | |
| CN106745210A (en) | A kind of Li doping SrTiO3The preparation method and product of porous surface nano particle | |
| CN1230378C (en) | Method for directly synthesizing nano zinc phosphate crystal by using low-heat solid phase chemical reaction | |
| CN1152825C (en) | Synthesis method of nano zinc oxide powder |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060906 Termination date: 20100702 |